Title of Invention

MODIFIED ANIONICALLY POLYMERIZED POLYMERS

Abstract Oligomer-modified anionically polymerized polymers, reinforced materials made with the polymers and articles made from the reinforced materials are provided. The oligomer-modified polymers are made by reacting anionically polymerized polymers with low molecular weight acrylic oligomers. The oligomer-modified polymers may be used as adhesives, compatibilizers, reinforcing agents and impact modifiers.
Full Text FIELD OF THE INVENTION
The invention relates to functionally modified anionically polymerized polymers,
reinforced materials containing the polymers, and articles made from the reinforced
materials.
BACKGROUND OF THE INVENTION
Anionic polymerization is a well-known technique for manufacturing plastics and
elastomers. Due to the "living" character of the polymer chains during the anionic
polymerization process, anionic polymerization allows for the production of polymers
having well-defined polymer blocks and narrow molecular weight distributions. Anionic
polymerization has long been used to polymerize conjugated diolefins such as butadiene
and isoprene and to copolymerize such diolefins with other anionically polymerizable
monomers, such as vinyl aromatics and substituted vinyl aromatics. Commercial
polymers commonly made through the anionic polymerization process include plastics
such as polystyrene, elastomers such as polybutadiene and polyisoprene, and
thermoplastic elastomers such as block copolymers of styrene, butadiene and isoprene
with varying sizes and numbers of blocks.
Many commercial applications for anionically polymerized polymers may be
found in the literature. The anionically polymerized polymers may be useful in their own
right as elastomers for tires and other industries, adhesives, sealants and coatings. In
addition anionically polymerized polymers may be used to modify the characteristics of
various materials such as plastics and rubbers. For example, the anionically polymerized
polymers may be used as compatibilizers and reinforcing agents in asphalt and
compatibilizers or tie layers in polymer blends. Anionically polymerized polymers may
be used as impact modifiers, reinforcing agents or viscosity modifiers in plastics used to
manufacture molded and extruded goods such as injection molded parts and engineering
components, films and fibers.
Anionically polymerized polymers may be functionally modified in order to
improve their characteristics for their intended applications. Many modification routes


have been developed over the years. The most common anionically polymenzed polymer
modifications include introducing chemical functionalities through end-capping reactions;
chain coupling through reactions of multifunctional species with living anions to convert
the polymers from linear structures to radial, comb or arm-like structures; hydrogenation
of residual double bonds; and combinations of the above modifications. The end-capping
reactions and chain coupling reactions may be carried out using either small molecules or
high molecular weight polymers as reactants. Examples of small molecules typically used
as capping or coupling agents in conventional anionically polymerized polymer
modification techniques include di- or polyfunctional compounds such as divinyl
benzenes, diisopropenyl benzenes, trivinyl benzenes, divinyl naphthalenes, trivinyl
naphthalenes, tin tetrachloride and various silane compounds. Examples of typical high
molecular weight polymers used as end-capping and coupling agents in the modification
of anionically polymerized polymers include polyolefins and halogenated styrene-based
polymers. Many of these modification techniques have become routine practice and the
modified products produced using these modification techniques are of commercial
importance.
However, many problems remain in the area of anionic polymer modification.
These problems are related to the inability of modified or unmodified anionically
polymerized polymers to perform in different applications due to a lack of compatibility,
miscibility, adhesion or dispersibility in or with other materials when the anionically
polymerized polymers are included in a physical or reactive blend. For example, many
styrene/butadiene-based and styrene/isoprene-based polymers are insufficiently
compatible with polar plastics, such as polyamides, polyurethanes, polyethers,
polysulfones, polyether-ketones, polyetherether ketones, polyimides, polyetherimides
polycarbonates and polyesters, to be suitable in applications using these plastics.
Unfortunately, current modifications of anionically polymerized polymers, which
introduce polar or chemical groups into the polymers, have not been successful in
resolving these limitations.
Another important application where currently available anionically polymerized
polymers have met with limited success is in the reinforcement of asphalt for paving and
roofing applications. Although styrene/butadiene- and styrene/isoprene-based polymers,


both linear and nonlinear, are widely used in reinforcing asphalt, problems related to the
dispersibility of the anionically polymerized polymers in the asphalt and to the
morphology stability of the resulting asphalt formulations ultimately have a negative effect
on the long-term performance of the asphalt. Similar problems have arisen in applications
where anionically polymerized polymers are used as pressure sensitive adhesives and hot
melt adhesives and when the anionically polymerized polymers are used as impact
modifiers in plastics for (co)extrusion or (co)injection molding applications. Additional
problems remain when anionically polymerized polymers are used as elastomers for tires
showing poor adhesion to other tire components such as metals and fillers.
Thus, a need exists for a method of modifying anionically polymerized polymers to
produce modified anionically polymerized polymers that are compatible with a wide
variety of rubber and plastic materials and other substrates and suitable for a broad range
of applications.
SUMMARY OF THE INVENTION
Oligomer-modified anionically polymerized polymers, polymer blends and
mixtures containing the polymers, methods for producing the polymers, reinforced
materials containing the polymers and articles made from the reinforced materials are
provided.
One aspect of the invention provides a modified anionically polymerized polymer
made from the reaction product of an anionically polymerized polymer and an oligomer
made from at least one acrylic monomer and functionalized with at least one functional
group selected from esters, carboxylic acids, anhydrides and epoxies.
Another aspect of the invention provides a method for preparing a modified
anionically polymerized polymer that includes the step of reacting an anionically
polymerized polymer with an oligomer made from at least one acrylic monomer and
functionalized with at least one functional group selected from esters, carboxylic acids,
anhydrides and epoxies.
Also provided are compositions composed of mixtures of the oligomer-modified
anionically polymerized polymers with non-modified anionically polymerized polymers


and/or anionically polymerized polymers that have been modified with capping or
coupling agents, other than the oligomers provided herein. For the purposes of this
disclosure, a non-modified anionically polymerized polymer refers to anionically
polymerized polymers that have undergone anionic polymerization termination reactions
rather than end-capping or coupling reactions with other molecules. The nature and ratios
of each of these components in a mixture may be selected to provide the appropriate
properties for a given application.
Other aspects of the invention provide articles and compositions made from the
oligomer-modified anionically polymerized polymers, reinforced materials made from a
mixture of the oligomer-modified anionically polymerized polymers with a material to be
reinforced and articles made from the reinforced materials. Other aspects of the invention
provide oligomer-modified anionically polymerized polymers with enhanced adhesion to
specific substrates and articles made from the adhesion enhanced materials.
The oligomers used to functionally modify the anionically polymerized polymers
are characterized by low molecular weights. Throughout this disclosure, the molecular
weights cited are measured using gel permeation chromatography under ASTM D 3536
with a linear polystyrene standard. For example, in some instances the oligomers have a
number average molecular weight (Mn) of no more than about 10,000 and a weight
average molecular weight (Mw) of no more than about 60,000. In some instances, the
oligomers have a weight average molecular weight of no more than about 40,000. This
includes oligomers having a number average molecular weight of about 1,000 to about
10,000 and oligomers having a weight average molecular weight of about 1,500 to about
40,000. However, the oligomers are significantly larger than small molecules which have
been used to modify anionically polymerized polymers. Typically, the oligomers have a
number average molecular weight of at least about 500, desirably at least about 1000 and a
weight average molecular weight of at least 1000, desirably at least about 1500.
The oligomers are made from at least one acrylic monomer and are functionalized
with at least one functional group which is selected from esters, carboxylic acids,
anhydrides and epoxies. In addition to the acrylic monomer, the oligomers may be made
from at least one additional free radically-polymerizable monomer such as, but not limited
to, styrene or modified styrene monomers.


By controlling the comonomer composition, the molecular weight distribution, and
the functionality type and distribution in the oligomers, the chemical and physical
characteristics of the oligomers can be tailored to provide an oligomer-modified
anionically polymerized polymer having suitable qualities to provide appropriate
miscibility, dispersibility, compatibility and/or adhesion characteristics for a desired
application. Particular applications for which the oligomer-modified anionically
polymerized polymers of the present invention are well suited include asphalt reinforcers,
modifiers and asphalt morphology stabilizers. Other suitable applications include use as
compatibilizers, viscosity modifiers, flow modifiers, process aids, rheology control agents,
and impact modifiers for polar plastics and polar plastics blends and alloys, and
composites. The oligomer-modified anionically polymerized polymers may also be
designed with tailored surface activities to provide adhesives with optimal adhesion to
polar substrates, useful in typical adhesive applications but also on tire rubbers with
enhanced metal adhesion.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

FIG. 1 is a schematic diagram of a first reactor apparatus that may be used to
produce oligomer-modified anionically polymerized polymers.
FIG. 2 is a schematic diagram of a second reactor apparatus that may be used to
produce oligomer-modified anionically polymerized polymers.
FIG. 3 is a fluorescence micrograph of a polymer-modified asphalt made from 3.5
wt. % APP-1 in AC-20, as described in Example 2.
FIG. 4 is a fluorescence micrograph of a polymer-modified asphalt made from 3.5
wt. % OMAPP-3 in AC-20, as described in Example 2.
FIG. 5 is a fluorescence micrograph of a polymer-modified asphalt made from 11
wt. % APP-1 in AC-20, as described in Example 3.
FIG. 6 is a fluorescence micrograph of a polymer-modified asphalt made from 11
wt. % OMAPP-3 in AC-20, as described in Example 3.


DETAILED DESCRIPTION
The present invention provides oligomer-modified anionically polymerized
polymers, methods for producing the polymers, compositions and articles made from the
polymers, reinforced materials containing the polymers and articles made from the
reinforced materials.
The oligomer-modified anionically polymerized polymers of the present invention
are produced by reacting oligomers with anionically polymerized polymers to produce
modified polymers having tailored chemical and physical properties that make them
suitable for use in a broad range of commercial applications. In particular, some of the
oligomer-modified anionically polymerized polymers provided herein are well suited for
use as adhesives, including pressure sensitive adhesives and hot melt adhesives. The
oligomer-modified anionically polymerized polymers may also be designed for use as
compatibilizing or reinforcing agents in asphalt and in polymer blends. Asphalts which
may benefit from the compatibilizing or reinforcing agents provided herein include those
commonly used for road paving and roofing applications. Roofing applications include
reinforcement of roof shingles, as well as modification of materials for roof waterproofing,
repair, and maintenance. Certain types of oligomer-modified anionically polymerized
polymers may also be used as reinforcing agents, viscosity modifiers, flow modifiers,
processing aids and impact modifiers in rubbers and plastics. Polar plastics and polar
engineering plastics are types of plastic that may benefit from the oligomer-modified
anionically polymerized polymers. Polar plastics include, but are not limited to
polyamides, polyurethanes, polyethers, polysulfones, polyether-ketones, polyetherether
ketones, polyimides, polyetherimides polycarbonates and polyesters.
By controlling oligomer characteristics, including comonomer composition,
molecular weight distribution and type and degree of functionalization, oligomer
properties such as solubility parameters, refractive indices, glass transition temperatures,
and surface activities may be tailored to provide oligomers suited for a desired application.
As a result, anionically polymerized polymers may be modified with the oligomers to
provide oligomer-modified anionically polymerized polymers having carefully tailored
characteristics. Thus, for a desired application, an oligomer-modified anionically


polymerized polymer may be designed such that it has the appropriate adhesive properties
or is appropriately compatible, miscible or dispersible with or in other materials.
The anionically polymerized polymers to be modified according to the present
invention may be any anionically polymerized polymers capable of undergoing end-
capping or coupling reactions with the oligomers. Anionic polymerization is a well-
known technique which uses initiators, such as organo alkali metal initiators, to
polymerize conjugated diolefins or other anionically polymerizable monomers or to
copolymerize conjugated diolefins with other anionically polymerizable monomers.
Anionic polymerization may be carried out in a continuous, batch or semi-batch process.
A general description of the anionic polymerization process may be found in Polymer
Chemistry, An Introduction; Chapter 7, pages 250-261,2nd Ed., M.P. Stevens editor
(1990), which is incorporated herein by reference. The polymers produced by anionic
polymerization are commonly referred to as "living polymers" because each monomer
reaction step creates a new reactive carbanion, allowing the polymer to continue to grow
until the monomers are depleted. The polymers remain "alive" even after the monomers
are depleted and will continue to react and grow once additional reactive monomer is
supplied. Thus, anionic polymerization is a particularly attractive process for the
production of well-defined block copolymers. The anionically polymerized polymers may
be either radial, linear or branched polymers depending upon the functionalities of the
initiators, monomers or coupling agents used to make them.
Anionic polymerization is typically carried out in inert hydrocarbon solvents at low
temperatures under vacuum or an inert atmosphere with highly purified reagents in order
to prevent the premature termination of the polymerization reaction. Anionically
polymerized polymers include thermoplastic, elastomeric, and thermoplastic-elastomer
polymers. The polymers may be homopolymers or copolymers including both random
and block copolymers. The anionically polymerized polymers for use in the present
invention typically have a number average molecular weight from about 3,000 to about
300,000. This includes anionically polymerized polymers having a number average
molecular weight from about 20,000 to 300,000 although the invention is not limited to
anionically polymerized polymers falling within these molecular weight ranges.


