Title of Invention

"PROPYLENE POLYMERS INCORPORATING POLYMETHYLENE MACROMERES"

Abstract A polyolefin product is provided Which compris  a branched olefin Copolymer having an isotactic polypropylene backbone, polyethyiere branches and, optionally, one or more comonomers. The total comonomer contenl of the branched olefin copolymer is from 0 to 20 mols percent. Also, the mass ratio of the isotactic polypropylene to the polyethylene ranges from 99.1 to 50:50, Additionally, a process is provided for preparing a branched olefin copolymer which comprises: a)  copolyrnerizing ethylene, optionally with one or more ccpolymerizable monomers, in a polymer ization reaction under conditions sufficient to form copolymer having greater than 40% chain end-group unsaturavion; bl  copnlymerizing the product of a) with propylene and, optiorially, one or more copolyrnerizable monomers, in a polymerization reactor under suitable polypropylene polymerization conditions using a shiral, stereorigid transition metal catalyst capable of producing isotactic polypropylene; and c)  recover ng a branched olefin copolymer
Full Text The present invention relates to a process for preparing a branched olefin copolymer.
FIELD OF THE INVENTION
The present invention relates to propylene polymers incorporating macromers and a method for the preparation of branched polypropylene utilizing chiral, stereorigid tranition metal catalyst compounds.
BACKGROUND OF THE INVENTION
Polypropylene and related polymers are known to have low melt strength. This is a significant deficiency in key application areas such as thermoforming, blow molding, and fiber spinning. Polyethylene on the other hand is used extensively in blown film applications requiring good melt strength. The limitations in the melt strength of polypropylenes show up as excess sag in sheet extrusion, rapid thinning of walls in parts thermoformed in the melt phase, low draw-down ratios in extrusion coating, poor bubble formation in extrusion foam materials, and relative weakness in large-part blow molding. Thus, it would be highly desirable to produce polypropylene and related polymers having enhanced melt strength as well as commercially valuable processability.
Increasing the melt strength of polymers such as polypropylene has been an industrial goal of well over ten years, however, success has been limited. The desirable properties that have made low density polyethylene commercially successful are attributed in large part to high melt strength and excellent processability. Both of these properties are attributed to the presence of long chain branching which is thought to occur under high pressure polymerization conditions.
There has been some success in increasing the melt strength of polypropylene. For example, EP 190 889 A2 discloses high energy irradiation of
polypropylene to create what is believed to be polypropylene having substantial free-end long branches of propylene units. EP 384 431 discloses the use of peroxide decomposition of polypropylene in the substantial absence of oxygen to obtain a similar product.
Other attempts to improve the melt properties of polypropylene include US Patent 5, 541,236, which introduces long chain branching by bridging two PP backbones to form H-type polymers, and US Patent 5,514,761, which uses dienes incorporated in the backbones to achieve a similar effect. However, it is difficult to avoid cross-linking and gel formation in such processes.
Thus, there is still a need for propylene polymers having improved melt strength and good processability.
SUMMARY OF THE INVENTION

