Title of Invention

"POLYMER BLEND COMPOSITIONS"

Abstract Thermoplastic compositions having miscible and compatible immiscible polymer blends are disclosed. The miscible polymer blends have a single glass transition temperature. The compatible polymer blends have two glass transition temperatures.
Full Text POLYMER BLEND COMPOSITIONS
BACKGROUND OF THE INVENTION
[0001] Compositions having a polymer blend are disclosed herein
[0002] Polymer blends are widely employed in a range of applications For example, substitution of metal parts with parts made from plastic materials (polymer compositions) results m parts having lighter weight and similar or improved performance properties In many applications, such as parts used under an automobile hood, plastic matenals with a high heat resistance are required Frequently though, plastic materials having a high heat resistance are difficult to mold Blending polymers is one approach to achievmg a plastic matenal with a desired set of physical properties such as high heat resistance and processabihty Polymer blends may comprise miscible polymers, immiscible polymers, or a combination of miscible and immiscible polymers Blends comprising immiscible polymers have two or more phases and such blends may be compatible or mcompatible Incompatible blends of immiscible polymers can suffer from phase separation as demonstrated by delamination or the formation of skin-core layered structures during polymer processing operations, especially injection molding The term, "delamination," as used when referring to such materials, descnbes visually observed separation of a surface layer giving a flaking or onion skm effect Incompatibility may also result in poor mechanical properties and marginal surface appearance (streaking, pearlescence, etc) Compatible blends of immiscible polymers typically do not show any delamination and can result in acceptable end-use properties
[0003] Miscible polymer blends, on the other hand, may offer desirable end-use properties and the advantage of tailoring product properties intermediate of the individual components across the miscible composition range Miscible blends do not suffer from delamination and generally have consistent physical properties
[0004] So while a miscible blend of two polymers is generally desirable it can be difficult to achieve Blends of two polymers of a same or similar class might be expected to have a better chance of miscibility However, polymers from the same class are frequently immiscible and form multiphasic compositions For example, ACUDEL 2000 from Solvay is an immiscible blend of two polysulfones - PPSU and PSU In addition, many such examples of immiscible blends of polymers in the same class exist in the literature Thus, polymer miscibility is difficult to predict, even within the same class of polymers
[0005] For the foregoing reasons there remams an unmet need for non-delaminated polymer blends, l e , blends free of delamination, which are either miscible blends or immiscible, but nonetheless compatible, blends More particularly, there remains an unmet need to develop blends havmg high heat resistance, and methods of forming such polymer blends
BRIEF DESCRIPTION OF THE INVENTION
[0006] The invention includes thermoplastic compositions comprising a non-delaminated polymer blend The polymer blend is derived from a pre-polymer and a polymer The a pre-polymer comprises a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof, and further comprises structural units derived from a dianhydnde and a diamine The polymer compnses a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof The reactive member is reactive with the free anhydride groups, the free amine groups, or combmations thereof The polymer blend is non-delaminated
[0007] The polymer may comprise structural units derived from a dianhydnde and a diamine In embodiments where the pre-polymer and polymer employ a common diamine or dianhydnde the polymer blend has a smgle glass transition temperature In embodiments where the pre-polymer and the polymer employ different diamines and
dianhydndes the polymer blend has greater than one glass transition temperatures but does not show delamination after agmg at 280°C for 240 hours
[0008] In some embodiments the polymer may comprise structural units derived from bisphenol-A dianhydndes and diamino diaryl sulfones and the pre-polymer compnses structural units derived from oxydiphthahc anhydrides and diamino diaryl sulfones In one embodiment the polymer blend has a single glass transition temperature In one embodiment the polymer blend has greater than one glass transition temperature but does not show delamination after agmg at 280°C for 240 hours
[0009] In one embodiment a composition comprises a polymer blend derived from a pre-polymer and a polyethenmide polymer The pre-polymer compnses a component selected from the group consisting of free amine groups, free anhydnde groups, and combmations thereof, and further comprises structural units denved from oxydiphthahc anhydnde and diamino diaryl sulfone The polyethenmide polymer compnses a reactive member selected from the group consistmg of structural groups, end groups, and combinations thereof and further comprises structural units denved from bisphenol-A dianhydnde and diamino diaryl sulfone The composition further comprises a stabilizer selected from the group consistmg of antioxidants, phosphites, and combmations thereof The polymer blend has a heat deflection temperature greater than or equal to 200°C accordmg to ASTM D648, a tensile strength greater than or equal to 90 megaPascals according to ASTM D638, and a coefficient of thermal expansion of less than or equal to 60 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute Pnor to the formation of the polymer blend the pre-polymer is present an amount of 50 to 95 weight percent and the polyethenmide polymer is present m an amount of 5 to 50 weight percent, based on the combmed weight of the pre-polymer and the polymer
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Figure 1 is a photograph of a sample showing delamination
[0011] Figure 2 is a photograph of a sample essentially free from delamination
DETAILED DESCRIPTION OF THE INVENTION
[0012] The invention is based on the unexpected discovery that it is now possible to form non-delaminated compositions that are denved from (a) pre-polymers having free amine groups and/or free anhydride groups and (b) a polymers having structural groups and/or end groups that are reactive with the pre-polymer's free anhydride groups and/or free amine groups Surprisingly, the compositions (and articles derived from the compositions) can overcome the problem of delamination typically found m immiscible, incompatible blends Compositions (and articles denved from the compositions) can also exhibit improved miscibihty and mcrease the range of miscible blend compositions