Suitable conjugated diolefins for use in building the anionically polymerizable
polymers for use in the present invention include, but are not limited to, 1,3 butadiene,
isoprene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 2,3-dimethyl-1,3-butadiene,
2,4-hexadiene, 1,3-hexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-octadiene, 4,5-diethyl-1,3-
octadiene and the like. Other anionically polymerizable monomers that may be used in the
production of the anionically polymerizable polymers include, but are not limited to,
vinylaromatic monomers, such as styrene and styrene derivatives including 3-
methylstyrene, α-methylstyrene, p-methylstyrene, a,4-dimethylstyrene, t-butylstyrene, o-
chlorostyrene, 2-butenyl naphthalene, 4-t-butoxystyrene, 3-isopropenyl biphenyl, 4-
vinylpyridine, 2-vinylpyridine and isopropenyl naphthalene, 4-n-propylstyrene. Other
anionically polymerizable monomers include acrylamides, acrylonitriles, nitrobutene,
vinylisocyanates, anhydrides, methacrylates, acrylates, vinyl pyridines, carbodiimides,
lactones, lactams, dienes, cyclic siloxanes, and ethylene.
Examples of anionically polymerized polymers that may be made from anionically
polymerizable monomers include, but are not limited to, polystyrene, polybutadiene,
polyisoprene, polyethers, polyacetals, and polyphenylene oxides. The anionically
polymerizable polymers may also be elastomers and thermoplastic elastomers made from
block copolymers of styrene (S), butadiene (B), ethylene(E) and isoprene (I) of varying
sizes and number of blocks. Examples of such elastomers and thermoplastic elastomers
include SB, SI, SBR, (SB)mS (where m is an interger), SBS, SIS, BSB, ISI block
copolymers as well as their hydrogenated and partially hydrogenated counterparts,
including SEBS, SEB and others.
By way of illustration, examples of anionically polymerized polymers that are
well-suited for use as modifiers asphalts and adhesives include linear elastomers produced
by the copolymerization of at least one vinyl aromatic monomer and at least one
conjugated diene monomer. Some such linear elastomers are copolymers that may be
characterized by the following structures, depending on the order of addition of monomers
and monomer reactivity:
AB(AkBj)i
BA(BjAk)i


where A is a block homopolymer or a random or tapered copolymer predominantly
composed of polymerized vinylaromatic compounds and B is a block homopolymer or a
random or tapered copolymer predominantly composed of polymerized conjugated diene
compounds. In the structures above, i is zero or a positive whole number 1 or higher, and j
and k may be independently either zero or one. This means that the A and B segments
present in the vinylaromatic/conjugated diene polymer can form diblocks, triblocks, and
multiblocks. In the case of triblock and multiblock polymers, the length and composition
of the A and B homopolymers or copolymers can be different within the same polymer.
For example, in an ABA polymer, the two A blocks can have a different size and
composition.
In some embodiments of the linear elastomers, the molar ratio of vinyl aromatic
monomer to conjugated diene monomer desirably ranges from about 0.1 to about 1.0,
desirably, from about 0.2 to about 0.5 and more desirably about 0.3 to 0.4. The vinyl
group content of the linear elastomer based on the conjugated diene incorporated therein
may range desirably from about 8 to about 70 mole %, and more desirably, from about 8
to about 55 mole %.
Many anionic polymerization initiators are well known and commercially
available. Organo lithium compounds, such as butyl lithium, are examples of commonly
used initiators. Specific examples of these initiators include methyllithium, ethyllithium,
t-butyllithium, n-butyllithium, n-decyllithium, isopropyllithium, eicosyllithium,
cylcloalkyllithium compounds, such as cyclohexyllithium, and aryllithium compounds,
such as phenyllithium, naphthllithium, p-toluyllithium, and the like.
The anionic polymerization reactions may take place in a variety of organic
solvents. Examples of suitable solvents include, but are not limited to, pentane, hexane,
heptane, octane, cyclopentane, cyclohexane, cycloheptane, benzene, naphthalene, toluene,
xylene, methyl ether, methyl ethyl ether, diethyl ether, tetrahydrofuran, acetone and
methyl ethyl ketone. Cyclohexane and n-hexane, in particular, are well suited for use as
the solvents in anionic polymerizations.
The oligomers used to modify the anionically polymerized polymers are made
from free-radically polymerizable monomers. The oligomers are functionalized with at


least one functional group selected from esters, carboxylic acids, anhydrides and epoxies,
which may be located on one of the polymerizable monomers. The monomers useful in
this invention include acrylic and non-acrylic monomers. Suitable non-acrylic monomers
include aromatic monomers, olefins, unsaturated dicarboxylic anhydrides, acrylonitrile,
and the like. An acrylic monomer having only a methacrylate or acrylate group (i.e., a
non-functional acrylate or methacrylate) is considered an ester-functional monomer for the
purposes of this disclosure. Thus, the oligomers may be multifunctional oligomers
comprising at least two, and in some instances at least three or more, functionalities.
Preferred ratios of acrylic to non-acrylic monomers depend on the desired properties of the
oligomer, such as solubility parameter, refractive index, glass transition temperature, and
surface activity. The desired properties will, in turn, depend on the intended application of
the modified anionically polymerized polymer.
The extent of oligomer functionalization may be measured as number average (Fn)
and weight average (Fw) number of functional groups per chain. Optimal Fn and Fw
values for a given oligomer will depend on the intended application. In some
embodiments, the oligomers have an Fn value of no more than about 20. This includes
embodiments where the oligomers have an Fn value of no more than about 10 and further
includes embodiments where the oligomers have an Fn value of no more than about 1. For
example, some of the oligomers provided herein have an Fn value ranging from about 1 to
20, desirably about 1 to 10. Similarly, in some embodiments, the oligomers have an Fw
value of no more than about 100. This includes embodiments where the oligomers have
an Fw value of no more than about 20 and further includes embodiments where the
oligomers have an Fw value of no more than about 1. For example, some of the oligomers
provided herein have an Fw value ranging from about 1 to 100, desirably about 2 to 25.
Generally, smaller Fn and Fw values will be preferred where end-capping reactions are
desired and larger Fn and Fw values will be preferred where coupling reactions are
desired.
Although the ester groups provide potentially reactive functional groups, Fn and
Fw values for the oligomers are determined by the most reactive functional group
presented on the oligomer molecule. For this reason, the Fn and Fw values and ranges
quoted herein do not take the ester groups into consideration, i.e. for an epoxy-functional


oligomer, a cited Fn value of 1.4 refers only to the epoxy moiety. However, it should be
understood that for some oligomers, such as polyacrylates, the inherent ester groups are
also functional groups present on the oligomers, yet, for the purposes of this disclosure,
the Fn and Fw values for these polyacrylates are zero. Therefore the Fn and Fw values
and ranges cited above would not be applicable to such oligomers. The optimal extent of
oligomer functionalization will vary depending upon the intended application for the
modified anionically polymerized polymer. By way of illustration, preferred ranges are
provided in the Applications section below for various applications.
Suitable acrylic monomers include functional and non-functional acrylates and
methacrylates. Examples of suitable acrylic monomers include, but are not limited to,
methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-
butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl
acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
iso-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate,
cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-
butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, n-
hexyl methacrylate, i-amyl methacrylate, s-butyl-methacrylate, t-butyl methacrylate, 2-
ethylbutyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, iso-octyl
methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate,
cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, and
isobornyl methacrylate.
Examples of suitable epoxy functional acrylic monomers include, but are not
limited to, those containing 1,2-epoxy groups such as glycidyl acrylate, glycidyl
methacrylate, and 4-vinyl-l-cyclohexene 1,2 epoxide.
Examples of suitable acid functional acrylic monomers include, but are not limited
to, those containing carboxylic acid groups such as acrylic acid, methacrylic acid, and
maleic acid.
Examples of suitable anhydride functional acrylic monomers include, but are not
limited to, maleic anhydride, itaconic anhydride, and citraconic anhydride.
In addition to the acrylic monomers, the oligomers may include other free-radically
polymerizable monomers, such as vinyl aromatic monomers. Suitable vinyl aromatic

monomers include styrenic monomers. Suitable styrenic monomers include, but are not
limited to, styrene, a-methylstyrene, p-methylstyrene, t-butylstyrene, o-chlorostyrene, and
vinyl pyridine.
The chain extenders listed in United States Patent Application No. 10/342,502 filed

Jan 15TH 2003, may be used as oligomers in the production of the oligomer-modified
anionically polymerized polymers described herein. The entire disclosure of United States
Patent Application No. 10/342,502 is incorporated herein by reference.
The oligomers are characterized by low molecular weights. For example, the
oligomers may have a number average molecular weight of no more than about 10,000
and may have a weight average molecular weight of no more than about 60,000. This
includes oligomers having a number average molecular weight of about 1,000 to about
10,000 and further includes oligomers having a number average molecular weight of about
1,500 to about 5,000. Also included are oligomers having a weight average molecular
weight of about 1,500 to about 40,000 and oligomers having a weight average molecular
weight of about 2,500 to about 20,000. However, the oligomers are significantly larger
than small molecules which have been used to modify anionically polymerized polymers.
Typically, the oligomers have a number average molecular weight of at least about 500,
desirably at least about 1000 and a weight average molecular weight of at least 1000,
desirably at least about 1500.
The use of oligomers having low molecular weights as capping and coupling
agents for anionically polymerized polymers is advantageous because it allows the
properties of the modified anionically polymerized polymers to be tailored to a degree that
is not possible with small molecule and high molecular weight polymer capping and
coupling agents. These properties that it is frequently desirable to control are the
solubility parameters, glass transition temperatures, and surface activities of the oligomers.
These properties are important in many applications because they may affect the adhesion,
compatibility, miscibility and dispersibility characteristics of the oligomers and of the
oligomer-modified anionically polymerized polymers made therefrom.
The properties of the oligomers may vary over a wide range depending on the
comonomer composition, the molecular weight distribution and the functionalization of
the oligomers. For example, oligomers having glass transition temperatures ranging from


about -80°C to about 150°C may be used to make oligomer-modified anionically
polymerized polymers.
The oligomers provided herein may have a wide range of solubility parameters.
Generally, the solubility parameters for the oligomers may vary over a range of about 0 to
30. This includes oligomers having a solubility parameter of about 13 to about 20. The
compatibility of an oligomer (and the oligomer-modified anionically polymerized polymer
made therefrom) for a given application may be predicted by the difference between the
solubility parameter the oligomer and the solubility parameter of the polymer component
or components present in the composition to which the oligomer-modified anionically
polymerized polymer is to be added. Thus oligomers may be selected for a given
application by matching the solubility parameter of the oligomer to that of a polymer
component in a composition with which the oligomer-modified anionically polymerizable
polymer is to be combined. For example, oligomers intended to modify anionically
polymerizable polymers for use in asphalt may be designed to have solubility parameters
similar to those of the aromatic and natural fractions present in the asphalt. For example,
the solubility parameters of the oligomers may be tailored to come within four, and
desirably two, units or less of the optimum solubility parameter for a given application.
By way of illustration, oligomers having solubility parameters that are sufficiently
"matched" to various polymer systems for various applications are described in the
Applications section below.
The surface energy of the oligomers may be tailored to lie within 10, and desirably
within 5, dyne or less of the optimum surface energy for a given application.
The oligomers may be made using conventional polymerization techniques,
including continuous, batch and semi-batch polymerizations. However, the oligomers are
desirably made using the production techniques described in United States Patent
Application No. 09/354,350 and United States Patent No. 6,552,144, the entire disclosures
of, which are incorporated herein by reference. Briefly, these processes involve
continuously charging into a reactor at least one acrylic monomer, and optionally one or
more other monomers that are polymerizable with the acrylic monomer, wherein at least
one of the monomers is an ester-functional, carboxy-functional, anhydride-functional, or
epoxy-functional monomer. In one embodiment the reactor charge includes at least one
14

epoxy-functional (meth)acrylic monomer, at least one styrenic and/or (meth)acrylic
monomer, and optionally one or more other monomers that are polymerizable with the
epoxy-functional monomer, the styrenic monomer, and/or the (meth)acrylic monomer,
wherein "(meth)" is used to indicate both methacrylic and acrylic.
The reactor may also optionally be charged with at least one free radical
polymerization initiator and/or one or more solvents. Examples of suitable initiators and
solvents are provided in United States Patent Application No. 09/354,350. Briefly, the
initiators suitable for carrying out the process are compounds which decompose thermally
into radicals in a first order reaction, although this is not a critical factor. Suitable
initiators include those with half-life periods in the radical decomposition process of about
1 hour at temperatures greater or equal to 90°C and further include those with half-life
periods in the radical decomposition process of about 10 hours at temperatures greater or
equal to 100°C. Others with about 10 hour half-lives at temperatures significantly lower
than 100°C may also be used. Suitable initiators are, for example, aliphatic azo
compounds such as 1-t-amylazo-l-cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-
butylazo-cyanocyclohexane, 2,2'-azo-bis-(2-methyl)butyronitrile and peroxides and
hydroperoxides, such as t-butylperoctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-
butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide and the
like. Additionally, di-peroxide initiators may be used alone or in combination with other
initiators. Such di-peroxide initiators include, but are not limited to, 1,4-bis-(t-butyl
peroxycarbo)cyclohexane, 1,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl
peroxy)hexyne-3, and other similar initiators well known in the art. The initiators di-t-
butyl peroxide and di-t-amyl peroxide are particularly suitable. Other free-radical
polymerization techniques suitable for producing the oligomers may be found in U.S.
Patent No. 6,605,681, the entire disclosure of which is incorporated herein by reference.
The initiator may be added with the monomers. The initiators may be added in any
appropriate amount, but preferably the total initiators are added in an amount of about
0.0005 to about 0.06 moles initiator(s) per mole of monomers in the feed. For this purpose
initiator is either admixed with the monomer feed or added to the process as a separate
feed.


The solvent may be fed into the reactor together with the monomers, or in a
separate feed. The solvent may be any solvent well known in the art, including those that
do not react with acrylic monomers at the high temperatures of the continuous process
described herein. The proper selection of solvent may help decrease or eliminate the gel
particle formation during the continuous, high temperature reaction. Such solvents
include, but are not limited to, xylene, toluene, ethyl-benzene, Aromatic-100®, Aromatic-
150®, Aromatic-200® (all Aromatics available from Exxon), acetone, methylethyl ketone,
methyl amyl ketone, methyl-isobutyl ketone, N-methyl pyrrolidinone, and combinations
thereof. When used, the solvents are present in any amount desired, taking into account
reactor conditions and monomer feed. In one embodiment, one or more solvents are
present in an amount of up to 40 % by weight, up to 15 % by weight in a certain
embodiment, based on the total weight of the monomers.
The reactor is maintained at an effective temperature for an effective period of time
to cause polymerization of the monomers to produce an oligomer from the monomers.
A continuous polymerization process allows for a short residence time within the
reactor. The residence time is generally less than one hour, and may be less than 30
minutes. In some embodiments, the residence time is generally less than 20 minutes, and
may be less than 15 minutes.
The process for producing the oligomers may be conducted using any type of
reactor well-known in the art, and may be set up in a continuous configuration. Such
reactors include, but are not limited to, continuous stirred tank reactors ("CSTRs"), tube
reactors, loop reactors, extruder reactors, or any reactor suitable for continuous operation.
A form of CSTR which has been found suitable for producing the oligomers is a
tank reactor provided with cooling coils and/or cooling jackets sufficient to remove any
heat of polymerization not taken up by raising the temperature of the continuously charged
monomer composition so as to maintain a preselected temperature for polymerization
therein. Such a CSTR may be provided with at least one, and usually more, agitators to
provide a well-mixed reaction zone. Such CSTR may be operated at varying filling levels
from 20 to 100 % full (liquid full reactor LFR). In one embodiment the reactor is more


than 50 % full but less than 100 % full. In another embodiment the reactor is 100 % liquid
full.
The continuous polymerization is carried out at high temperatures. In one
embodiment, the polymerization temperatures range from about 180°C to about 350°C,
this includes embodiments where the temperatures range from about 190°C to about
325°C, and more further includes embodiment where the temperatures range from about
200°C to about 300°C. In another embodiment, the temperature may range from about
200°C to about 275°C.
The anionically polymerized polymers can be made by any suitable method known
in the art, such as those described in U.S. Patent Nos. 3,281,383, and 3,753,936 which are
incorporated herein in their entirety by reference. In these methods the anionically
polymerized polymers are made by contacting anionically polymerizable monomers with
an organolithium compound as an initiator. The preferred class of these compounds can
be represented by the formula RLi wherein R is a hydrocarbon radical selected from the
group consisting of aliphatic, cycloaliphatic, and aromatic radicals containing from 1 to 20
carbon atoms, although higher molecular weight initiators can be used. Examples of these
initiators include methyllithium, ethyllithium, t-butyllithium, n-butyllithium, n-
decyllithium, isopropyllithium, eicosyllithium, cylcloalkyllithium compounds, such as
cyclohexyllithium, and aryllithium compounds, such as phenyllithium, naphthllithium, p-
toluyllithium, and the like. The amount of initiator varies depending upon the desired
molecular weight of the product anionically polymerized polymer. Number average
molecular weights between about 20,000 and 300,000 can be obtained by adding about 5.0
to 0.33 millimoles of the RLi initiator per mole of monomers corrected by the factor
100/(MW of monomer).
In the case of anionically polymerized homopolymers such as polystyrene,
polyisoprene and polybutadiene, the corresponding monomer is added to contact the
initiator in a suitable reaction zone under an effective temperature and residence time to
complete the monomer addition reactions. One convenient way to make anionically
polymerized block copolymers such as SB, SBS, SI and SIS, and the like, is by
polymerizing the styrenic monomer in the presence of the organolithium initiator to form