Accordingly, there is provided a process for preparing a branched olefin copolymer Characterzed in that it comprisses the step of
a) copolymerizing ethylene, optionally with one or more copolymerizable monomers selected from the group consisting of C3-C20 α olefins, germinally disubstitured monomers, C5-C25 cyclic olefins,C5-C25 styrenic olefins, lower carbon number C3-C8 alkyl substituted analogs of the cyclic and styrenic olefins, dienes, acetylene, and aldehyde monomers, in a polymerization reaction at a temperature between -60°C to 280°C under conditions sufficient to form copolymer having greater than 40% chain end-group unsaturation;
b) copolymerizing the product of a) with propylene and, optionally, one or more copolymerizable monomers selected from the group consisting of C3-C20 a olefins, germinally disubstitured monomers, C5-C25 cyclic olefins, C5-C25 styrenic olefins, lower carbon number C3-C8 alkyl substituted analogs of the cyclic and styrenic olefins, in a polymerization reactor at a temperature between -60°C to 280°C under suitable polypropylene polymerization conditions using a chiral, stereorigid transition metal metallocene catalyst capable of producing isotactic polypropylene; and
c) recovering said branched olefin copolymer.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graphic illustration of the GPC-FTIR data for the polymer produced in Example 4-
Figure 2 is ft graphic illustration of the complex viscosity vs. sheer rate curve for the polymer products produced in Example S and Comparative Example 7.
DETAILED DESCRIPTION OF THE INVENTION
The polyolefin compositions of this invention are comprised of branched polyrrers wherein the polymer backbone is derived from propylena and the polymer branches are derived from polyethylene. The branches and backbone are polynrerized undere coordination or insertion conditions with activated transition metal organomeiallic catalyst compounds. The branches are composed of polyethylene which may exhibit crystalline, semi-crystalline or glassy properties suitable for hard phase domains in accordance with the art understood meaning of those terms, and are attached to a polymeric backbone that may also be crystalline. The backbone is composed of stereospecific polypropylene and, optionally, one or more comonomeis. In addition, the backbone has a melt point of 80°C or higher. Preferably, the backbone is isotactic polypropylene. These compositions are useful as thermoforming resins and exhibit improved processability over current polypropylene compositions.
In the branched olefin copolymer of the present invention, the mass ratio of the is otactic polypropylene to the polyethylene ranges from 99.9:0.1 to :50;50. Preferably, the mass ratio of the isotactic polypropylene to the polyethylene ranges
from 95:5 to 50:50.
As used herein, "isotactic polypropylene" is defined as having, at least 70% isotactic pentads according to analysis by 13C-NMR. "Highly isotactic polypropylene" is. defined as having at least 90% isotactic pentads according to analysis by13C-NMR. "Syndiotactic polypropylene" is defined as polypropylene having at least 70% syndiotactic penteds according to analysis by 13C-NMR. Preferably, the backbone of the present invention is highly isotactic polypropylene
The M acromer Sidechaias
The branches of the polymer (also referred to as "sidechains") are comprised ethylene and, optionally, one or more comonomers. Preferably, the comonomers are chemical units capable of forming crystalline or glassy polymeric segments under conditions of insertion polymerization. Suitable comoromers include C3-C20 cc-olefins, geminaTy disubstihitcd monomers, C5-C25 cyclic olefins, C5-C25styrenic olefins and lower carbon number (C3-C8) alkyl-substitxited analogs of the cyclic and styrenic olefins. Thus, typically, the branches can comprise from 85-100 mol% ethytcne, and from 0-15 mol% comcnomer, preferably 90 -99 mol% ethylene and 1-10 mol% comonomer, most preferably 94 -98 mol% ethylene and 2-6 mol% comonomer. In particular, as the sidechain Mn increases above about 3,000, it is preferable to introduce small amounts of comonomer to minimize embrittlement, e.g., about 0.2 - 4.0 mol.% comonomer. The selection of comonomer can be based upon properties other than crystallinity disrupting capability, for instance, a longer olefin comonomer, such as 1-octene, may be prefeired over a shorter olefin such as 1-butene for improved polyethylere film
tear. For improved polyethylene film elasticity or barrier properties, a cyclic comonomer such as norbornene or alkyl-sibstilu'ed norbornene may be preferred
over an α-olefin.
The sidechains can have narrow or broad molecular weigltt distribution (Mw/Mn), for example, from 1.1 to 30, typically 2-8. Additionally, the sidechains can have different comonomer compositions, eg., including the orthogonal compositional distributions described in U.S. patent 5,382,630 (CDBl >50%), incorporated by reference for purposes of U. S. patent practice Optionally, mixtures of sidechains with different molecular weights and/or compositions may be usod.
The Mnof the sidechains are within the range of from greater than or equal to 503 and less i.han or equal to 45,000, Preferably the Mn of the sidechains is from 1500 to 30,000. and more preferably the Mn is from 150C to 25,000. A prefeired branched olefmic copolymer within this class will have a melt enthalpy (Hm) as measured by differential scanning calorimetry of ≤ 90 cal/g (measured by
integruting heat flows recorded at temperatures ≥ 80 °C while scanning at ≥5 oC/min).
Conditions sufficient to form the sidechain copolymer include using suitable ethylene and comonomer reactanr ratios to assure the described sidechain olefin-dcrived unit constitution, plus catalyst and process conditions conducive to forming the unsaturated chain ends. The teachings of copernding provisional application U.S. Ser. No. 60/037323 filed 02/07/97 are specific to suitable catalyst select!cm and use to prepare macroroeric copolyiner chains with a high yield of vinyl unsaturation. The metallocene catalyst used in the step a) preparation of the unsaturation-containing macromer can be essentially any catalyst capable of insertion polymerization of ethylone, it can be one capable of high comotiomcr incorporation capability (see below) or of low comonomer incorporation capability Those of low incorporation capability are typically those that are mere congested at the metal coordination site, thus unbrictged and substituted unbridged metallocene catalysts are particularly suitable. See also the teachings of U.S. Patent 5,498,809 and international publications WO 94/19436 and WO 94/13715, describing means of preparing vinytidene-termimited ethylene-1-bitten* copolymers in high yields See also, the tea:hings of copending application U.S. Ser. No. 08/65;,030, filed 21 May 1996, as to the preparation of ethylene-isobuiylene copol} mers having high levels of vinylidene chair-end unsaturation. Throughout the description above, and below, the phrase "chain-end" or "terminal" when referring to unsaturation means olefin unsaturation suitable for insertion polymerization whether or not located precisely at the terminus of a chain All documents of this paragraph are incorporated by reference for purposes of U.S. patent practice.
In a particular embodiment, polymeric unsaturation-cuntaining rnacromet product suitable a.s branches for a subsequent copolymerization reaction can be prepared under solution polymerisation conditions with preferred molar ratios of aluminum in the alkyl alumoxane activator, e.g, methyl alumosane (MAO)), to transit on metal. Preferably that level is i 20 and » 175, more preferably ≥ 23 and = 140 and, most preferably≥20 and = 100 The temperature, pressure and time
of reaction depend upon the selected process but are generally within the normal ranges for a solution process. Thus temperatures can range from 20°C to 200°C, preferably from 30°C to 150eC, more preferably from 50°C to 140°C, and most preferably between 55°C and 135°C. The pressures of the reaction generally can vary from atmospheric to 345 MPa, preferably to 182 MPa. For typical solution reactions, temperatures will typically range from ambient to 250°C with pressures from ambient to 3.45 MPa. The reactions can be run batchwise. Conditions for suitable slurry-type reactions are similar to solution conditions except reaction temperatures are limited to those below the mell temperature of the polymer. In an additional, alternative reaction configuration, a supercritical fluid medium Can be used with temperatures up to 250°C and pressures up to 345 MPa. Under high temperature and pressure reaction conditions, macromer product of lower molecular weight ranges are typically produced, e g., Mn about 1,500
Suitable catalyst compounds that when activated can achieve high chain-end unsaturations specifically include those identified above with respect to the preparation of high vinyl or vinylidene-containing macromers. Catalyst compounds which are suitable for preparing the branched olefin copolymer of the present invention are discussed in more detailed below
The polypropylene macroniers can have narrow or broad molecular weight distribution (Mw/Mn), for example, from 1.5 to 5, typically 1.7 to 3. Optionally, mixtures of sidechains with different molecular weights may be used.
Preferably, the macromers; of the present invention are made using solution-phase conditions. Preferred solvents for solution phase reactions are selected on the basis of polymer solubility, volatility and safety/health considerations. Non-polar alkanes or aromatics are preferred. The polyolefin Bacckbone
The polyolefin backbone of the present invention is composed of propylene monomers and, optionally, one or more comonomers. In one embodiment of the present invention, no comonomers are present in the polyolefin backbone, resulting in a polymer having an isotactic polypropylene backbone and polyethylene sidechains.
In another embodiment of the present invention, one or more comonomers are present in the backbone. Comonomers which are useful in the present invention include ethylene, C4-C20 ct-olefins, and lower carbon number (C3-C8) alkyl substituted analogs of the cyclic and styrenic olefins. Other oopolymc:rizable monomers include geminalry disubstituted oletlns .such as isobutylene, C5-C25 cyclic olefins such as cyclopentene, norbornene and alkyl-substituted norhornenes, and styreric monomers such as styrene and alkyl substituted styrenes. Comonomers are selected for use based on the desired properties of the polymer product and the
metallocene employed will be selected foi its ability to incorporate the desired
amount of okfins.
When comonomers are used, they preferably comprise from 3 to 20 mole percent of the branched olefin copolymer. More preferably, the comonomers compose from 5 to 17 mole percent of the branched olefin copolymer.
In another embodiment of the present invention, the backbone of the present invention contains syndiolactic polypropylene and, optionally, one or more comoiomers. Essentially all of the backbone can be syndiotactic, resulting in a polyir-er having a syndiotactio polypropylene backbone and polyethylene sidechains Alternatively, the backbone can be a combination of syndiotactic and isotactic polypropylene with, optionally, one or more comonomers.
The mass of the backbone will typically comprise at least 40 wt% of the total polymer muss, that of the backbone: and the sidechains together, so the backbone typically will have a nominal weight-average molecular weight (Mw) weight of at least equal to or greater than about 60,000. The term nominal i.i used to indicate that direct measuremert of Mw of the backbone is largely impossible but that characterization of the copolymer product will exhibit measurements of Mw that correlate to a close approximate weight of tic polymeric backbone inclusive only of the mcnooiefin mer derivatives and the insertion moieties of the sidebranches when the macromer consists of less than 50% of the total polymer mass Catalysts
Catalysts which are useful for producing the branched polyolefin of the present invention include all catalysts which are capable of producing isotactic polypropylene and incorporating significant quantities of the isotactic polyethylene macromers of the present invention. Preferably, aetallocene catalysts are used.
As used herein "metallocene" refers generally to compounds represented by the formula CPmMRaXq wiierein CP is a cyclopentadienyl ring which may be substituted, or derivative thereof which may be substituted, M is a Group 4, 5, or 6 transi ion metal, for example titanium, zirconium, hafnium, vanadium, niobium, tantalam, chromium, molybdenum and tungsten, R is a hydrocarbyl group or hydrocarboxy group having from one to 20 carbon atoms, X is a halogen, and m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to the oxidation state of the transitionmetal.
Methods for making and using metadocenes are well known in the an. For example, metalkcenes are detailed in United States Patent Nos. 4,530,914; 4,542,199; 4,769,910, 4,308,561; 4,871,705; 4,933,403; 4,937,299; 5,017,714; 5,057,475; 5,120,867, 5,278,119; 5,304,614; 5,324,800; 5,350,723; 5,391,790; and 5 635,573 each fully incorporated herein by reference.
Preferred metallocenes arc those that are stereorigid and comprise a 'Group 4, 5, or 6 transition metal, biscyulopentadienyl derivative, preferably bis-indenyl metallocene components having the following general structure:
(Structure Removed)
wherein M1 is a metal of Group 4, 5, or 6 of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molytdenum and tungsten, preferably, zirconium, hamium and titanium, most preferably zirconium and hamium;
Rl and R2 are identical or different, are one of a hydrogen atom, a Cj-CjQ alkyl group, preferably a C1-C3 alkyl group, a C1-C1o alkoxy group, preferably a C1-C3 alkoxy group, a C6-C10 aryl group, preferably a C6-C8 aryl group, a C6-C10 aryloxy group, preferably a C6-C8 aryloxy group, a C2-C10 alkenyl group, preferably a C2-('4 alkenyl group, a Cj-C^Q arylalkyl group, preferably a C7-C10 arylalkyl group, n C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a C8-C4o arylalke«yl group, preferably a C8-C12arylalkenyl group, or a hiiiogen atom, preferably chlorine;
R3 and R4 are hydrogen atoms;
R5 and R6 are identical or different, preferably identical, are on« of a hydrogen atom, halogen atom, preferably e fluorine, chlorine or bromine atom, a C1-C10 alkyl group, preferably a C1-C4alkyl group, which may be halogenated, a
C6-C10 aryl group, which may be halogenated, preferably a C6-C8 aryl group, a C2-C10 alkenyl group, preferably aC2-C4 alkenyl group, a C7-C40 -arylalkyl group, preferably a C7-C10 arylaJkyi group, a C7-C40 alkylaryl group, prefembly a C7-C12 alkylaryl group, a C8-C40 arylalkenyl group, preferabjy a C8-C12 arylalkenyl group, a -NR215, -SR15, -OR15. -OSiR315 or --PR215 ndical, wherfin R15 is one of a halogen atom, preferably a chlorine atom, a C1-C10 alkyl group, preferably a C1-C3 alkyl group, or a C6-C10 aryl group. preferably a C6-C9 aryl group; R7is