the initial polymer block and subsequently adding the conjugated diene to the
polymerization mixture to produce a block copolymer of the styrenic and conjugated diene
monomers. Additional blocks can be added by continuing alternating feeds of styrenic
and conjugated diene monomers. In addition to anionically polymerized homopolymers
and block copolymers, anionically polymerized random copolymers such as different
grades of SBR and SIR can be made by adding several types of monomer simultaneously
to the reaction zone. The sequence length distributions of the monomers in these random
chains can be further altered by the use in the reaction mix of chemical compounds known
as randomizers. Alternatively, anionically polymerized tapered block copolymers such as
SB and SI can be obtained by adding the conjugated diene monomer to the reaction zone
prior to the full consumption of the styrenic monomer, in this manner a transition random
copolymer is formed between the styrenic and conjugated diene monomer blocks. People
skilled in the art understand the differences in characteristics, properties and applicability
that these different kinds of anionically polymerized polymers and copolymers have.
The anionic polymerization is normally carried out at temperatures in the range of-
100°C to 150°C, preferably between -75°C and 75°C. Normally 50 to 90% of a reaction
solvent is used to control the viscosity inside the reaction zone, preferably 70 to 85%.
Examples of suitable solvents include, but are not limited to, pentane, hexane, heptane,
octane, cyclopentane, cyclohexane, cycloheptane, benzene, naphthalene, toluene, xylene,
methyl ether, methyl ethyl ether, diethyl ether, tetrahydrofuran, acetone and methyl ethyl
ketone. Typical residence times for anionic polymerization vary depending on the
reaction temperature and initiator level between 0.1 and 5 hours, preferable from 0.2 to 2
hours.
The resulting anionically polymerized polymers contain a very high percentage of
molecules in which a lithium atom is positioned at the chain end as a counterion to the
anion at the chain end monomer unit of the polymer chains. Impurities present in the
system, such as water or alcohol will tend to reduce the amount of lithium terminated
anionically polymerized polymer formed. The lithium terminated anionically polymerized
polymer is called a "living polymer" and can be further reacted with functional
compounds such as the oligomers of this invention.


The oligomer-modified anionically polymerized polymers may be made following
well known methods in the art such as those described in U.S. Patent Nos. 3,281,383 and
3,753,936 by charging the oligomers into an anionic polymerization reaction zone after the
"living" anionically polymerized polymers have been formed, that is, prior to any addition
of materials such as water, acid or alcohol commonly added to inactivate and/or remove
the lithium atoms present in the polymer. The oligomers may be added to the reaction
zone after being dissolved in a suitable reaction solvent. The solvent is desirably the same
as the one used during the anionic polymerization and the oligomer contents in this solvent
is desirably controlled such that the viscosity of the oligomer solution is equal to or less
than the viscosity of the anionically polymerized polymer solution in the reaction zone.
Normally the oligomers of this invention are tailored to be soluble in the same solvents
used in the anionic polymerization and the right viscosities are achieved between 10 and
60% solids. Because anionic polymerization is typically carried out in cyclohexane or n-
hexane, it is advantageous to use oligomers that are soluble in these solvents. The
functional groups on the oligomers readily react with the carbanions on the anionically
polymerized polymers to produce the modified polymers.
The ratio of oligomer to anionically polymerized polymer in the oligomer-
modified anionically polymerized polymers may vary over a broad range, depending on
the intended application for the reaction product. In some illustrative embodiments, the
molar ratio of oligomer to anionically polymerized polymer in the reaction product is
about 0.05 to 2. This includes embodiments where the molar ratio of oligomer to
anionically polymerized polymer in the reaction product is about 0.1 to 1. The weight of
the oligomer-modified anionically polymerized polymers will also vary depending on the
intended application. Typically, the number average molecular weight of the oligomer-
modified anionically polymerized polymer will range from about 5,000 to 1,800,000
g/mol, desirably about 60,000 to about 1,500,000 g/mol and more desirably about 20,000
to about 600,000 g/mol. For example, the oligomer-modified anionically polymerized
polymers may have number average molecular weight of about 5,000 to 1,000,000 or from
about 20,000 to 1,800,000.
The anionic polymerization reactions and the oligomer modification reactions may
take place in situ, that is in a single reaction zone, as described above, or in different


reaction zones. The former design tends to favor faster reactions while the latter design
may be preferred when end-capping reactions are desired over coupling reactions. In
some embodiments, a reaction apparatus having two or more reaction zones (e.g., reaction
chambers) may be employed. In these embodiments, the anionic polymerization to form
the anionically polymerized polymers may be carried out in a first reaction zone and the
polymerization of the oligomers and the reaction of the oligomers with the anionically
polymerized polymer may be carried out in a second reaction zone. In a variation of this
embodiment, shown in FIG. 1, the reactor apparatus 100 may include a first reaction
chamber 102, a second reaction chamber 104 in fluid communication with the first
reaction chamber 102 and a third reaction chamber 106 in fluid communication with both
the first 102 and second 104 reaction chambers. Each of the chambers is desirably
equipped with mixing and heating means. Using this apparatus, solvents and monomers
may be fed from their respective storage tanks (not shown) into the first reaction chamber
102 where anionic polymerization takes place. A portion of the living anionically
polymerized polymer is then passed from the first reaction chamber 102 into the second
reaction chamber 104 where it undergoes end-capping and/or coupling reactions with the
oligomer. The second reaction chamber 104 is equipped with solvent and oligomer
storage tanks (not shown) to allow the oligomer modifiers and appropriate solvents to be
fed into the second reaction chamber. Another portion of the living anionically
polymerized polymer is passed from the first reaction chamber 102 into the third reaction
chamber 106 wherein it is fully or partially reacted with an anionic polymerization
terminator and/or a conventional small molecule or polymeric coupling agent. This third
reaction chamber 106 is equipped with solvent, terminator, and/or coupling agent storage
tanks (not shown). The anionic polymer from the third reaction chamber 106 is then
passed into the second reaction chamber 104 to provide a polymer mixture containing
oligomer-modified anionically polymerized polymer and non-oligomer-modified
anionically polymerized polymer and/or conventionally-modified anionically polymerized
polymer.
FIG. 2 shows another apparatus 200 that may be used to produce the oligomer-
modified anionically polymerized polymers provided herein. Using this apparatus,
purified solvent from a first solvent tank 202 is pumped into a first reaction zone 204 to


the appropriate level. The desired amount of purified monomer is then pumped into the
first reaction zone 204 from a monomer storage tank 206. The contents of the first
reaction zone 204 are then blanketed with nitrogen and thoroughly stirred while being
cooled or heated to the appropriate polymerization temperature. Once the desired
polymerization temperature is achieved, a predetermined amount of anionic
polymerization initiator is rapidly injected into the first reaction zone 204 from an initiator
tank 208 to obtain the desired polymer molecular weight. Anionically polymerizable
comonomers can be added to first reaction zone 204 at any time during the polymerization
stage to obtain random, block, or tapered block copolymers. Samples can be removed
from the first reaction zone 204 at anytime during the polymerization stage and collected
in a first sample vessel 210 for analysis and/or use. Purified solvent from a second solvent
tank 212 is pumped into a second reaction zone 214 to the appropriate level. The desired
amount of oligomer modifier is fed into the second reaction zone 214 from an oligomer
storage tank 216, using the appropriate feeding system. The contents in the second
reaction zone 214 are then blanketed with nitrogen and thoroughly stirred while being
cooled or heated to the appropriate modification temperature. Once the desired degree of
polymerization is achieved in the first reaction zone 204, the modifier solution in the
second reaction zone 214 can be pumped into the first reaction zone 204 when chain
coupling is desired. Conversely, the contents of the first reaction zone 204 can be pumped
into the second reaction zone 214 when end-capping is desired. Samples can be removed
from the second reaction zone 214 at anytime during the modification stage and collected
in a second sample vessel 218 for analysis and/or use. Terminating agents can be added
anytime during the polymerization and modification processes from terminator storage
tanks 220, 222 to fully or partially quench the anionic species present. At the completion
of this process the contents of either the first or second reaction zone 204,214 may be
pumped through a polymer isolation unit 224 for analysis and use.
By controlling the rate of addition of the oligomer solution to the living anionically
polymerized polymer solution and the oligomer to lithium stoichiometry ratio, reactions
between the oligomer and the living anionically polymerized polymer may favor either
chain end-capping or chain coupling reactions. The reaction between the oligomer and the
anionically polymerized polymer may be quite rapid. In some instances, the oligomer and


the anionically polymerized polymers are allowed to react for less than about 1 minute and
up to about 20 minutes. This includes embodiments where the oligomer and the
anionically polymerized polymers are allowed to react for about 5 seconds to 5 minutes.
Typical reaction temperatures for the production of the oligomer-modified anionically
polymerized polymers include temperature of room temperature (i.e. about 20°C) to about
150°C.
Chain end-capping, means that the most favored reaction product of the reaction
between the oligomer and the living anionically polymerized polymer is that in which one
oligomer chain is covalently bound to one anionically polymerized polymer chain,
resulting primarily in a SO, BO, SBO, SBRO, (SB)mSOIO (where m is an interger), SIO,
SBSO, SISO oligomer-modified anionically polymerized polymer, where O represents the
oligomeric "block" formed at the chain end, with the corresponding deactivation of the
living character of the resulting polymer molecule. Chain end-capping structures are
favored whenever oligomer to lithium stoichiometry ratios larger than or equal to 1:1 are
used (i.e., molar excess of oligomer over lithium). In certain embodiments ratios from 2:1
to 1:1 are used and rapid additions of the oligomer to the living anionically polymerized
polymer is carried out. Alternatively, slow additions of the living anionically polymerized
polymer may be made to the oligomer solution previously placed in the reaction zone.
Chain coupling means that the most favored reaction product of the reaction
between the oligomer and the, living anionically polymerized polymer is that in which one
oligomer chain is covalently bound to more than one anionically polymerized polymer
chain, resulting primarily in (S)„0, (B)nO, (SB)nO, (I)nO, (SI)nO, (SBS)nO and (SIS)nO
oligomer-modified anionically polymerized polymers, where O represents the oligomeric
"block" formed in the chain interior, with the corresponding deactivation of the living
character of the resulting polymer molecule, and (n) represents all numbers of the
distribution characterized by Fn and Fw. Thus, given the functionality distribution of the
oligomer, defined by its molecular weight distribution, the oligomer-modified anionically
polymerized polymer obtained through favored chain coupling reactions may be a
collection of mono, di, tri, tetra, penta blocks, etc. covalently bound to the oligomer where
the number of blocks (n) has a number average equal to the oligomer Fn and a weight


average equal to the oligomer Fw. Chain coupling structures are favored whenever
oligomer to lithium stoichiometry ratios less than 1:1 are used (i.e., molar excess of
lithium over oligomer), preferably when 1 :(1/Fn) ratios are used (i.e., 1 equivalent of
lithium per equivalent of oligomer functionality), and when slow additions of the oligomer
to the living anionically polymerized polymer are carried out. In some instances the chain
coupling reactions produce oligomer-coupled anionically polymerized polymers wherein
the average number of anionically polymerized polymer chains couple to each oligomer is
about 2 to 30, desirably about 5 to 15 and more desirably about 5 to 10.
When the anionically polymerized polymers are mixed and reacted with the
oligomers a combination of end-capping and chain coupling reactions may result. In some
instances at least about 10 mole % of the anionically polymerized polymers have
undergone end-capping reactions. In some instances about 2 to 70 mole % of the
anionically polymerized polymers have undergone chain coupling reactions. This includes
embodiments where about 5 to 50 mole % of the anionically polymerized polymers have
undergone chain coupling reactions and further includes embodiments where about 20 to
50 mole % of the anionically polymerized polymers have undergone chain coupling
reactions.
In some embodiments of the methods provided herein, the living anionically
polymerized polymers undergo partial termination prior to being exposed to or reacting
with the oligomer. Partial termination means that a portion of the total living anionically
polymerized polymers are deactivated to limit reactions between these anionically
polymerized polymers and the oligomers. Partial termination may be carried out by
adding a proton donor to the reaction to partially terminate the anionic polymerization or
by increasing the temperature to thermally deactivate the living polymers. Suitable
terminating agents that may be used to deactivate the living polymers include, but are not
limited to, alcohols, water, impeded phenolic compounds and acids. Specific examples of
such agents include isopropanol, octadecanol, butyl hydroxy toluene (BHT), and mixtures
thereof. The portion of the anionically polymerized polymers that have undergone
deactivation may be mixed with a portion of anionically polymerized polymers that has
been oligomer-modified to provide a polymer blend with desired properties.


In some embodiments of the methods provided here, the living anionically
polymerized polymers undergo partial coupling and/or end-capping reactions before being
exposed to or reacting with the oligomers provided herein. Partial coupling and/or end-
capping means that a portion of the total living anionically polymerized polymers undergo
coupling and/or end-capping reactions with coupling or end-capping agents, other than the
oligomers provided herein. The coupling agents desirably couple between 2 and 4
anionically polymerized polymer chains, although coupling agents capable of coupling a
greater number of chains may also be employed. Suitable coupling agents for use in the
partial coupling step include, but are not limited to, tin halides, silicon halides, or another
functionalized silicon compound, such as a silane. Silicon tetrachloride or tin tetrachloride
are specific examples of suitable coupling agents, with silicon tetrachloride being
particularly well-suited for this application. The portion of the anionically polymerized
polymers that have been so coupled or end capped may be mixed with a portion of
anionically polymerized polymers that have been oligomer-modified and, optionally, a
portion of the deactivated anionically polymerized polymers, to provide a polymer blend
with desired properties.
A polymer blend containing a mixture of oligomer-modified anionically
polymerized polymer with deactivated anionically polymerized polymer and/or
anionically polymerized polymer that has been modified with an end-capping or coupling
agent other than an oligomer may be produced in situ using stepwise reactions in a single
reaction zone. Alternatively, the partial termination/partial coupling/end-capping and
oligomer-modification reactions can be carried out on separate portions of the living
anionically polymerized polymers in separate reaction zones and the resulting products
may subsequently be blended together. The ratio of oligomer to living anionically
polymerized polymer used to make the blend will affect the level of coupling, and
therefore, the properties of the final blend. Therefore, by adjusting the relative degrees of
oligomer modification, partial termination and partial coupling reactions, the blends may
be tailored for use in a variety of applications. One illustrative application is as a
compatibilizer in asphalt. This application is discussed in greater detail in the
Applications section below.