(Formula Remove)
wherein:
R11, R12 and R13 are identical or differert and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, preferably a C1-C10 alkyl group, a C1-C20 fluoroalkyl group, preferably a C1-C10 fluoroalkyl group, a C6-C30 aryl group, preferably a C6-C20 aryl group, a C1-C30 fluoroaryl group, preferably a C1-C20 fluorcaryl group, a C1-C20 alko:ty group, ptefeiably a C1-C10 alkuxy giuuu, a C2-C20 alkenyl group, preferably a C2-C10 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C20 arylalkyl group, a C8-C40 aiytalkenyl group, preferably a C8-C22 arylalkenyl group, a C7-C40 alkylaryl group, preferably a C7-
C20 alkykaryl group or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin. preferably silicon or germanium, . most preferably silicon,
R8 and R9 are identical or different and have the meanings stared forR11;
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, m plt4 n being zero, 1 or 2, preferably zero or 1; and
the radicals R10 are identical or different and have the meanings stated for R11, R12 and R13. Two adjacent R10 radicals can be joined together to form a ring system, preferably a ring system containing from about 4-6 carbon atoms.
Alkyl refers to straight or branched chain substituenis. Halogen (halogenated) is fluorine, chJorine, bromine or iodine atoms, preferably fluorine or chlorne.
Particularly preferred metaliocenes are compounds of the structures:
(Structure Removed)
wherein.
M1 is Zr or Hf, R1 and R2 are methyl or chlorine, and R5, R6 R8, R9,R10, R11 (.nd R12 have the above-mentioned meanings
The chiral metallocenes may be used as a racemate for the preparation of highly isotactic polypropylene polymers ami copolymers. It is also possible to use the pure R or S form An optically active polymer can he prepared with these pure stereoisomerie forms. Preferably the meso form of the metalloccre is removed to ensur? the center (i.e., the metal atom) provides stereoregular polymeri.tation. Sepaiation of the stereoisomers can be accomplished by known literature techn ques. For special products t is also possible to use rac/meso mixtures.