An exemplary in situ approach may be carried out according to the following
procedure. An anionic polymerization reaction is carried out to produce "living" polymer
chains having a carbanion at one end of each chain. A portion (e.g., about 0 to about 95%)
of the living polymer chains is then deactivated in a partial termination reaction to
deactivate the chain ends to provide a linear anionically polymerized polymer and/or in a
partial coupling reaction to couple the living chains to a coupling agent to provide radial
polymers. A portion (e.g., 0.5 to 70%) of the polymer chains still living is then modified
with an oligomer as previously described. Finally, a termination reaction is carried out to
deactivate any remaining living polymer chain ends. Thus, this process may be used to
produce a polymer blend including the oligomer-modified anionically polymerized
polymers, linear anionically polymerized polymers and/or coupled radial polymers.
For either chain coupling or chain end-capping reactions carried out using a variety
of oligomers, oligomer addition modes and stoichiometrics, the temperature of these
reactions may vary over a wide range to obtain the oligomer-modified anionically
polymerized polymers. As one of skill in the art would understand, the reaction
temperature may be selected to provide for a desired degree of reactivity based on the
functionalities present. For example, temperatures ranging from about -78°C to 150°C
may be employed. More typically, temperatures between 25°C and 120°C may be used.
Faster reactions may be carried out at temperatures between 40°C and 120°C. Under these
conditions the reaction occurs very rapidly upon mixing the oligomer stream and the living
anionically polymerized polymer. The reaction may continue for several hours. More
commonly, a residence time in the reaction zone of less than 30 minutes, and desirably
less than 10 minutes is sufficient for the full reaction between the oligomer and the living
anionically polymerized polymer at the prescribed conditions. In some instances a
residence time in the reaction zone of no more than about 3 minutes is sufficient.
As one of skill in the art would recognize, the described synthesis of the
anionically polymerized polymer and the oligomer-modified anionically polymerized
polymer can occur in a reaction setting comprising either a batch, a semi-continuous or a
continuous processes operated at temperatures, solvent ratios and stream flow rates
necessary to reach the described residence time and stoichiometry conditions.


APPLICATIONS
As one of skill in the art would recognize, the optimal properties of the oligomer
will depend on the intended application. Several exemplary applications for the oligomer-
modified anionically polymerized polymers are provided below, along with a description
of some suitable properties of the oligomers used in each application. These applications
are provided for illustrative purposes only and are not intended to limit the scope of the
invention.
In what follows, the cited solubility parameters for the oligomers and the oligomer-
modified anionically polymerized polymers were measured according to the method for
determining solubility parameters in Hansen Solubility Parameters - A Users Handbook,
C. M. Hansen, CRC Press, 2000, pp. 1-13, which is incorporated herein by reference.
The glass transition temperatures (Tg) for the oligomers and/or of a given oligomer-
modified anionically polymerized polymer were measured according to the standard DSC
methods described in American Society for Testing and Materials (ASTM) standard
procedures ASTM D 3417 & ASTM D 3418. Number (Fn) and Weight average (Fw)
functionality per chain of the oligomer were obtained by a simple mass balance
computation from the known oligomer composition using the Molecular Weight
Distribution measured by GPC according to the Handbook of Plastics Testing Technology,
2nd Edition, Wiley-Interscience pp. 189-194, which is incorporated herein by reference.
The surface energies of the oligomers and oligomer-modified anionically polymerized
polymers were determined using a classical contact angle approach. A FibroDat 1100
instrument was employed and contact angles were measured using 5 ul water droplets and
the droplet profile was captured using an imaging technique at 01, 1.0 and 10 seconds.
Asphalt Reinforcement:
Asphalt modification presents unique challenges for the following reasons.
Experts generally consider asphalt an emulsion of two main fractions: i) malthenes, which
are divided into saturated compounds, aromatic naphthenes and polar aromatics; and ii)
asphaltenes, which include the highest molecular weight compounds insoluble in solvents
such as n-pentane or n-heptane (for example, see Analytical Chemistry 1969, Vol. 41, No.
4, 576-579; Energy & Fuels 2000, 14, 6-10; Energy and Fuels 2000, 14, 160-163; Energy


& Fuels 2000, 14, 677-684). Asphalt is typically obtained from the residuum of a crude
oil vacuum distillation tower, and generally has a boiling point of at least 350°C at
atmospheric pressure.
For asphalt to be used as a road and highway pavement, it should possess a series
of physical characteristics that ensure long life and proper performance. For this reason
asphalt is commonly modified with styrene-butadiene elastomers to improve its properties.
These elastomer-modified asphalts are known in the industry as "asphalt binders."
Although these elastomers allow notable improvement in some of asphalt's
properties, when the modified asphalt is stored, the elastomer-asphalt mixture separates
into two phases. One is a polymer phase, comprising mostly a polymer "swollen" with
several compounds contained in asphalt, and the other is composed mostly of asphaltenes
that are immiscible with the elastomer. This is due, at least in part, to the poor
compatibility between polymers of the prior art and asphalt, due to the complexity of
asphalt.
The inventors have discovered that the addition of the polymer compositions
provided herein to asphalt, improves the performance of the asphalt and reduces or
eliminates phase separation. Without wishing or intending to be bound to any particular
theory of the invention, the inventors believe this improvement is due, at least in part, to
the vinyl aromatic components of the anionically polymerized polymers and the
oligomers, since vinyl aromatics, such as polystyrene are vitreous and may contribute a
high elasticity value - a property related to the rigidity of a material - when they have a
high Tg (e.g., close to 100°C, as for polystyrene). Also, at low temperatures, the
conjugated diene component of the anionically polymerized polymers may provide
adequate dissipation of thermal or mechanical fracture forces in the modified asphalt.
This made possible by the low temperature of the conjugated diene component (i.e.,
significantly below Tg). In contrast, asphalt modifiers lacking a low-Tg monomer can not
be successfully used in asphalts that will be subjected to low temperatures. Furthermore,
it is believed that the oligomer-modified anionically polymerized polymers described
herein function as asphalt reinforcers because they contain a balance of linear structures
(i.e., the deactivated anionically polymerized polymers) and radial structures which form


physical and/or chemical crosslinks in the asphalt matrix. This tends to raise the softening
point and to decrease the phase segregation.
In countries, such as the United States, modified asphalts are evaluated according
to the standards of the American Association of State Highway and Transportation
Officials (AASHTO), which rates asphalts according to performance grade (PG). The
standards of the American Society for Testing and Materials (ASTM) are also used for
asphalt evaluation. Among the properties evaluated in modified asphalts are the
following:
1) Ring and ball softening point (RBSP). This may be measured in
accordance with ASTM D 36, which indicates the temperature at which asphalt softens
and becomes unsuitable for the subject application. The softening point or temperature is
taken using the Ring and Ball apparatus, also known as R&B.
2) Penetration at 25°C a parameter relating to the rigidity of the modified
asphalt. Penetration may be measured in accordance with ASTM D5, as the distance a
weighted needle or cone will sink into the asphalt during a set period of time.
3) Brookfield Viscosity is a property relating to the stable stationary flow of
asphalt. Brookfield Viscosity may be measured in accordance with ASTM D4404.
4) Resilience is a property that measures the elasticity of the asphalt material.
Resilience may be measured in accordance with ASTM D 113.
5) Ruting factor: G /sin8 at various temperatures is useful for determining the
performance of modified asphalt at high temperatures. This factor indicates how resistant
a pavement is to the permanent deformation that can occur over time with repeated loads
at high temperature, or when the pavement is subjected to a load much greater than the
maximum allowed in the original design. Therefore, higher Ruting factor values at high
temperatures indicate that the asphalt can withstand greater deformation than materials
that have lower Ruting factors at the same test temperature. The Ruting factor may be
measured in accordance with AASHTO TP5.
6) Upper temperature limit. By determining the Ruting factor, it is possible to
determine the upper temperature limit in accordance with AASHTO standards. The upper
temperature limit relates to the maximum temperature at which the asphalt may retain
adequate rigidity to resist rutting.


7) Lower temperature limit. By determining the Ruting factor, it is possible to
determine the lower temperature limit in accordance with AASHTO standards. The lower
temperature limit relates to the minimum temperature at which the asphalt may retain
adequate flexibility to resist thermal cracking.
8) Phase segregation is a critical factor in the modification of asphalt with
styrene-butadiene elastomers, due to the aforementioned problems.
It has been discovered that when about 0.1 to 10 parts by weight, and desirably
about 0.2 to 5 parts by weight, of oligomers containing about 1 to 40 mole %, and
desirably about 3 to 10 mole %, of epoxy or acid functional monomer with a balance of
monomers and oligomer molecular weights designed to provide a solubility parameter of
about 15 to 25, desirably 16 to 22, more desirably 17 to 20, Tg of about 60°C to -80°C,
desirably about -20°C to -70oC, Fn of about 1 to 6, desirably about 1 to 2, and Fw of about
1 to 15, desirably about 2 to 8, are used to modify anionically polymerized SB, SI, SBS, or
SIS polymers having a Mn of about 20,000 to 300,000, and desirably about 50,000 to
200,000, by end-capping reactions and/or coupling reactions, the resulting oligomer-
modified anionically polymerized polymers have enhanced performance as asphalt
reinforcing agents and compatibilizers.
The polymer compositions used for asphalt modification may include at least one
of: 1) linear oligomer-modified anionically polymerized polymers made by end-capping
reactions between the anionically polymerized polymers and oligomers, and 2) radial
oligomer-modified anionically polymerized polymers made by coupling reactions between
the anionically polymerized flplymers and oligomers. The polymer compositions may
optionally include linear anionically polymerized polymers made by the termination of the
anionic polymerization with a termination agent (known as "non-modified anionically
polymerized polymer" for the purposes of this disclosure). In addition the polymer
compositions may also include linear anionically polymerized polymers that were end
capped using end-capping agents other than the oligomer end-capping agent described
herein and/or radial anionically polymerized polymers coupled with coupling agents other
than the oligomer coupling agents described herein.


The oligomer-modified anionically polymerized polymers used for asphalt
reinforcement are desirably composed of an anionically polymerized polymer,
polymerized from at least one vinyl aromatic monomer and at least one conjugated diene
monomer, and at least one functional oligomer obtained as described in this same patent
application. In some embodiments, the fraction of radial oligomer-modified anionically
polymerized polymer account for about 2 to 90 mole %, and desirably about 2 to 50 %, of
the total polymer composition (i.e. the oligomer-modified polymer plus any non-modified
anionically polymerized polymer, and the fraction of non-modified linear anionically
polymerized polymer and/or linear oligomer-modified anionically polymerized polymer
desirably accounts for about 10 to 98 mole % and desirably about 50 to 98 mole % of the
total polymer composition. In certain embodiments, the radial oligomer-modified
anionically polymerized polymers have about 2 to 25 anionically polymerized polymer
chains, and desirably about Zto 18 anionically polymerized polymer chains coupled per
oligomer, on average.
Two specific applications for which the reinforced asphalts may be used are road
paving applications and roofing/waterproof coating applications. In some instances when
the reinforced asphalt is used in a road paving application, 1 to 10 parts of the oligomer-
modified anionically polymerized polymer, and desirably 2 to 5 parts, may be mixed with
99 to 90 parts, and desirably 98 to 95 parts, of an asphalt to improve the performance
characteristics thereof. In some instances when the reinforced asphalt is used in a roofing
or waterproof coating application, 5 to 20 parts of the oligomer-modified anionically
polymerized polymer, and desirably 8 to 16 parts, may be mixed with 95 to 80 parts, and
desirably 92 to 84 parts, of an asphalt to improve the performance characteristics thereof.
In certain embodiments, the oligomer-modified anionically polymerized polymers
may confer asphalt compositions with one or more of the following properties: a)
maximum application temperature of about 50°C to 90°C, measured as the temperature at
which the Rutting Factor or Dynamic Shear Stiffness (G*/sin8) (wherein G* is the
complex modulus and 8 is the phase angle measured as per AASHTO TP5) takes a value
of 1.0 KPa); b) RBSP (measured as per ASTM D36) of about 40 to 70°C; c) asphalt
penetration at 25°C (as per ASTM D5) of about 30 to 75 dmm for road paving


applications or about 65 to 100 for roofing and waterproof coating applications; and d)
morphology stability or phase separation index of no more than about 5% and desirably no
more than about 2% for road paving applications and no more than about 25% and
desirably no more than about 10% for roofing and waterproof coating applications. The
phase separation index is measured as the percent difference between the RBSP measured
at the top and bottom surfaces of a cylindrical probe, made in the interior of a sealed tube
containing the formulated asphalt and aged at 163°C for 48 hours in a vertical position
without agitation, and frozen at 30°C. The percentage difference in RBSP provides a
measure of the compatibility between the asphalt-rich phase and the polymer-rich phase in
an asphalt/polymer blend. Compared to the same asphalt compositions made with the
same anionically polymerized polymer, without the oligomer modification, the above
referenced properties may represent an improvement of about 20 to 80% in dynamic shear
rheometer stiffness; an increase of about 2°C to 5°C in RBSP; an improvement of about 5
to 20% in asphalt penetration; and an improvement of about 50 to 100% in phase
separation.
Suitable asphalts for use with the oligomer-modified anionically polymerized
polymers include, but are not limited to, AC-20 asphalts or other asphalt widely used in
road paving such as native rock asphalts, lake asphalts, petroleum asphalts, airblown
asphalts, cracked asphalts, and residual asphalts.
Impact Modification of Plastics and Engineering Thermoplastics:
It has been discovered that when about 0.1 to 20 parts by weight, and desirably
about 0.3 to 10 parts by weight of oligomers are used to modify anionically polymerized
polybutadiene, polyisoprene, SB, SI, SBS, (SB)mS or SIS or (SI)mS polymers having a Mn
of about 20,000 to 300,000 g/mol, and desirably about 50,000 to 100,000 g/mol, by a
coupling reaction and/or an end-capping reaction, the resulting oligomer-modified
anionically polymerized polymers have enhanced performance as impact modifiers for
polar plastics blends, alloys and composites of polar plastics. In some such applications,
the oligomers contain 0.5 to 50 mole %, desirably 1 to 15 mole %, of epoxy, anhydride, or
acid functional monomer. In other such applications, the oligomers may be polyacrylates
composed entirely of (meth)acrylate monomers. The oligomer molecular weights are


desirably designed to provide a solubility parameter that differs from the solubility
parameter of the plastic to be modified by about 0 to 6 units, desirably 0 to 2 units, a Tg of
about 120°C to -70°C, desirably about 100°C to -60°C, Fn of about 1 to 10, desirably
about 1.2 to 5, and Fw of about 1.5 to 40, desirably about 2 to 10.
In some such applications, about 1 to 15 parts by weight of the oligomer-modified
anionically polymerized polymer, desirably about 2 to 10 parts by weight, compounded
with about 99 to 85 parts by weight of a polar plastic, and desirably 98 to 90 parts by
weight, confer such plastic compositions with the following properties compared to those
obtained with the same composition, employing the same anionically polymerized
polymer, without the oligomer modification: Izod Impact resistance (as per ASTM D256)
improved by 5% to 150%.
Suitable polar plastics for use with the impact modifiers include, but are not
limited to, a polyamide (PA), a polyester (PE), a polycarbonate (PC), a polysulfone, a
polyether, a polyurethane (PU), and other polar plastics and blends and alloys thereof.
Specific plastics that may be modified include, but are not limited to, PA 6, PA 6,6, PA
12, PBT, PET, PETG, PS, PS copolymers, SAN, ABS, PC/ABS, HIPS, PPE, PPE/PS,
PPE/PA, PA/ABS, PC/ABS, PEI, PEK, PEEK, PSu, POM, and TPU.
Improved Adhesion of Pressure Sensitive Adhesives (PSA) and Hot Melt Adhesives
(HMA):
It has been discovered that when about 0.1 to 20 parts by weight, and desirably
about 0.1 to 10 parts by weight, of oligomers containing 0.5 to 10 mole % of epoxy, acid,
or ester functional monomer with a balance of monomers and oligomer molecular weights
designed to provide a solubility parameter that differs from the solubility parameter of the
substrate to which the adhesive is to be applied by about 0 to 4 units, preferably 0 to 2
units, a Tg of about 20°C to -80°C, desirably about -10°C to -80°C, Fn of about 0.25 to 5,
desirably about 0.5 to 2, and Fw of about 0.5 to 15, desirably about 1 to 10, are used to
modify anionically polymerized polybutadiene, polyisoprene, SB, SI, SBS, (SB)mS, SIS or
(SI)mS polymers having a M„ of about 20,000 to 300,000 g/mol, desirably about 40,000 to
200,000 g/mol by a preferential end-capping reaction to yield a linear polymer in a
proportion of about 40 to 60 mole %, preferably about 45 to 60 mole %, the resulting


oligomer-modified anionically polymerized polymers provide enhanced performance as
PSAs or HMAs, depending on the Tg of the composition. Radial polymers may also be
present due to coupling reaction with oligomer. The radial polymers typically have a Mn
of about 80,000 to 1,600,000 g/mol wherein at least 5 mole % of the oligomer-modified
anionically polymerized polymer has a Mn of about 800,000 to 1,600,000 g/mol.
In some such applications, about 10 to 40, desirably 15 to 30, and more desirably
18 to 25, parts by weight of the oligomer-modified anionically polymerized polymer is
mixed with other conventional adhesive formulation components, such as tackifiers,
stabilizers, plasticizers and antioxidants to confer such plastic compositions with improved
properties compared to adhesives made with the same composition, employing the same
anionically polymerized polymer, without the oligomer modification. Examples of
suitable tackifiers include resins with high and low softening points which are compatible
with the polymer. These include hydrogenated resins, rosin esters, polyterpene resins,
terpene phenolic resins, and indene-cumarone resins. In some illustrative embodiments,
the amount of tackifier resins in the composition ranges from about 45 to 65 % by weight.
Plasticizers, generally known as extending oils, include mineral oils, paraffinic oils, and
naphtenic oils. In some illustrative embodiments, the amount of plasticizer in the
composition ranges from about 15 to 30 % by weight. The antioxidants may be used to
inhibit the thermal and UV oxidation processes, and are typically added to the adhesive
composition in amounts of about 0.05 to 3 % by weight. Examples of antioxidants include
phenolic compounds, phosphites, amines, and thio compounds. Some examples of
commercially available adhesive components are listed in Table A below.



Examples of properties and improvements that may be provided by the oligomer-
modified anionically polymerized polymers include one or more of the following: a)
tensile strengths (as per ASTM-D3759) above 4.0 kg/cm2; b) peel strengths (as per ASTM
D903) above 1.18 kg/cm with 100% cohesive failure; c) loop tack strengths above 3.2
kg/cm ; d) shear strengths (as per ASTM D3654, using stainless steel plaques and weights
of 500 g at 23°C) above 10 days; and e) Brookfield viscosities (as per ASTM D1084) of
10 to 60, desirably 20 to 50 poise at 150°C. Compared to the same adhesive compositions

made with the same anionically polymerized polymer, without the oligomer modification,
the above referenced properties may represent an improvement of about 50 to 300% in
tensile strength; an improvement of about 20 to 100% in peel strength; an improvement of
about 50 to 300% in tack; and an improvement of about 100% to 800% in shear strength.
Elastomers and Thermoplastic Elastomers with Improved Adhesion to Metal, Wood.
Glass, and Polar Plastic Substrates:
It has been discovered that when about 1 to 45 parts by weight, and desirably about
3 to 35 parts by weight, of oligomers containing 1 to 50 mole %, desirably 1 to 10 mole %,
of epoxy, acid, or anhydride functional monomer with a balance of monomers and
oligomer molecular weights designed to provide a surface energy level (dyne) that differs
from the surface energy of the substrate to which the elastomer is to be applied by about 0
to 10 units, preferably 0 to 5 units, a Tg of about -80°C to 80°C, desirably about -70°C to
70°C, Fn of about 1 to 10 and Fw of about 2 to 40, desirably about 3 to 25, are used to
modify a linear anionically polymerized plastic, such as polystyrene or a thermoplastic
elastomer, such as polybutadiene, polyisoprene, random SBR, tapered SBR, SB, SI, SBS,
(SB)mS, SIS or (SI)mS polymers having a Mn of about 2,000 to 40,000 g/mol, desirably
about 4,000 to 25,000 g/mol, by an end-capping reaction and/or coupling reaction, the
resulting oligomer-modified anionically polymerized polymers have enhanced adhesion to
polar substrates such that the oligomer-modified anionically polymerized polymers, and
related plastic compositions show enhanced adhesion to the substrates compared to their
non-oligomer-modified counterparts. For example the adhesion ratings (as per ASTM
D3359 Method B) of the oligomer-modified anionically polymerized polymers may be
improved by 1 to 3 units compared to their non-oligomer-modified counterparts. This
property may enhance performance in tire and other rubber applications such as protective
coatings and tie layers.
Suitable substrates for use with the oligomer-modified anionically polymerized
polymers include metal, plastic, wood and glass. Metal substrates are particularly suited
for use with the adhesives provided herein. Specific examples of substrate materials
include, but are not limited to, stainless steel, carbon steel, iron, copper, and other metals,


polar plastics such as polyamides, polycarbonates, ABS, PC/ABS alloys, SAN, polyesters
and other plastics, polar substrates such as wood, glass, and other polar substrates.
Thermoplastics and Thermoplastic Elastomers with Improved Rheological and
Mechanical Properties for Soft Touch and Injection Molding Applications:
It has been discovered that when about 0.1 to 5 parts by weight, and desirably
about 0.1 to 2 parts by weight, of oligomers are used to modify 99.9 to 95 parts of a linear
anionically polymerized plastic, such as polystyrene, or a thermoplastic elastomer, such as
a SB, SI, SBS, (SB)mS, SIS or (SI)mS polymer having a Mn of about 20,000 to 300,000
g/mol, desirably about 20,000 to 100,000 g/mol, by a preferential chain coupling reaction,
the resulting oligomer-modified anionically polymerized polymer processed by extrusion
molding, injection molding or compression molding has enhanced rheological and
mechanical properties compared to similar compositions employing the same anionically
polymerized polymer without the oligomer modification. In some such applications the
oligomer contains about 0.5 to 60 mole %, desirably about 3 to 15 mole %, of epoxy, or
acid, functional monomer. In other such applications the oligomer may be polyacrylates
composed entirely of (meth)acrylate monomers. The oligomer molecular weights are
desirably designed to provide a Tg of about -70°C to 120°C, desirably about -60°C to
100°C, Fn of about 1 to 15, desirably about 1.2 to 10, and Fw of about 1 to 60, desirably
about 2 to 25.
Thermoplastics and Engineering Thermoplastics with Improved Flow Modification and/or
Rheologv Control:
It has been discovered that when about 0.05 to 40 parts by weight, and desirably
about 0.05 to 30 parts by weight, of oligomers are used to modify 99.95 to 60 parts by
weight, and desirably 99 to 70 parts by weight, of an anionically polymerized
thermoplastic, such as polystyrene, having a Mn of about 3,000 to 40,000 g/mol, desirably
about 5,000 to 30,000 g/mol, by a chain coupling and/or end-capping reaction, the
resulting oligomer-modified anionically polymerized polymer has enhanced flow and
rheological properties compared to similar compositions employing the same anionically
polymerized polymer without the oligomer modification. In some such applications, the
oligomers contain about 1 to 60 mole %, desirably about 5 to 15 mole %, of epoxy or acid


functional monomer. In other such applications the oligomers are polyacrylates composed
entirely of (meth)acrylate monomers. The oligomer molecular weights are desirably
designed to provide a Tg of about -80°C to 80°C, desirably about -70°C to 70°C, Fn of
about 1 to 10 and Fw of about 1 to 20, desirably about 2 to 10.
In some such applications, about 1 to 10 parts by weight of the oligomer-modified
anionically polymerized polymer, and desirably about 2 to 7 parts by weight, may be
mixed with 99 to 90 parts by weight of a thermoplastic, and desirably about 98 to 93 parts
by weight of the thermoplastic to improve the characteristics thereof.
The resulting thermoplastic/oligomer-modified anionically polymerized polymer
blends may have melt flow indices (as per ASTM D 1238) that vary over a wide range. In
some instances, the oligomer-modified anionically polymerized polymers may be used to
decrease the melt flow index, while in other instances the oligomer-modified anionically
polymerized polymers may be used to increase the melt flow index. In either case, in
some embodiments of the blends, the melt flow index is changed by at least about 5% due
to the inclusion of the oligomer-modified anionically polymerized polymers. This
includes embodiments where the melt flow index is changed by at least about 10%, at least
about 30%, at least about 50% and even at least about 100%.
Plastics with Improved Rheoloev:
It has been discovered that when about 0.1 to 40 parts by weight, and desirably
about 1 to 30 parts by weight, of oligomers are used to modify 99.9 to 60 parts by weight,
and desirably 99 to 70 parts by weight, of an anionically polymerized thermoplastic, such
as polystyrene, having a Mn of about 3,000 to 50,000 g/mol, desirably about 5,000 to
28,000 g/mol, by a chain coupling and/or end-capping reaction, the resulting oligomer-
modified anionically polymerized polymers has enhanced flow and rheological properties
compared to similar compositions employing the same anionically polymerized polymer
without the oligomer modification. The resulting oligomer-modified anionically
polymerized polymers exhibit enhanced reheological properties, as characterized by
parallel plate viscometry using a Rheoletric Scientific SR 5000 with 25 mm diameter
parallel plates at 0.01 and 4.0 s-1, compared to similar anionically polymerized polymers


without the oligomer modification. The degree of shear thinning can be determined by the
ratio of the viscosity at 0.01 s-1 to viscosity at 4. s-1. In some such applications, the
oligomers contain about 1 to 60 mole %, desirably about 5 to 45 mole %, of epoxy or acid
functional monomer. In other such applications, the oligomers are polyacrylates
composed entirely of (meth)acrylate monomers. The oligomer molecular weights are
desirably designed to provide a Tg of about -80°C to 80°C, desirably about -70°C to 70°C,
Fn of about 1 to 10 and Fw of about 1 to 40, desirably about 2 to 25.
The resulting oligomer modified anionically polymerized polymers may exhibit
enhanced rheological properties, as characterized by parallel plate viscometry compared to
similar linear materials without oligomer modification. For example, these oligomer
modified anionically polymerized polymers may demonstrate enhanced shear thinning
compared to similar linear materials without oligomer modification. This includes at least
about a 50% increase in shear thinning, at least about 100%, at least about 250%, and even
at least about 500% increase in shear thinning.
The invention will be further described by reference to the following examples
which are presented for the purpose of illustration only and are not intended to limit the
scope of the invention.
EXAMPLES
Example 1 - Preparation of Oligomers. Anionically Polymerized Polymers and Oligomer-
Modified Anionically Polymerized Polymers
Preparation of Functional Oligomers I:
Fourteen different functional oligomers, labeled oligomers 01 to 014 below, were
designed and prepared in 8 to 1200 liter free radical continuous polymerization reactor
systems according to the teachings of U.S. Patent Application 09/354,350. The specific
synthesis conditions and oligomer characterization parameters are given in the Tables 1a.
- 1b. below. The abbreviations used below are defined as follows, STY = styrene, 2-EHA
= 2-ethylhexyl acrylate, MMA = methyl methacrylate, i-BMA = iso-butyl methacrylate,
38

MA = methyl acrylate, GMA = glycidyl methacrylate, AA = acrylic acid, MAH = maleic
anhydride, and BA = butyl acrylate.



Preparation of Living Anionically Polymerized Polymers I:
Eight different living anionically polymerized polymers (APP) were designed and
prepared in 1 to 200 Liter reactor systems operated in batch, semi-continuous or
continuous mode according to the teachings of this invention. Briefly, prior to being fed
into the reactor, solvent and monomers were purified to decrease their moisture content to
a maximum of 8 ppm by flowing through a set of columns packed with alumina and
molecular sieves. Purified solvent was then loaded into the reactor zone followed by the
1st monomer feed. This reaction mixture was heated to the initial reaction temperature
(Ti). As Ti was reached, n-butyl lithium or other suitable initiator was added neat or in a
suitable solvent solution to the reaction zone. The amount of initiator is stoichiometrically
calculated to form individual blocks and/or final living anionically polymerized polymers
with number average and weight average molecular weight about a target value. The
polymerization step was then allowed to proceed in either isothermal or quasi-adiabatic
mode to a final temperature (Tf) and/or for a prescribed residence time (RTp). During the
polymerization step sequential addition(s) of different monomers were carried out in a
programmed batch or semi-batch mode depending on whether a homopolymer, random
copolymer, block copolymer or tapered block copolymer was desired. At the end of this
process living anionically polymerized polymer were obtained.
The specific synthesis conditions and APP characterization parameters are given in
the Table 2 below. The abbreviations used below are defined as follows, STY = styrene,
B = 1,3 butadiene, n-BuLi = n-butyl lithium, CH = cyclohexane, and TMEDA=N,N,N'N'-
tetramethyl ethylene diamine. In Table 2, "the first peak temperature" refers to the
temperature recorded after the first monomer addition and polymerization, and "the final
peak temperature" refers to the temperature after the last monomer addition and
polymerization.