Generally, the metallocenes are prepared by a multi-step process involving repeated deprotonations/metallations of the aromatic ligands and introduction of the bridge and the central atom by their halogen derivatives. The following reaction scheme illustrates this generic approach
(Scheme Removed)
Additional methods for preparing metallocenes of the present invention are fully described in the Journal of Organometallic Chem.. volume 288, (1958), pages 63-67, and in EP'-A- 320762, for preparation of the metallocenes described, both of which are herein fully incorporated by reference.
Illustrative but non-limiting examples of some preferred metallocenes include: Dimethyisilandiylbis (2-methyl-4-phenyl- 1 -indenyl)ZrCl2
Dimethylsilandiylbis(2-methyl-4,5 benzoindenyl)ZrCl2;
Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)ZrCl2,
DimcthyIsilandiylbis(2-ethyM-phcnyl-I-indcnyl)ZrCl2;
Dimethylsilandiylbis(2-cthyl-4-naphthy1-l-indenyl}ZrCl2,
Dimethylsilandiylbis(2-methyl-4-phenyl-l -indenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-4-( 1 -naphthyl)- 1 -indenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-4-(2-naphthy1)- 1 -inclenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-indenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-4,5-diisopropyl- 1 -indenyl)ZrCl2,
Diraethylsilandiylbis(2,4,6-trimethyl-l-indenyl)ZrCl2,
Phenyl(Methyl)silandiylbis(2-methyl-4,6-diisopropyl-l-indenyl)ZrCl2,
1 ,2-Ethandiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrCl2