Preparation of Living Anionically Polymerized Polymers II:
Ten different living APPs were designed and prepared using a reactor system
comprised of two stirred reactors in series separated with a Rotafio® stopcock, as shown
in FIG. 2. The first reactor was fit with a side arm with an ampoule attached for collection
of samples. An initiator injection arm, and monomer and solvent feed ampoules were also
attached. This reactor was used to carry out the anionic polymerization reaction to obtain
living APP. The second reactor was subsequently used to perform the oligomer
modification when end-capping was sought. Initiator was injected into the polymerization
reactor through the injection arm and solvent was then fed to the reactor directly after
distillation. The reactor was then sealed and blanketed with nitrogen, and heated to the
reaction temperature. At this temperature the purified monomer(s) was added and the
reaction was allowed to proceed for a prescribed residence time. At the end of the reaction

a sample of the living APP was quenched with a suitable termination agent (TA) to
establish its physical characteristics prior to the modification with the functional
oligomers.
The specific synthesis conditions and APP characterization parameters are given in
the Tables 3a and 3b below. The abbreviations used below are defined as follows, STY =
styrene, sec-BuLi = sec-butyl lithium, and BZ = Benzene.


Preparation of Living Anionically Polymerized Polymers III:
Five different living APPs were designed and prepared in 1 to 200 Liter reactor
systems operated in batch, semi-continuous or continuous mode according to the teachings
of this invention. Briefly, prior to being fed into the reactor, solvent and monomers were
purified to decrease their moisture content to a maximum of 8 ppm by flowing through a
set of columns packed with alumina and molecular sieves. Purified solvent was then
loaded into the reactor zone followed by the 1st monomer feed. This reaction mixture was
heated to the initial reaction temperature (Ti). As Ti was reached n-butyl lithium or other
suitable initiator was added neat or in a suitable solvent solution to the reaction zone. The
amount of initiator was stoichiometrically calculated to form individual blocks and/or final
living anionically polymerized polymers with number average and weight average
molecular weight about a target value. The polymerization step was then allowed to
proceed in either isothermal or quasi-adiabatic mode to a final temperature (Tf) and/or for
a prescribed residence time (RTp). During the polymerization step sequential addition(s)
of different monomers was carried out in a programmed batch or semi-batch mode
depending on whether a homopolymer, random copolymer, block copolymer or tapered
block copolymer was desired. At the end of this process living anionically polymerized
polymer were obtained.
The specific synthesis conditions and APP characterization parameters are given in
the Table 4 below. The abbreviations used below are defined as follows, STY = styrene,
B = 1,3 butadiene, n-BuLi = n-butyl lithium, and CH = cyclohexane.



Preparation of Oligomer-Modified Anionically Polymerized Polymers I:
The living APPs described in Table 2 were modified with the functional oligomers
01 to 05 described in Table 1, according to the teachings of this invention, to form
oligomer-modified anionically polymerized polymers (OMAPPs). Briefly, this
anionically polymerized polymer modification step can be described as follows: at the end
of the polymerization step a modification temperature (Tm) is set in the reaction zone.
Once the reaction mixture containing the living anionically polymerized polymer attains
Tm the oligomer is added to this reaction zone neat or in solution in a suitable solvent.
The desired amount of the functional oligomer may be computed from the Mn of the
living anionically polymerized polymer and the Fn of the functional oligomer. The
amount of functional oligomer and the mode and temperature at which it is added to the
reaction zone may be tailored to favor either end-capping or chain coupling of the living
anionically polymerized polymer onto the functional oligomer. In some embodiments, a
residence time less than 30 minues is required to carry out the end-capping or chain
coupling reaction between the living anionically polymerized polymer and the functional
oligomer.

As previously described, stoichiometric excesses of oligomer functionality over the
anion (or lithium) concentration, and rapid additions of the functional oligomer to the
reaction zone containing the living anionically polymerized polymer, or slow additions of
the latter to a second reaction zone at Tm containing the functional oligomer solution, all
favor the end-capping of the APP with the functional oligomer. Conversely,
stoichiometric deficits of the functional oligomer versus the anion concentration, and slow
additions of this oligomer to the reaction zone containing the living anionically
polymerized polymer favor the coupling of living APP chains onto the functional
oligomer. As the teachings of this invention show, in some instances, it is advantageous to
modify only a portion of the living APP chains with oligomer. To this end a suitable
partial termination agent (PTA) may be added to the living APP at the end of the
polymerization stage and prior to the introduction of the functional oligomer to the
reaction zone. The PTA can be added to the reaction zone neat or in a suitable solvent
solution.
The stoichiometry of the PTA can be calculated to deactivate a given percent,
always less than 100%, of living APP chains, thus allowing the functional oligomer
modification of the remainder of living APP chains to occur subsequently. With or
without partial termination, once this modification step is completed, an additional amount
of a termination agent (TA) may be added to ensure that all living chains have been
deactivated, thus allowing for the subsequent separation of the lithium from the oligomer-
modified APP product. The TA can be the same as the PTA or different, and can be also a
chemical compound that acts as an antioxidant or thermal stabilizer in the final OMAPP
application. Optionally, other formulation compounds and additives can be added at this
point. The oligomer-modified anionically polymerized polymer can be isolated from this
reaction mixture by means of known separation and drying stages downstream of the
reaction zone, as described previously.
The specific synthesis conditions used and OMAPP characterization parameters
are given in the Table 5 below. The abbreviations used below are defined as follows, PTA
= partial termination agent, TA= termination agent, CH = cyclohexane, OD = octadecanol,
BHT = butyl hydroxyl toluene, and UX = Ultranox-877A.



In Table 5 and the other tables presented herein, Mp is the molecular weight of the
highest peak in a gel permeation chromatogram of the oligomer-modified anionically
polymerized polymer.
Preparation of Oligomer-Modified Anionically Polymerized Polymers II:
The living APPs described in Tables 3a and 3b were modified with the functional
oligomers 06 through 09 described in Table 1, according to the teachings of this
invention, using the two reactor apparatus shown in FIG. 2 as follows: during the living
polymerization taking place in the first reaction zone, a solution of the functional oligomer
and distilled reaction solvent were prepared in the second reaction zone. The resulting

solution was cooled to 0°C with the aid of a chilling medium and blanketed with nitrogen.
When end-capping of the living anionically polymerized polymer with the functional
oligomer was sought, the contents of the first reaction zone were added over 2 to 4
minutes through the transfer line connecting the first and second reaction zones into the
oligomer solution contained in the second reaction zone. When chain coupling of the
living anionically polymerized polymer with the functional oligomer was sought, the
oligomer solution in the second reaction zone was added over 2 to 4 minutes through the
transfer line connecting the first and second reaction zones into the first reaction zone. In
either case the modification reaction was then allowed to proceed for the prescribed
residence time at the selected temperature. In these reactions no partial termination was
employed and all reactions were quenched with degassed methanol at the end of the
modification reaction. The resulting oligomer-modified anionically polymerized polymer
was then isolated in the given reactor or downstream through vacuum evaporation of the
solvent.
The specific synthesis conditions used and OMAPP characterization parameters
are given in the Tables 6a and 6b below. The abbreviations used below are defined as
follows, TA = termination agent, BZ = benzene, and MeOH = methanol.



Preparation of Oligomer-Modified Anionically Polymerized Polymers III:
The living APPs described in Table 4 were modified with the functional oligomers
011, 012, and 014 described in Table 1, according to the teachings of this invention, to
form OMAPP. The process employed in these experiments was the same as that used to
produce the OMAPPs reported in Table 5.
The specific synthesis conditions used and OMAPP characterization parameters
are given in the Table 7 below. The abbreviations used below are defined as follows: CH


Example 2 - Applications in Polymer Reinforced Asphalt for Road Paving
Dry, gel-free oligomer-modified anionically polymerized polymers, OMAPP-1 to
5 and 7 (Table 5), prepared as described in Example 1, were used as asphalt modifiers or
asphalt reinforcing agents in road paving formulations. To this end, AC-20 asphalt (PG-
64-22) was formulated by a hot-mix process. In this process a high-shear mixer
configured as rotor-stator (Euromix 33/300P) was employed. First 96.5 parts of AC-20
asphalt were heated without agitation to 120°C to soften the asphalt under a nitrogen

atmosphere. During this stage very slow agitation was employed to prevent asphalt
overheating and oxidation. Once the asphalt was soft, heating continued to 185°C +/- 5°C
and the mixer agitation was increased to 2000 RPM. As 185°C was reached, 3.5 parts of
the oligomer-modified anionically polymerized polymer were added to the asphalt at a rate
of 2 grams/minute. The agitation was maintained for 55 to 100 minutes for the effective
and total dispersion of the OMAPP acting as reinforcing agent. To ensure that the same
level of dispersion was achieved in all formulations, the OMAPP dispersion in asphalt was
monitored through fluorescence microscopy using an Olympus microscope with filters
around 350 to 480 nm.
The asphalt formulations thus obtained were characterized against the AC-20
unmodified asphalt control by RBSP according to ASTM D36. Penetration (PI) was
measured per ASTM D5 at 25°C, 10 seconds and 100 grams using a Humboldt model
H1200 Penetrometer. Maximum application temperature ("Max use T") was measured as
the temperature at which the Ruting Factor or Dynamic Shear Stiffness G*/sin8 takes the
value of 1.0 KPa, where G* is the complex modulus and 8 is the phase angle as measured
per AASHTO TP5. Morphology stability or phase segregation was measured as per
ASTM D5976 as the percent difference between the RBSP (measure as per ASTM D36) at
the top and bottom sections of a cylindrical probe, made in the interior of a sealed tube
containing the formulated asphalt, and aged at 163°C for 48 hours in vertical position
without agitation. The values obtained for the properties in the upper and lower sections
are used as follows to calculate the percent of phase separation:
1) % Separation A(RBSP)
A (RBSP) = highest RBSP value - lowest RBSP value
% separation RBSP = (A (RBSP) / highest RBSP value) * 100
Results are given in Table 8 below and show the enhanced performance of the
OMAPP reinforced asphalts.


Reviewing Table 8, we can see a marked difference between the values of the
properties measured for the neat AC-20 (PG 64-22) asphalt and for the control-modified
asphalt APP-1. Specifically, the asphalts modified with OMAPP-3 and 7 demonstrate a
noticeably higher softening temperature, lower penetration, and a lower percentage of
separation compared to the asphalt modified with the control.
Fluorescence microscopy images were obtained from reinforced asphalts with
APP-1 (control), and with OMAPP-1 to 5, and 7 using an Olympus optical microscope
with a fluorescence source and 380-480 filters to observe the morphology of both
polymer-rich phase and asphalt-rich phase. FIG. 3 shows the fluorescence micrograph of
the control system and FIG. 4 shows the fluorescence micrograph of the OMAPP-3
modified asphalt. The polymer-rich phase is observed as the brighter regions and asphalt
rich phase as the darker regions. Micrographs were taken at a magnification of 1000x. As
an illustrative example, a qualitative comparison of the fluorescent microscopy images for
APP-1 and OMAPP-3 revealed that the polymer particles in OMAPP-3 were smaller than
those in APP-1. This reduction in particle size is evidence of enhanced compatibility with
asphalt, in agreement with the findings of L. H. Lewandoski (1994), Rubber Chemistry
and Technology, Rubber Reviews, Vol. 67, No. 3, pp. 447-480.

Example 3 - Applications in Polymer Reinforced Asphalt for Roofing and Waterproof
Coatings
Dry, gel-free oligomer-modified anionically polymerized polymers, OMAPP-2, 3
and 5 (Table 5), prepared in Example 1, were used as asphalt modifiers or asphalt
reinforcing agents for Roofing and Waterproof Coatings applications. To this end, 89
parts of AC-20 asphalt (PG-64-22) were formulated with 11 parts of the oligomer-
modified anionically polymerized polymer, by a hot-mix process following the procedure
and testing methods described in Example 2. Results are given in Table 9 below and show
the enhanced performance of the OMAPP reinforced asphalts against unmodified controls.

Reviewing Table 9, we can see some marked differences between the values of the
properties measured for the APP-1 - modified asphalt (control) and the OMAPP-2 -
modified asphalt. Specifically, the asphalts modified with OMAPP-2 and 3 demonstrate a
noticeably lower penetration at 25°C and lower percentage of separation.
Fluorescence microscopy images were obtained as in Example 2. A qualitative
comparison of the fluorescent microscopy images for APP-1 (see FIG. 5) and OMAPP-3
(see FIG. 6) revealed that the asphalt particles in OMAPP-3 were more defined and
smaller than those in APP-1. This reduction in particle size is also evidence of enhanced
compatibility with asphalt.
Example 4 - Applications in Pressure Sensitive Adhesives. Hot Melt Adhesives and Hot-
Melt Pressure Sensitive Adhesives

Dry, gel-free oligomer-modified anionically polymerized polymers, OMAPP-6, 7
and 8 (Table 5), prepared in Example 1, were used in pressure sensitive adhesive (PSA)
and hot-melt adhesive (HMA) formulations. The adhesive formulation were prepared by
mixing at 180°C in a propeller mixer operating at 300 RPM, 18 to 25 % by weight of a
naphtenic plasticizer such as SHELLFLEX 371, with 45 to 60 % by weight of a
combination of tackifiers such as Permalyn 3100 (rosin ester of pentaerithritol,
RBSP=100°), Sylvatac RE100 (Rosin ester, RBSP= 100°C), Eastotac H130 (C5
hydrogenated hydrocarbon resin, RBSP= 130°C), Sylvares TR1115 (polyterpene resin,
RBSP= 115°C), Sylvares ZT105LT (terpene/styrenic resin, RBSP=105°C) and Sylvares
TP2040 (terpene/phenolic resin, RBSP=118°C). The blend was maintained until a good
dispersion of the components was achieved. Then 0.5 to 2.0 % by weight of an
antioxidant such as Irganox-1076 or Ultranox 877 was added to the mix, followed by 20 to
25 % by weight of the oligomer-modified anionically polymerized polymer. The mix was
left to achieve homogeneity and then the resulting adhesive was cooled to room
temperature.
The performance of the adhesive formulations was evaluated through shear,
tensile, and Brookfield viscosity tests. Shear tests were conducted according to ASTM
D3654 at 23 °C using stainless steel probes as substrates and a weight of 500 g. The result
was measured as the shear resistance that is proportional to take the adhesive off from the
substrate and is expressed as time to fail in days. Tensile tests were measured as per a
modified ASTM D3759. In this method, 10 cm long and 1 cm2 cross-section probes of
the adhesive formulations were employed. The probes were subjected to a tensile test in
an universal mechanical tester Zwick model 1445 at a constant strain rate of 508
mm/minute until the probe was broken, and the results report the tensile strength
(resistance to break) of the adhesive formulation. Brookfield viscosities of the adhesive
formulations were measured at 150°C according to ASTM D1084. Adhesive formulations
and evaluation results are shown below in Table 10 against an unmodified control.



Example 5 - Preparation of Rheology Enhanced Plastic Compositions
Oligomer-modified anionically polymerized polystyrene bearing multi-arm
structures were prepared in Example 1 (Table 6). From these, OMAPP-12 through 15
were chosen for rheology evaluation (Mw ranging from 50,000 to 95,000). The melt
rheology of OMAPP-12 through 15 was measured and compared to two linear PS controls
bearing similar molecular weights (Mw). The melt rheology of these materials were
measured using a parallel plate viscometer (Rheoletric Scientific SR5000) under a shear
rate sweep between 125 and 200°C. Comparative results, consisting of viscosity at 1/sec
and 100/sec shear rates and rheological ratio defined as the ratio of the viscosity at 1/100
sec to 1/sec, are shown below in Table 11.