,
l,2-Batadiylbis(2-methyl-4,6-diisopropyl- 1 -indenyl)ZrCl2,
DDimethylsilandiylbis(2-methyl-4.elhyl- 1 -indenyl)Zr Cl2,
Dimethylsilandiylbis(2-methyl-4-isopropyl-l-indonyl)ZrCl2,
Dimeihylsilandiylbis(2-methyl-4-t-butyl- 1 -indenyl)ZrCl2,
Pheny l(Methyl)silandiylbis(2-methyl-4-isopropyl - 1 -indenyl)ZrCl2,
Dimethylsilandiylbis(2'ethy.-4-melhyl- l-indenyl),ZrCl2,
Dimethylsilandiylbis(2,4-dimethyl- 1 -indenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-4.ei;hyl-l-indenyl)ZrCl2,
Dimethylsilandiylbis(2-methyl-a-a.cenaphth- 1 -indenyl)ZrCl2,
Phenyl(Methyl)silandiylbis(2-methyl-4,5-benzo-J-indenyl)ZrCl2,
Phenyl(Methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-l-indenyl)ZrCl2,,
Phenyl(Methyl)si]andiy]bis(2-methyl-4,5-(telrametaylbenzo)-l-indenyl)ZrCl2,
Phenyl(Methy i)siiandiyibis 1.2-methyi-a-acenaphth- i -indenyl)ZrCl2,
l,2-Ethandiylbis(2-methyl-4,5-benzo-l-indenyl)ZrCl2,
Dimetliylsilandiylbis (2-methyl,4,5-benzo-l-indenyl)Zrcl2, 1,2-Ethandiylbis(2,4,7-trimcthyl- 1 -indenyl)ZrCl2, Dimetliylsilandiylbis (2-methyl-1 -indenyl)ZrCl2, 1,2-Ethandiylbis(2 -methyl-1 -indenyl)ZrCl2, Phenyl(Mcthyl)silandiylbis{2-methyl-1 -indenyl)ZrCl2, Diphenylsilandiylbis is(2-methyl-1-indcnyl)ZrCl2, 1,2-Butandiylbis(2-methyl-1 -indenyl)ZrCl2, Dimet hylsilandiylbis(2-ethyl-1-indenyl)ZrCl2, Dimet JiylsiIandiylbis(2-rnethyl-5-isobutyl-1 -indenyl)ZrCl2, Pheny ,(Methyl)si;andiylbis(2-metliyl-5-isobutyl- i -inde«yl)ZrCl2, Dimetliylsilandiylbis (2-methyl-5-t-butyl-l-indenyl)ZrCl2, Dimethylsilandiylbis(2,5,6-trimethyl-l-indenyl)ZrCl2, and the like.
Some preferred metallocene catalyst components are described in detail in U.S. Patent Nos 5,149,819, 5,243,001, 5,239,022, 5,296,434 and 5,276,208 all of which are herein fully incorporated by reference. In addition, the bis-amido and bis-arylamido transition metal catalysts of U.S. patent 5,318,935 and copending U.S. patent application 08/ 803,687, filed 2/24/97, and the α-diimine nickel catalyst complexes of WO 96/23010 can be useful in incorporating the macromers of the preser t invention into the backbone
Most preferably, the catalyst used to produce the branched polyolefin of the preser.t invention is a dimethylsilyl-bridged bis-indenyl zirconocee or hafnocene such as dimethy silyl bis(2-methyl-indenyl) ZrCl2, dimethylsilyl bis(2-methyl-4-phenyi-l-indenyl) ZrCl2, ditnethylsilyl bis(2-methyl-4-(1-naphthyl)-l-in'Jenyl) ZrCl2, or dimethyisilyl bis(indenyl)haihium dimethyl.
Preferably, the cattlysts used to produce the syndiotaclic polypropylene backbone of the present invention are those disclosed in U.S. Patents 4,892,851, 5,155080, and 5,132,381, the d sclosures of wliich are hereby incorporated by reference.
The terms "cocatalyst" and "activator" are used herein interchangeably and are defined to be any compound or component which can activate a. bulky ligand
transition metal compound or a metatlocene, as defined above. Alumoxane may be used as an activator. There are a variety of methods for preparing alumoxano, non-limiting examples of which are described in U.S. Patent No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329.032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180. each of which is fully incorporated herein by reference. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear .Uumoxane can be decanted from the cloudy solution.
It is also within the scope of this invention to use ionizing activators, neutril or ionic, or compounds such as tri(n-butyl)ammonium tetrakis(pentaflurophenyl)boron, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with but not coordinated or only loosely coordinated to the remaining ion ofthe ionizing compound. Combinations of activators are also contemplated by the invention, for example, alumoxane and ionizing activators in combinations, see for example, WO 94/C7928.
Descriptions of ionic catalysts for coordination polymerization comprised of miitallocene cations activated by non-coordinating anions appear in th« early work in EP-A-0 277 003, EP-A-0 277 004 and US patent 5,198,401 and WO-A-92/00333 (incorporated herein by reference). These teach a preferred method of preparation wherein metallocenes (bisCp and monoCp) are protonated by an. anion precursor such that an alkyl/hydnde group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating arion.
The term "noncoordinating anion" means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remainirg sufficiently labile to be displaced by a neutral Lewis base. "Compatible" noncoordinating unions are those which are not degraced to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic sitbstituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product
from the anion. Noncoordinating anions useful in accordance with this invention are those which are compatible, stabilize the metailocene cation in the seme of balancing its ionic charge in a +1 state, yet retain sufficient lability to permit displacement by an ethylenically or acctvfenically unsaturated monomer during polymerization.
The use of ionizing ionic compounds not containing an active proton but capable of producing the both the active metallocene cation and an nonccordinating amion is also known. See, EP-A-0 426 637 and EP-A- 0 573 403 (incorporated herein by reference). An additional method of making the ionic catalysts uses ionizing anion pre-cursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) boron. See EP-A-0 520 732 (incorporated herein by reference). Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion pre-cursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference).
Where the metal ligandu include halogen moieties (for example, bis-cyclopentadienyl zirconium dicliloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyis, alkylalumcxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 582 (incorporated herein by reference) for in situ processes describing the reaction of allcyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds Support Materials
The metallocenes described herein arc preferably supported using a porous paniculate material, such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
The most preferred support materials are porous inorganic axide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixtures thereof are
particularly preferred. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
Preferably the support material is porous silica which has a surface area in the range of from about 10 to about 700 m2/g, a total pore volume in the range of from about 0.1 to about 4.0 cc/g and an average particle size in the range of from about 10 to about 500 µm.. More preferably, the surface area is in the range of from about 50 to about 500 m2/g, the pore volume is in the range of from about 0.5 to about 3.5 cc/g and the average particle size is in the range of from about 20 to about 200 µm. Most preferably the surface area is in the range of from about
100 to about 400 m2/g, the pore volume is in the range of from about 0.8 to about 3.0 cc/g and the average panicle size is in the range of from about 3C to about 100 µm. The average pore size of typical porous support materials is in the range of from about 10 to about 1000A. Preferably, a support material is used that has an average pore diameter of from about 50 to about 500A, and most preferably from about 75 to about 3 50A. It may be particularly desirable to dehydrate the silica at a temperature of from about 100°C to about 800°C anywhere from about 3 to about 24 hours.
The metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U. S Patent Nos. 4,808 561 and 4,701,432 (each fully incorporated herein by reference.). Preferably the mjtallocenes and activator an; combined and their reaction product supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/ 28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference.) Alternatively, the metatlocenes may Ix preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they ars dried then combined as a powder before use in polymerization.
Regardless of whether the metallocene and activator are separately precontacted or whether the metallocene and activator are combined at once, thetotal volume of reaction solution applied to porous support is preferalby less than about 4 times the total pore volume of the porous support, more preferably less than about 3 times the total pore volume of the porous support and even more prefe-ably in the range of from more than about I to less than about 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. The preferred method is described in Volume 1, Experimental Methods in Catalyst Research, Acidemic Press, 1968, pages 67-96
Methods of supporting ionic catalysts comprising metallocene cations and noncorodinating anions are described in WO 91/09882, WO 94/03506, WO 96/0-1319 and U.S. patent 5,643,847 (incorporated herein by reference). The methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strung Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the Lewis acid becomes ccvalently bound und the hydrogen of the hydroxy group is available to plotonate the metallocene compounds.
The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art. For details regarding prepolymerization, see United States Patent Nos. 4,923,833 and 4,921,825, EP 0 279 863 and BP 0 354 893 each of which is fully incorporated herein by reference. Polymerization Processes
The branched polyolefin of the present invention may be produced using the catalysts described above in any process including gas, slurry or solution phase or high pressure autoclave processes. (As used herein, unless differentiated, "polymerization" includes copolymerizaticn and "monomer" includes comonomer.) Additionally, combinations of the above reactor types in multiple, series reactors and/or multiple reaction conditions and/or multiple catalyst configurations are explicitly intended. Preferably, a gas or slurry phase process is used, most preferably a bulk liquid propylenc polymerization process is used.

In the preferred embodiment, this invention is directed toward the bulk liquid polymeriration and copolymerization of propyiene in a slurry or gas phase polymerization process, particularly a slurry polymerization process. Another embodiment involves copolymerization reactions of propyiene with one or more comonomers Such comonomers include alpha-olefin monomers having from 4 to 20 carbon atoms, preferably 4-12 carbon atoms, for example alpha-olefin comonomers of ethylene, butene-1, pentene-1, 4-methylpcntene-l, hexene-l, octene-l, decere-1. Other suitable comonomers include geminally disubstituted monomers, C5-C25 cyclic olefins such as cyclopentene or norbornene, styrenic olefins such as styrene, and lower carbon number (C3-C8) alkyl substituted analogs of the cyclic and styrenic olefins. In addition, comonomers sjch as polar vinyl, diolcfins such as dienes, for example, 1,3-butadiene, 1,4-hexadiene, norbornadiene or v nylnorbomene, acetylene and aldehyde monomers are suitable.
Typicall;/ in a gas phase polymerization process a continuous cycle is employed wherein one part of the cycle of a reactor, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. The recycle stream usually contains one or more monomers continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions This heat is removed in another part of the cyde by a cooling system external to the reactor. The recycle stream is withdrawn from the fluicized bed and recycled back into the reactor Simultaneously, polymer product is withdrawn from the reactor and new or fresh monomer is added to replace the polymerized monomer (See for example U.S. Patent Nos. 4,543,399; 4,588,790; 5,02 8,670; 5,352,749; 5,405,922, and 5,436,304 ail of which are fully incorporated herein by reference.)
A slurry polymerization process generally uses pressures in the range of from about 1 to about 500 atmospheres or even greater and temwratures in the range of from -SO°C to about 280°C. In a slurry polymerization, a suspension of solid, particulale polymer is formed in a liquid or supercritical polymerization medium to which propyiene and comonomers; and often hydrogen along with catalyst are added. The liquid employed in the polymerization medium can be, for

example, an alkane or a cycloatkane. The medium employed should be liquid under the conditions of polymerization and relatively inert fuch as hexane and isobutane. In tie preferred embodiment, propylene servts as the polymerization diluent and the polymerization is carried out using a pressure of from about 200 kPa to about 7,000 kPa at a temperature in the range of from about 50°C to about 120oC.
The periods of time for each stage will depend upon the catalyst system, comonomcr and reaction conditions In general, propylene should be homopolymeriajd for a time period sufficient to yield a composition having from about 110 to about 90 weight percent homopolymer based on the total weight of the polymer, preferably from about 20 to about 80 weight percent, even more preferably from about 30 to about 70 homopolymer weight percent based on the total weight of the polymer.
The above-described temperatures, reaction times and other conditions are considered suitable polypropylene polymerization conditions for the purposes of this invention.
The polymerization may be conducted in batch or continuous mode and the entire polymerization may take place in one reactor or, preferably, the polymerization may be carried out in a series of reactors. If reactors in series are used, then the comonomer may be added to any reactor in the series, however, preferably, the comonomer is added to the second or subsequent reactor.
Hydrogen may be addtid to the polymerization system as a molecular weight regulator in the first ;xnd/or subsequent reactors depending upon the particular properties of the product desired and the specific metillocenes used. When metallocemes having different hydrogen responses are used, the addition of hydrogen will affect the molecular weight distribution of the polymer 'product accordingly, A preferred product form is to have the comonomer be present in the high molecular weight species of the total polymer composition to provide a favorable balance of good film stretchabllity without breaking, coupled with low extnctables, low haze and good moisture barrier in the film. Accordingly in this preferred case, the same or lower levels of hydrogen are utilized during