Example 6 - Applications in Flow Modifcation or Rheology Control of Plastics and
Engineering Thermoplastics
Given their outstanding rheological characteristics, oligomer-modified anionically
polymerized polymers bearing a multi-arm structures OMAPP-9,10, and 11 prepared in
Example 1 (Table 6) were evaluated as flow modifiers, process aids, or rheology control
agents for plastics and engineering thermoplastics. To this end, 4 parts of the oligomer-
modified anionically polymerized polymers were melt blended with 96 parts polyamide-6
(Ultramid B3, BASF), polybutylene terephthalate (Valox 325, GEP), and Polycarbonate
(Lexan 131, GEP) at a prescribed temperature and residence time, in a 64 cc Brabender
mixing bowl operating at 50 RPM. The compounds thus obtained were grinded into small
pellets, and their Melt Flow Indices (MFI) characterized in a Plastometer (Tinius
Olsen PPDT-600) according to ASTM D 1238, and their Tg was established through DSC
(TA Insturments 2910 and 2020) as per ASTM D 3417 and D3418 to assess effects on
thermal properties of the compounds. The Polycarbonate compounds were additionally
characterized with a Waters 510 GPC, using a differential refractometer detector, THF
mobile phase, and a flow rate of 1.0 ml / min, maintained at 40°C to verify the stability of
the modified thermoplastics during compounding with the OMAPP. The results showing

the outstanding changes in MFI of the engineering thermoplastic compounds compared to
the unmodified controls with similar thermal history are shown below in Table 12.

Example 7 - Applications in Surface Energy Modification and Surface Adhesion
Enhancement of Thermoplastics
Oligomer-modified anionically polymerized polymers bearing substantial amounts
of (meth)acrylate containing functional oligomers have shown enhanced surface energy
and improved adhesion to polar substrates. Dried OMAPP-16,17, and 18, were
characterized in their surface energy using a FibroDat contact angle instrument. Their
adhesion characteristics were evaluated over aluminum against a commercial PS controls.
Comparative results, are shown below in Table 13.


Example 8 - Applications in Impact Modification of Plastics and Engineering
Thermoplastics
Oligomer-modified anionically polymerized polymers OMAPP-19, 20, and 21
were prepared as described in Example 1 (Table 7). These oligomer-modified anionically
polymerized polymers were selected for impact modification of several plastics and
engineering thermoplastics due to the small solubility parameter difference between the
functional oligomer employed in their preparation (Table 1) and these plastics.
Impact modified plastics formulations consisting of 90 to 95 parts of a plastic
chosen from the families of polyamides (PA), particularly PA-6, PA-6,6, PA-12,
polyesters (PEs), particularly PET and PBT, polycarbonates (PC), PS, PS copolymers,
SAN, ABS, PC/ABS, HIPS, PPE, PPE/PS, PPE/PA, PA/ABS, PC/ABS, PEI, PEK, PEEK,
PSu, POM, TPU, and the like, were dry-blended, co-fed or separate fed with 5 to 10 parts
of OMAPP. These formulations were compounded in a 25 mm Werner & Pfleiderer co-
rotating twin screw extruder (L/D = 24) or a CW Brabender 15 mm co-rotating conical
twin screw extruder, operating under a prescribed RPM, temperature profile, and residence
time. The resulting impact modified plastic compounds were injection molded into
standard ASTM probes in a Battenfeld 39 ultraplus injection molding machine with 40 ton
of nominal clamping pressure, injection conditions were set in agreement with the
recommendations for the plastics employed. The compounded pellets were characterized
by MFI, and the injection molded probes were characterized by Tensile Mechanical
Testing, HDT, and Notched Izod Impact techniques according to ASTM D1238, D638 &
D256, respectively. Results are given in Table 14 below and show the enhanced impact
performance of the OMAPP over the unmodified plastic and engineering thermoplastic
and against other suitable impact modifier controls.



Example 9 - Enhancement of Thermoplastic Elastomer Properties for Soft Touch and
Injection Molding Applications
Oligomer-modified anionically polymerized polymers OMAPP-19 & 21, were
prepared as described in Example 1 (Table 7). These oligomer-modified anionically
polymerized polymers were selected to demonstrate the enhanced thermoplastic elastomer
(TPE) properties of OMAPP over their unmodified APP counterparts. Soft touch and
injection molding TPE formulations consisting of 70 to 100 parts of OMAPP and 0 to 30
parts of naphthenic, parafinic, or aliphatic oil additives and 0 to 2 parts heat stabilizers
were made. These formulations were compression molded into ASTM probes as
described in Example 8. The resulting TPE compositions were characterized by Shore A
Hardness and Tensile Mechanical Testing according to ASTM D2240 and D412,
respectively. Results are given in Table 15.

Example 10 - Polymer Blends for Use as Asphalt Compatibilizers
Production of a First Polymer Blend (PB1):
An 80-liter stainless steel reactor was loaded with 50.4 kg of cyclohexane and a
total of 8 kg of: i) styrene monomer and ii) butadiene monomer, at a weight ratio of 0.33
(styrene to butadiene). Both the solvent (cyclohexane) and the monomers were purified in
advance to reduce humidity content. An anionic polymerization reaction was initiated at

50°C by adding 0.12 moles of 0.3 M n-butyllithium, plus a slight excess to eliminate
poisons in the reactor system. After the reaction temperature peaked, anionic
polymerization residence time was 20 minutes, producing a styrene-butadiene anionically
polymerized polymer with living chains. Immediately following this, a partial termination
reaction was performed, adding 0.0705 kg of a butyl hydroxy toluene (BHT) solution at a
concentration of 30% by weight in cyclohexane. The partial termination continued until
the temperature was adiabatically reduced to 100°C. Subsequently, an oligomer coupling
reaction was performed, adding 0.324 kg of an oligomer containing styrene, 2-ethyl-hexyl
acrylate, and glycidyl methacrylate dissolved in cyclohexane at a concentration of 10% by
weight. The residence time for this reaction was 3 minutes. A specified number of the
living styrene-butadiene anionically polymerized chains remaining after the partial
termination stage were thus coupled to each molecule of the oligomer added. Finally, the
entire reaction mixture was terminated by adding 0.03 kg of a butyl hydroxy toluene
solution at a concentration of 30% by weight. This terminated any living linear styrene-
butadiene anionically polymerized polymer chains and any living oligomer-modified
anionically polymerized polymers, producing a composition of linear anionically
polymerized polymers and radial oligomer-modified anionically polymerized polymers.
The resulting polymer blend was coagulated and dried and characterized by gel
permeation chromatography (GPC). The highest peak in the chromatogram, corresponded
to the linear anionically polymerized polymer, had an average molecular weight
(designated "Mp") of 109,122 g/mol and a polydispersity of 1.1. Quantitative analysis of
this chromatogram revealed that the composition also contains a broad distribution of
radial oligomer-modified anionically polymerized polymers.
Based on the broad distribution seen in the chromatogram, it was determined that
the radial structures contain a family of molecules having a variable number of polymer
chains coupled to the oligomer, typically forming radial structures containing from 3 to 18
branches, with an oligomer core.
Three additional polymer blends (PB2 - PB4) were produced using the same
procedure described above. For each composition, the level of partial termination and/or
the quantity of polar random oligomer added was varied.


Preparation of Control:
A styrene-butadiene anionically polymerized polymer was synthesized in parallel
according to the procedure described above, but without partial termination, partial
coupling, or oligomer modification (Control). The resulting anionically polymerized
polymer contained a styrene to butadiene weight ratio of 0.33. This anionically
polymerized polymer is commonly used in the prior art as an asphalt modifier.
Table 16 shows the average molecular weight of the linear anionically polymerized
polymer in each blend, the extent of partial termination and oligomer modification in each
blend, the degree of branching for the oligomer-modified anionically polymerized
polymers in each blend and the weight percent of oligomer-modified anionically
polymerized polymer in each blend.

Modification of Asphalt with Polymer Blends:
Each polymer blend (PB1-PB4) and the control was mixed with an asphalt
produced at the AC-20 refinery in Salamanca, Mexico. The properties of this asphalt are
shown in Table 17:

More specifically, for each polymer blend (i.e., compatibilizer) and the control,
three modified asphalts were obtained, containing concentrations of 3.5%, 7%, and 11% of
compatibilizer by weight. The procedure for producing compatibilizer/asphalt mixtures
began with addition of polymer blends to the asphalt at 185°C, ± 5°C, using a heavy-duty

shearing mixer at high agitation speed. Mixing time depends on polymer type; however,
for purposes of comparison, it was set at 100 minutes.
The compatibility of the modified asphalts (MAI - MA15) was evaluated using
the tube phase separation test, as specified in ASTM Standard D5976. In this test, the hot
compatibilizer/asphalt mix is placed in a metal tube 2 cm in diameter and 12 cm in height,
then stored in a 160°C oven for 48 hours, followed by sudden cooling. The tube is cut into
three equal sections, and the physical properties (softening point and penetration) and flow
properties (modules or loss angle) of the upper and lower sections are examined.
The values obtained for the properties in the upper and lower sections are used as
follows to calculate separation:
1) % Separation ∆(RBSP)
∆ (RBSP) = highest RBSP value - lowest RBSP value
% separation RBSP = (∆ (RBSP) / highest RBSP value) * 100
The difference in loss angle (∆δ) between the upper and lower parts of the tube
measures the heterogeneity or uniformity of the modified asphalt system. This
measurement is expressed as the difference in loss angle 8 in degrees, measured at 25°C
and 10 rad/s. The smaller the difference in phase angle, the more homogeneous the
compatibilizer/asphalt mixture.
The properties measured for each of the 15 modified asphalts (MAI-MAI 5)
produced are shown in Table 18a and 18b.



Fluorescence microscopy images were obtained of modified asphalts MA1, MA4,
MA7, MA10, and MA13, 6, 9,12,15, and 18, using an Olympus optical microscope with
a fluorescent source and a 380-480 nm filter to observe the morphology of the
asphalt/compatibilizer compositions. Micrographs were taken at a magnification of 100X.
Reviewing Tables 18a and 18b, we can see a marked difference between the values
of the properties measured for the MA10 asphalt and for the control-modified asphalt,
MA13. Specifically, the asphalt modified with MA10 demonstrates a noticeably higher
softening temperature, lower penetration, and a lower percentage of separation compared
to the asphalt modified with the control.
A comparison of the fluorescent microscopy images for MA10 and MA13 revealed
that the polymer particles in MA10 were smaller than those in MA13, where the phase
morphology shows particles with an average diameter of up to 45 µm. In MA10, the
particles are no larger than 20 µm. This reduction in particle size is evidence of greater
compatibility with the asphalt, in agreement with the findings of L. H. Lewandoski (1994),
Rubber Chemistry and Technology, Rubber Reviews, Vol. 67, No. 3, pp. 447-480.
This evidence of greater compatibility in the modified asphalts containing the
polymer blends of the present invention was confirmed by examination of the fluorescent
microscopy of MA1, MA4 and MA7, which showed smaller polymer-rich particles
dispersed in the asphalt, as well as a reduction in the percentage of separation in asphalts
modified with these polymer blends. This behavior is also observed at higher
concentrations of polymer in asphalt. For example, when 11% was used in the production

of MA2, an improvement in the temperature of softening and penetration was seen, as well
as improved compatibility (Table 18a).
As will be understood by one skilled in the art, for any and all purposes,
particularly in terms of providing a written description, all ranges disclosed herein also
encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any
listed range can be easily recognized as sufficiently describing and enabling the same
range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As
a non-limiting example, each range discussed herein can be readily broken down into a
lower third, middle third, and upper third, etc. As will also be understood by one skilled in
the art, all language such as "up to," "at least," "greater than," "less than," and the like,
include the number recited and refer to ranges which can be subsequently broken down
into sub-ranges as discussed above.
It should be understood that the invention is not confined to the particular
formulations illustrated and described, but embraces all such modified forms thereof as
come within the scope of the following claims.

WE CLAIM:
1. An oligomer-modified anionically polymerized polymer comprising the reaction product
of:
(a) a free radically polymerized oligomer consisting of the reaction product of at least
one monomer selected from the group consisting of vinyl aromatic monomers and ester
functional monomers and at least one monomer selected from the group consisting of epoxy
functional monomers, anhydride functional monomers, ester functional monomers and
carboxylic acid functional monomers the oligomer having a number average molecular weight of
1,000 to 5,000 g/mol, a weight average molecular weight of 1,500 to 20,000 g/mol and a number
average number of functional groups of from 1 to 10; and
(b) an anionically polymerized polymer ;
wherein the number average number of functional groups is calculated based upon functional
groups selected from the group consisting of epoxy functional groups, anhydride functional
groups and carboxylic acid functional groups.
2. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
oligomer has a solubility parameter from 13 to 30.
3. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer comprises a polymer selected from the group consisting of
polystyrene, polybutadiene, polyisoprene, and random, block or tapered copolymers made from
monomers selected from the group consisting of styrene, butadiene and isoprene.
4. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer has a number average molecular weight of 3000 to 300,000
g/mol.
5. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer has a number average molecular weight of 20,000 to 300,000
g/mol.
6. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer is polymerized from at least one vinyl aromatic monomer and

at least one conjugated diene molecule.
7. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer is polymerized from vinyl aromatic monomers and conjugated
diene monomers in a molar ratio of vinyl aromatic monomer to conjugated diene monomer of 0.1
to 1.0.
8. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
anionically polymerized polymer is polymerized from conjugated diene monomers and has a
contents of 1,2-structures from 8 to 70 mole %.
9. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
oligomer-modifed anionically polymerized polymer has a percentage of coupled chains from 2 to
90 mole %.
10. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
oligomer-modified anionically polymerized polymer has a number average molecular weight
from 5,000 to 1,000,000 g/mol.
11. The oligomer-modified anionically polymerized polymer of claim 1, wherein the
oligomer is polymerized from vinyl aromatic and epoxy functional monomers.
12. The oligomer-modified anionically polymerized polymer of claim 1, wherein the reaction
product comprises 0.1 to 40 wt% oligomer based on the total amounbt of reacted oligomer and
anionically polymerized polymer.
13. The oligomer-modified anionically polymerized polymer of claim 12, wherein the
anionically polymerized polymer is a thermoplastic having a number average molecular weight
of 3,000 to 50,000 g/mol.
14. The oligomer-modified anionically polymerized polymer of claim 13, wherein the
oligomer is polymerized from 1 to 60 mole % epoxy-functional or carboxylic acid-functional
monomers.