copclymerization as were used during polymerization in the second or subsequent reactor.
For both polyethylene macromer product and branched polyolefin preparation, it in known that many methods and permutations of the ordering of addition of maciomer and monomer species to the reactor are possible, some more advantageous than others For example, it is widely known in the art that preactivation of the metallocene with alumoxane before addition to a continuous solui ion-phase reactor yields higher activities than continuous addition of metallocene and activator in two separate streams. Furthermore, it may be advantageous to control precontacting time to maximize catalyst effectiveness; e.g., avoiding excessive aging of the activated catalyst composition.
It is preferable to use the polyethylene macromers such that they are promptly functionalized or copolymerized after being prepared. The highly reactive vinyl groups appear to be susceptible to byproduct reactions with adventitious impurities and, even, dimerization or addition reactions with other unsaturated group-containing polymeric chains Thus maintaining in a coolctd, inert environment af:er preparation and prompt subsequent use will optimize the effectiveness of the use of the polyethylene macromer product A continuous process utilizing series reactors, or parallel reactors will thus be effective, the polyethylene macromer product being prepared in one and continuously introduced into the other. INDUSTRIAL UTILITY
The branched polyolefin polymers of the present invention exhibit improved melt strength ard shear thinning characteristics to standard propylerie copclymers. This results in improved proc assability of the polymers, e.g. increased shear thinning and high output for a constant energy input. These characteristics will resu!t in improved processing in blow molding and thermoforming operations. For example, in thermoforming operations sag will be decreased and power consumption will be lowered in the extruders.
In order that the invention may be more readily understood, reference it nude to the following examples, which are intended to illustrate the invention but not to limit the scope thereof. EXAMPLES General
All polymerizations were performed in a 2-liter Zlpperclave reactor equipped with a water jacket for temperature control. Liquids were measured into the reactor using calibrated sight glasses. High purity (>99.5%) toluene was purified by passing first through basic alumina activated at high temperature in nitrogen, followed by molecular sieve activated at high temperature in nitrogen, Polymerization grade ethylene was supplied directly in a nitrogen-jacketed line and used without farther purification. Propylene was purified by passing through activated basic alumina and molecular sieves. Methylalumoxane (MAO, 10% in toluene) was received from Albemarle Inc. in stainless steel cylinder, divided into 1-liter glass containers, and stored in a laboratory glove-box at ambient temperature.
For the polymer synthesis, propylene was measured into the reactor through a calibrated container. To ensure the reaction medium was well-mixed, a flat-paddle stirrur rotating at 750 rpm was used. Reactor Preparation
The reactor was first cleaned by heating to 150 °C in toluene to dissolve any polymer residues, then cooled and drained. Next, the reactor was heated using jacket water at 110 °C and the reactor was purged with flowing nitrogen for a period of-30 minutes Before reaction, the reactor was further purged using 3 nitrogen pressurize/vent cycles (to 100 psi). The cycling served two purposes: (1) to thoroughly penetrate all dead ends such as pressure gauges tc purge fugitive contaminants and (2) to pressure test the reactor. Catalysts
All catalyst preparations were performed in an inert atmosphere with branched olefin copolymer were dimethylsilyl bis(indenyl)hafnium dimethyl and dimnthylsilyl bis(2-methyl indenyl) zirconium dichloride. The dimethylsilyl bis(indenyl)hafnium dimethyl was activated with [DMAH]+ [(C6F5)4 B]. The dim«:thylsilyt bi5(2-methyl indenyl) zirconium dichloride was activated with MAO. To maximize solubility of the j netallocene, toluene was used as « Ethylene was added to the reactor as needed to maintain total system pressure at the reported levels (semi-batch operation). Ethylene flow rate was monitored using a Matheson mass flow metter (model number 8272-0424). To ensure the reac.ion medium was well-mined, a flat-paddle stimer rotating at 750 rpm was used Example 1
The reactor was simultaneously purged of nitrogen and pressure tested using two ethylene fill/purge cycles (to 300 psig). Then, the reactor pressure was raised to -40 psi to maintain positive reactor pressure during setup operations. Jacket water teriperature - was set to 120°C and ;200 milliliters of toluene were added to the reactor The stirrer was set to 750 rpm. Additional ethylene was added to maintain a positive reactor gauge pressure as gas phase ethylene was absorbed into solution The sysrem was allowed to reach a steady temperature. The ethylene prussurs regulator was next set to 40 psig and ethylene was added to the system until a steady state was achieved as measured by zero ethylene uptake The reactor was isolated and a pulse of toluene pressurized to 30C psig was used to fcrce the catalyst solution from the addition a be into the reactor. The ethylene supply marifold was immediately opened to the reactor in order to maintain a constant reactor pressure as ethylene was consaned by reaction.
After 60 minute.; of reaction, the reactor was isolated, cooled to room temperature ad methancl was added to precipitate the macromer product. The yielc was 48 g. The polymer product had an Mn of 7.500 and a vinyl end group percentage of 73. Eiample 2
The reactor was simulta lecusly purged cf nitrogen and pressure tested using two ethylene fill-purge cycles (to 300 psig) Then, the reaclor pressure was raised to -40 psi to inairl iin po .itive reaclor pressure during setup operatic ns filter water temperatur: was set to 120°C and 1200 milliliters of toluene were added to the reactor The stirrer was set to 750 rprn. Additional etiylene was addened to mantain a positive reactor gauge pressure as gas phase ethylene was absurbed iivo solution The sysiem was allowed 10 reach a steady temperature. The ethylen: pressure regulator was next set to 40 psig and ethylcne was added to the system until a steady state was achieved as mea-sured by zero ethylene uptake. The reactor WAS isolated and a pulse of toluene pressurized to 300 psig was used to force the catalyst solution ircm the addition tube into the reaclor The ei.hylene supply manifolc was immediately opened to the reactor in order to maintain a constant reacto pressure as eth;-lene was consumed by reaction
After 20 minutes of reaction, the re;.c:.or was tsolatei, coofed to room temperature and methanol was added to precipitate the macrcmer product. The yield was 23 3 g The polymer product hud an Kin of 4,300 and a viml end group percentage of 73 Example 3
A 2-liter reactor was charged with toluene (1 L), propylene (150 mL), 10 g of the polyethblene macromer irom Example 1 and Triisobuty aluminum (2.0 mL of 1M solution tn toluene) The reactor was beiiied to 90°C and equilibrated for 5 min Then 2 ing of dimeihyhilyl bis(indenyl)liafnium dimethyl and 6 mg of [DMAH] [(C6-F5]" in 5 mL of toluene were injected using a catalyst tube. After 15 min, the teactor was cooled to 25°C and vented The polymer was collected by the dried in air for 12 hems Yield 40 g.
Example 4
A 2-liter autoclave reactor was charged with toluene (1 L), propylene (ISO mL), 10 g of the polyethylene macromer from Example l and Triisobutylaluminum (2.0mL of 1M solution in toluene). The reactor was heated to 90oC and equilibrated for 5 min Then 2 mg of dimelhylsilyl bis(2-methyl indenyl) zirconium dichloride activated in 5 mL of toluene and 1 mL of MAO (10wt% in toluene) was injected using a catalyst tube. After 15 min, the reactor was cooled to 25°C and vented. The polymer was collected by filtration and dried in air for 12 hours Yield: 40 g. Eyarnplt 5
A 2-liter autoclave reactor was charged with toluene (1 L), propylene (150 mL), 10 g of the polyethylene macromer from Example 2 and Triisobutylaluminum (2.0 mL of 1M solution in toluene). The reactor was heated to SO^C and equilibrated for 5 min. Then 2 mg of dimethylsilyl bis(2-methyl indenyl) zirconium dichlnride activated in 5 mL of toluene and 1 mL of MAO (10wt% in toluene) was injected using a catalyst tube. After 15 min, the; reactor was cooled to 25°C and vented. The polymer was collected by filtration and dried in air for 12 hours. Yield: 53 g. Example 6
A 2-liter autoclave reactor was charged with toluene (1 L), propylene (150 raL), 5 g of the polyethylene macromer from Example 2 and Triisobutylaluminum (2.0 mL of 1M solution in toluene). The reactor was heated to 50oC and equilibrated for :5 min. Then 2 nig of dimethylsilyl bis(2-methyl indnyl) zirconium dichJoride activated in 5 mL of toluene and 1 ml of MAO (10wt% in toluene) was injected using a catalyst tube. After 15 min, the reactor was cooled to 25°C and vented. The polymer was colluded by filtration and dried in air for 12 hours. Yield: 51 g.
Comparative Example 7
A 2-liter reactor was charged with toluene (1 L), propyiene (150mL), and TnisobutylalLiminuni (20 mL of !M solution in toluene). The reactor was heated to 5D°C and equilibrated for 5 min. Then 2 mg of dimethylsilyl bis(2-methyl indenyl) zirconium dichloride activated in 5 ml, of toluene and 1 mL of MAO (10wt% in toluene) was injected using a catalyst tube. After 15 min, the reactor was cooled to 25°C and vented. The polymer was collected by filtntion and dried in air for 12 hours. Yield: 63 g. Product Characterization
Some general characterisation data for the polymers made in the Examples 3-6 and Comparative Example 7 are listed in Table 1 The polymer product samples were analyzed by gel permeation chromatography using a. Waters 150C high temperature system equipped with a DRI Detector, Shodisx AT-806MS colufin and operating at a system temperature of 145°C. The solvent used was 1,2,4-tricnIorobunzene, from which polymer sample solutions of 1.5 mg/ml concentration were prepared for injection. The total solvent flow rate was 1 ml/minute and the injection size was 300 microliters. After eluticn of the polymer samples, the resulting chromatograms were analyzed using the Waters Expert Ease program to calculate the molecular weight distribution and one or more of M^
Mw and Mz averages.
The melting point of the polymer product samples was determined on a DSC 2910 Differential Scanning Calorimeter (TA Instruments). The reported melting points were recorded at second melt with a temperature ramp of IO"C/min. "Wt % C2" indicates the percentage of polyethylene macromer (Ca) incorporated into the polymer samples which was determined by Analytical Composition Distribution analysis.
Table I Physical Data Summary