15. The oligomer-modified anionically polymerized polymer of claim 1, wherein the reaction
product comprises 0.1 to 5 wt.% oligomer based on the total amount of reacted oligomer and
anionically polymerized polymer.
16. The oligomer-modified anionically polymerized polymer of claim 15, wherein the
anionically polymerized polymer is a thermoplastic polymer having a number average molecular
weight of 20,000 to 100,000 g/mol.
17. The oligomer-modified anionically polymerized polymer of claim 16, wherein the
anionically polymerized polymer comprises a polymer selected from the group consisting of
polystyrene, polybutadiene, polyisoprene, and random, block or tapered copolymers made from
monomers selected from the group consisting of styrene, butadiene, and isoprene.
18. The oligomer-modified anionically polymerized polymer of claim 15, wherein the
oligomer is polymerized from 0.5 to 60 mole % epoxy-functional or carboxylic acid-functional
monomers.
19. The oligomer-modified anionically polymerized polymer of claim 12, wherein the
anionically polymerized polymer is a thermoplastic having a number average molecular weight
of 5,000 to 40,000 g/mol.
20. A method for preparing an oligomer-modified anionically polymerized polymer, the
method comprising reacting an anionically polymerized polymer with a free radically
polymerized oligomer consisting of the reaction product of at least one monomer selected from
the group consisting of vinyl aromatic monomers and ester functional monomers, and at least
one monomer selected from the group consisting of epoxy functional monomers, anhydride
functional monomers, ester functional monomers, and carboxylic acid functional monomers, the
oligomer having a number average molecular weight of 1,000 to 5,000 g/mol and a weight
average molecular weight of 1,500 to 20,000 g/mol, and a number average number of functional
groups from 1 to 10, and wherein the number average number of functional groups is calculated
based upon functional groups selected from the group consisting of epoxy functional groups
anhydride functional groups and carboxylic acid functional groups.

21. The method of claim 20, wherein the oligomer is polymerized in a reactor using a
continuous polymerization process at a polymerization temperature of from 180 C to 350 C with
a residence time in the reactor of less than 60 minutes.
22. The method of claim 20, wherein the oligomer is reacted with the anionically
polymerized polymer in the same reaction zone where the anionically polymerizable polymer is
polymerized.
23. The method of claim 20, wherein the anionically polymerized polymer is polymerized in
a first reaction zone and reacted with the oligomer in a second reaction zone.
24. The method of claim 20, comprising polymerizing the anionically polymerized polymer,
adding a sufficient amount of terminating agent to deactivate a portion of the living chains in the
anionically polymerized polymer and reacting at least some of the remaining living chains with
the oligomer.
25. The method of claim 20, wherein the molar ratio of oligomer to anionically polymerized
polymer in the reaction is between 0.02 and 1.
26. The method of claim 20, wherein reacting the anionically polymerized polymer with the
oligomer comprises coupling anionically polymerized polymer with the oligomer and further
wherein the average number of anionically polymerized polymer chains reacted with an oligomer
is 2 to 30.
27. The method of claim 26, wherein 2 to 90 mole % of the anionically polymerized polymer
undergoes coupling reactions.
28. The method of claim 20, wherein reacting the anionically polymerized polymer with the
oligomer comprises end-capping anionically polymerized polymer with oligomer and further
wherein at least 10 mole % of the anionically polymerized polymer undergoes end-capping
reactions.
29. A polymer composition comprising :
(a) the oligomer-modified anionically polymerized polymer of claim 1; and
(b) a linear anionically polymerized polymer.

30. The polymer composition of claim 29, wheein the linear anionically polymerized
polymer comprises a portion of the anionically polymerized polymer that has been deactivated
by a terminating agent.
31. The polymer composition of claim 30. wherein the linear anionically polymerized
polymer makes up 10 to 90 mole % of the polymer composition.
32. A reinforced material comprising the oligomer-modified anionically polymerized
polymer of claim 1 mixed with a material to be reinforced.
33. The reinforced material of claim 32, wherein the material to be reinforced is selected
from the group consisting of asphalt, plastics and rubbers
34. An article made from the reinforced material of claim 32.
35. The article of claim 34 wherein the article is an extruded article, an injection molded
article, a compression molded article or a tire.
36. A modified asphalt comprising asphalt mixed with the oligomer-modified anionically
polymerized polymer of claim 1.
37. The modified asphalt of claim 36 comprising 1 to 15 wt% of the oligomer-modified
anionically polymerized polymer based on the total weight of the asphalt and the oligomer-
modified anionically polymerized polymer.
38. The modified asphalt of claim 36 comprising 5 to 20 wt% of the oligomer-modified
anionically polymerized polymer based on the total weight of the asphalt and the oligomer-
modified anionically polymerized polymer.
39. A modified asphalt comprising asphalt mixed with the polymer composition of claim 29.
40. The modified asphalt of claim 39 comprising 1 to 20 wt% of the polymer composition
based on the total weight of the asphalt and the polymer composition.
41. An adhesive composition comprising the oligomer-modified anionically polymerized
polymer of claim 1, wherein the reaction product comprises 0.05 to 5 wt% oligomer based on the
total amount of reacted oligomer and anionically polymerized polymer.

42. The adhesive composition of claim 41, wherein the oligomer is polymerized from 0.5 to
30 mole % epoxy functional monomer.
43. The adhesive composition of claim 41, wherein the oligomer is polymerized from 10 to
75 mole % vinyl aromatic monomer.
44. The adhesive composition of claim 41 further comprising at least one additive selected
from the group consisting of tackifiers, stabilizers, plasticizers and antioxidants.
45. The adhesive composition of claim 41 comprising 15 to 30 wt% oligomer-modified
anionically polymerized polymer, 45 to 60 wt % tackifier. 15 to 30 wt% plasticizer and 0.05 to 2
wt % antioxidant.
46. A modified plastic comprising a plastic mixed with the oligomer-modified anionically
polymerized polymer of claim 1, the mixture comprising 1 to 15 wt% oligomer-modified
anionically polymerized polymer based on the total weight of the oligomer-modified anionically
polymerized polymer and the plastic.
47. The modified plastic of claim 46, whererin the plastic comprises a polymer selected from
the group consisting of polystyrene, polybutadiene, polyisoprene, and random, block or tapered
copolymers made from monomers selected from the group consisting of styrene, butadiene and
isoprene and having a number average molecular weight of 3,000 to 300,000 g/mol.
48. The modified plastic of claim 46 wherein the reaction product comprises 0.1 to 33 wt%
oligomer based on the total amount of reactor oligomer and anionically polymerized polymer.
49. The modified plastic of claim 48 wherein the oligomer comprises 0.5 to 50 mole%
epoxy-functional, anhydride-functional or carboxylic acid-functional monomer.
50. The modified plastic of claim 46, wherein the anionically polymerized polymer
comprises a polystyrene.
51. The modified plastic of claim 46, wherein the mixture comprises 1 to 10 wt% oligomer-
modified anionically polymerized polymer based on the total weight of the oligomer-modified
anionically polymerized polymer and the plastic.

52. The modified plastic of claim 48, wherein the reaction product comprises 10 to 30 wt%
oligomer based on the total amount of reacted oligomer and anionically polymerized polymer.
53. The modified plastic of claim 52, wherein the anionically polymerized polymer
comprises a polystyrene.
54. The modified plastic of claim 46, wherein the plastic is selected from the group
consisting of polyamides, polyurethanes, polyethers, polysulfones, polyether-ketones,
polyetherether ketones, polyimides, polyethermides, polycarbonates, polyesters, polystryrene and
copolymers thereof.
55. The modified plastic, comprising a plastic mixed with the oligomer-modified anionically
polymerized polymer of claim 19, wherein the modified plastic comprises 1 to 10 wt% of
oligomer-modifed anionically polymerized plastic based on the total weight of the plastic and the
oligomer-modified anionically polymerized polymer.
56. The oligomer-modified anionically polymerized polymer of claim 1, said free-radically
polymerized oligomer having a solubility parameter from 13 to 30; and is polymerized from 0.5
to 60 mole% epoxy-functional or carboxylic acid-functional monomers in a reactor using a
continuous polymerization process at a polymerization temperature of from 180°C to 350°C with
a residence time in the reactor of less than 60 minutes; and said anionically polymerized polymer
being polymerized from vinyl aromatic monomers and conjugated diene monomers in a molar
ratio of vinyl aromatic monomer to conjugated diene monomer of 0.1 to 1.0; wherein the
anionically polymerized polymer is a thermoplastic having a number average molecular weight
of 3,000 to 300,000 g/mol.
57. A reinforced material comprising a compound that is one of asphalt, plastics and rubbers
and the oligomer-modified anionically polymerized polymer of claim 1, wherein said free
radically polymerized oligomer is made in a reactor using a continuous polymerization process at
a polymerization temperature of from 180°C to 350°C with a residence time in the reactor of less
than 60 minutes.

58. An article comprising the reinforced material of claim 57.
59. The article of claim 58, wherein the article is an extruded article, an injection molded
article, a compression molded article or a tire.

60. A modified asphalt comprising asphalt and oligomer-modified anionically polymerized
polymer of claim 1, wherein said free-radically polymerized oligomer is made in a reactor using
a continuous polymerization process at a polymerization temperature of from 180°C to 350°C
with a residence time in the reactor of less than 60 minutes.
61. The modified asphalt of claim 59 comprising 1 to 20 wt% of the oligomer-modified
anionically polymerized polymer based on the total weight of the asphalt and the oligomer-
modified anionically polymerized polymer.

62. A composition comprising an adhesive composition including the oligomer-modified
aniononically polymerized polymer of claim 1, wherein said free-radically polymerized oligomer
is made in a reactor using a continuous polymerization process at a polymerization temperature
of from 180 C to 350 C with a residence time in the reactor of less than 60 minutes; and wherein
said reaction product comprises 0.05 to 5 wt% oligomer based on the total amount of reacted
oligomer and anionically polymerized polymer and wherein said composition further comprises
at least one additive selected from the group consisting of tackifiers, stabilizers, plasticizers and
antioxidants.
63. The adhesive composition of claim 61, wherein the oligomer is polymerized from 0.5 to 30
mole % epoxy functional monomer.

64. The adhesive composition of claim 61, wherein the oligomer is polymerized from 10 to
75 mole % vinyl aromatic monomer.
65. A modified plastic comprising a plastic mixed with the oligomer-modified anionically
polymerized polymer of claim 1, wherein said free-radically polymerized oligomer is made in a
reactor using a continuous polymerization process at a polymerization temperature of from
180°C to 350°C with a residence time in the reactor of less than 60 minutes; and wherein the
mixture comprises 1 to 15 wt% oligomer-modified anionically polymerized polymer based on
the total weight of the oligomer-modified anionically polymerized polymer and the plastic.
66. The modified plastic of claim 65 wherein the reaction product comprises 0.1 to 33 wt%
oligomer based on the total amount of reactor oligomer and anionically polymerized polymer.
67. The modified plastic of claim 65, wherein the oligomer comprises from 0.5 to 50 mole %
epoxy-functional, anhydride-functional or carboxylic acid-functional monomer.

68. The modified plastic of claim 65, wherein the anionically polymerized polymer
comprises a polystyrene.
69. The modified plastic of claim 65, wherein the plastic is selected from the group
consisting of polyamides, polyurethanes, polyethers, polysulfones, polyether-ketones, polyether
ether ketones, polyimides, polyetherimides, polycarbonates, polyesters, polystyrene and
copolymers thereof.


Oligomer-modified anionically polymerized polymers, reinforced materials made
with the polymers and articles made from the reinforced materials are provided. The
oligomer-modified polymers are made by reacting anionically polymerized polymers
with low molecular weight acrylic oligomers. The oligomer-modified polymers may
be used as adhesives, compatibilizers, reinforcing agents and impact modifiers.

Documents:

00390-kolnp-2006-abstract.pdf

00390-kolnp-2006-assignment.pdf

00390-kolnp-2006-claims.pdf

00390-kolnp-2006-description complete.pdf

00390-kolnp-2006-drawings.pdf

00390-kolnp-2006-form-1.pdf

00390-kolnp-2006-form-3.pdf

00390-kolnp-2006-form-5.pdf

00390-kolnp-2006-international publication.pdf

00390-kolnp-2006-international search authority.pdf

00390-kolnp-2006-others.pdf

00390-kolnp-2006-pct forms.pdf

390-kolnp-2006-assignment.pdf

390-KOLNP-2006-CORRESPONDENCE 1.2.pdf

390-KOLNP-2006-CORRESPONDENCE-1.1.pdf

390-KOLNP-2006-CORRESPONDENCE-1.3.pdf

390-KOLNP-2006-CORRESPONDENCE-1.4.pdf

390-kolnp-2006-correspondence-1.5.pdf

390-KOLNP-2006-CRROSPONDENCE.pdf

390-kolnp-2006-examination report.pdf

390-kolnp-2006-form 1.pdf

390-kolnp-2006-form 18.pdf

390-kolnp-2006-form 3-1.1.pdf

390-KOLNP-2006-FORM 3.pdf

390-kolnp-2006-form 5-1.1.pdf

390-KOLNP-2006-FORM 5.pdf

390-kolnp-2006-form 6.pdf

390-kolnp-2006-granted-abstract.pdf

390-kolnp-2006-granted-claims.pdf

390-kolnp-2006-granted-description (complete).pdf

390-kolnp-2006-granted-drawings.pdf

390-kolnp-2006-granted-form 1.pdf

390-kolnp-2006-granted-form 2.pdf

390-kolnp-2006-granted-specification.pdf

390-kolnp-2006-pa.pdf

390-kolnp-2006-reply to examination report.pdf

abstract-00390-kolnp-2006.jpg


Patent Number 247502
Indian Patent Application Number 390/KOLNP/2006
PG Journal Number 15/2011
Publication Date 15-Apr-2011
Grant Date 12-Apr-2011
Date of Filing 21-Feb-2006
Name of Patentee BASF CORPORATION
Applicant Address 1609 BIDDLE AVENUE, WYANDOTTE, MICHIGAN 48192, U.S.A.
Inventors:
# Inventor's Name Inventor's Address
1 VILLALOBOS, MARCO, A 2836 HAVEN LANE, LINDENHURST, IL 60046, U.S.A.
2 DEETER, GARY, A 1006 HIALEAH DRIVE, RACINE, WI 53402, U.S.A.
3 MOCTEZUMA ESPIRICUETO, SERGIO, ALBERTO ALAMO 143, COL. LA FLORIDA, TAMAULIPAS, ALTAMIRA, 89600, MEXICO
4 REVILLA VAZQUEZ, JAVIER 2 O RETORNO DE ZEMPOALA NO. 8, COL. JARDINES DEL ALBA, ESTADO DE MEXICO, CUAUTITLAN IZCALLI, 54750 MEXICO
5 ROJAS GARCIA, JOSE, MANUEL AV. REVOLUCION 1171 INT.2, COL. MERCED GOMEZ, DELEGACION BENITO JUAREZ, MEXICO, D.F. 03910, MEXICO
6 GUTIERREZ CRUZ, GERARDO 2A PRIVADA TIERRA Y LIVERTAD NO.36B, COL. ED-HACIENDA SAN JORGE, EDTADO DE MEXICO, TOLUCA, 50100 MEXICO
PCT International Classification Number C08G 81/00
PCT International Application Number PCT/US2004/024350
PCT International Filing date 2004-07-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/481,164 2003-07-31 U.S.A.
2 10/710,654 2004-07-27 U.S.A.