(Table Removed)
Additional analysis was conducted on the polymer produced in Example 4 to determine the amount of branching and branch distribution. Since the ethylene contents at various molecular weight regions can be readily determined by FTIR, it is possible to quantify the incorporation of macromer and calculate LCB distribution. Shown in Figure 1 is the GPC-FTIR analysis for the polymer made in Example 4. The dots indicate the ethylene content measured by F1TR at different molecular weight along the GPC curve Since the molecular weight (Mn) of the PE macromer is 7,500, the ethylene content detected at high molecular region clearly indicates; the incorporation of macromer in the PP backbones. More importantly, it is possible to calculate the statistical LCB-distribution (also shown in Figure 1). Assuming that all macromeni have the equal probability of incorporation (all macromers are equally spaced along the PP backbones), then, the number of long chain branches at certain molecular weight may be calculated according to the following equation:
(Equation Removed)
Figure 2 shows a complex viscosity vs.. shear rate curve for the polymers produced in Example 5 and Comparative Example 7. Example 5 demonstrates a steeper curve than Comparative Example 7. A steeper curve correlates to
improved shear "binning performance as the viscosity reduces more rapidly at high shear rites. Therefore, the polymer product which was produced using macromes demonstrates improved procsssability over a polymer which was prcxiuced without the use of macromers.
While certain representative embodiments and details have been shewn for the purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the process and products disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims.





CLAIM:
1. A process for preparing a branched olefin copolymer Characterized in
that it comprises the step of sow obloops
A
a) copolymerizing ethylene, optionally with one or more
copolymerizable monomers selected from the group consisting
of C3-C20 a olefins, germinally disubstituted monomers, C5-C25
cyclic olefins, C5-C25 styrenic olefins, lower carbon number C3-

C8 alkyl substituted analogs of the cyclic and styrenic olefins, dienes, acetylene, and aldehyde monomers, in a polymerization reaction at a temperature between -60°C to 280°C under conditions sufficient to form copolymer having greater than 40% chain end-group unsaturation;
b) copolymerizing the product of a) with propylene and, optionally,
one or more copolymerizable monomers selected from the
group consisting of C3-C20 a olefins, germinally disubstitu ted
monomers, C5-C25 cyclic olefins, C5-C25 styrenic olefins, lower
carbon number C3-C8 alkyl substituted analogs of the cyclic and
styrenic olefins, in a polymerization reactor at a temperature
between -60°C to 280°C under suitable polypropylene
polymerization conditions using a chiral, stereo-rigid transition
metal metallocene catalyst capable of producing isotactic
polypropylene; and
c) recovering said branched olefin copolymer.
2. The process as claimed in claim 1, wherein step a) is conducted by a solution process in which said ethylene and one or more copolymerizable monomers are contacted with a transition metal olefin
polymerization catalyst activated by an alumoxane cocatalyst, the mole ratio of aluminum to transition metal is less than 220 : 1.
3. The process as claimed in claim 1 wherein step b) is conducted in
a separate reaction by solution, slurry or gas phase polymerization.
4. The process as claimed in claim 1, wherein said chiral, stereo-rigid
transition metal catalyst compound in step b) is activated by said
alumoxane cocatalyst or non-coordinating anion precursor.
5. A process for preparing a branched olefin copolymer substantially
as hereinbefore described with reference to and as illustrated in the
accompanying drawings.

Documents:

316-del-1998-abstract.pdf

316-del-1998-assignment.pdf

316-del-1998-claims.pdf

316-del-1998-correspondence-others.pdf

316-del-1998-correspondence-po.pdf

316-del-1998-description (complete).pdf

316-del-1998-drawings.pdf

316-del-1998-form-1.pdf

316-del-1998-form-13.pdf

316-del-1998-form-19.pdf

316-del-1998-form-2.pdf

316-DEL-1998-Form-3.pdf

316-DEL-1998-Form-4.pdf

316-del-1998-form-6.pdf

316-del-1998-gpa.pdf

316-del-1998-pct-210.pdf

316-del-1998-pct-408.pdf

316-del-1998-pct-409.pdf

316-del-1998-pct-416.pdf

316-del-1998-petition-137.pdf

316-del-1998-petition-138.pdf

316-del-1998-petition-others.pdf


Patent Number 215108
Indian Patent Application Number 316/DEL/1998
PG Journal Number 10/2008
Publication Date 07-Mar-2008
Grant Date 21-Feb-2008
Date of Filing 09-Feb-1998
Name of Patentee EXXONMOBIL CHEMICAL PATENTS, INC.
Applicant Address 1900 EAST LINDEN AVENUE, LINDEN, NEW JERSEY, 07036, USA
Inventors:
# Inventor's Name Inventor's Address
1 WEQUING WENG 13707 SHADOW FALLS COURT, HOUSTON, TEXAS 77059, USA
2 ARMEN H DEKMEZIAN 2806 EVERGREEN CLIFF TR., KINGWOOD, TEXAS 77345, USA
3 ERICK JOHN MARKEL 4534 NATURAL BRIDGE DRIVE, KINGWOOD, TEXAS 77346, USA
4 AVINASH CHANDRAKANT GADKARI 13827 ROSEBRANCH COURT, HOUSTON, TEXAS 77059, USA
5 JEAN-MARK DEKONINCK 4007 ROARING RAPIDS DRIVE, HOUSTON, TEXAS 77059, USA
PCT International Classification Number C08K 5/521
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/067,782 1998-02-06 U.S.A.
2 60/037,323 1997-02-07 U.S.A.
3 60/046,812 1997-05-02 U.S.A.