[0013] Other than m the operating examples or where otherwise mdicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term "about" Various numerical ranges are disclosed in this patent application Because these ranges are contmuous, they mclude every value between the minimum and maximum values Unless expressly mdicated otherwise, the various numerical ranges specified in this application are approximations
[0014] The terms "first," "second," and the like, "primary," "secondary," and the like, "(a)," "(b)" and the like, as used herem do not denote any order, quantity, or importance, but rather are used to distinguish one element from another The terms "a" and "an" do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description mcludes instances where the event occurs and instances where it does not The endpoints of all ranges directed to the same component or property are mclusive of the endpomt and mdependently combmable Reference throughout the specification to "one embodiment," "another embodiment," "an embodiment," "some embodiments," and so forth, means that
a particular element (e g, feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments In addition, it is to be understood that the described element(s) may be combined in any suitable manner m the various embodiments
[0015] Compounds are described using standard nomenclature For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom A dash ("-") that is not between two letters or symbols is used to indicate a pomt of attachment for a substituent For example, -CHO is attached through carbon of the carbonyl group
[0016] The definition of benzylic proton is well known in the art, and as used herein it encompasses at least one aliphatic carbon atom chemically bonded directly to at least one aromatic ring, such as a phenyl or benzene rmg, wherem said aliphatic carbon atom additionally has at least one proton directly bonded to it
[0017] As used herem "substantially free of benzylic protons" or "essentially free of benzylic protons" means that the pre-polymer, such as for example a polyimide sulfone pre-polymer, has less than about 5 mole % of structural units, in some embodiments less uian about 3 mole % structural units, and in other embodiments less than about 1 mole % structural units denved containing benzylic protons "Free of benzylic protons", which are also known as benzylic hydrogens, means that the pre-polymer contams zero mole % of structural units denved from monomers and end cappers containmg benzylic protons or benzylic hydrogens The amount of benzylic protons can be determined by ordinary chemical analysis based on the chemical structure In one embodiment the polymer blend is essentially free of benzylic protons
[0018] The term "alkyl" is intended to include both Ci 30 branched and straight-chain, unsaturated aliphatic hydrocarbon groups havmg the specified number of carbon atoms Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, i-propyl,
n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n-and s-heptyl, and, n- and s-octyl The term "aryl" is intended to mean an aromatic moiety containing the specified number of carbon atoms, such as, but not limited to phenyl, tropone, indanyl or naphthyl
[0019] All ASTM tests are based on the 2003 edition of the Annual Book of ASTM Standards unless otherwise mdicated
[0020] The term "polymer blend" as used herein means a macroscopically homogeneous mixture of two or more different polymers The term "miscible blend" descnbes a polymer blend havmg a smgle glass transition temperature (Tg) and a monophasic resin morphology as determined by transmission electron microscopy at a magnification of fifteen thousand (15,000) "Delamination" describes the separation of a surface layer from the body of an article molded from a polymer composition The presence or absence of delamination can be determined by visual inspection (20/20 vision) at a distance of one half (1/2) meter as described m greater detail below
[0021] A "compatible" polymer blend is an immiscible polymer blend that exhibits macroscopically uniform physical properties throughout its whole volume, has more than one glass transition temperature (Tg), and shows multiphasic resm morphologies when viewed by electron microscopy as descnbed above, but shows no delamination
[0022] The term "non-delaminated" refers to the property of a composition or an article derived from the composition, m which the article or the composition does not exhibit visually observed separation of a surface layer showmg a flaking or onion skin effect A non-delaminated article may also be referred to herein as "essentially free from delamination "
[0023] "Essentially free from delamination" is defined as showing no delamination by visual inspection In one embodiment, the specimen used for inspection is an injection molded bar A specimen showmg delamination is shown in Figure 1 A specimen essentially free from delamination is shown m Figure 2 "Visual inspection" is
determined by unaided vision (e g, 20/20 vision in the absence of any magnifying device with the exception of corrective lenses necessary for normal eyesight) at a distance of one half (1/2) meter
[0024] The "pre-polymer" is an incompletely unidized oligomer comprising structural units derived from a dianhydride and a diamine Exemplary dianhydndes have the formula (I)
(Formula Removed)
wherein V is a tetravalent linker selected from the group consistmg of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycychc groups havmg 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups havmg 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups havmg 2 to 30 carbon atoms and combinations comprising at least one of the foregomg linkers Suitable substitutions and/or linkers mclude, but are not limited to, carbocyclic groups, aryl groups, ethers, sulfones, sulfides amides, esters, and combmations comprising at least one of the foregomg Exemplary linkers mclude, but are not limited to, tetravalent aromatic radicals of formula (II), such as
(Formula Removed)
wherein W is a divalent moiety such as -0-, -S-, -C(O)-, -SO2-, -SO-, -CyH2y- (y bemg an integer of 1 to 20), and halogenated derivatives thereof, including perfluoroalkylene groups, or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -
0-Z-O- group are m the 3,3', 3,4', 4,3', or the 4,4' positions, and wherein Z includes, but is not limited to, divalent moieties of formula (III)
(Formula Removed)
wherein Q mcludes, but is not limited to, a divalent moiety comprising -0-, -S-, -C(O)-, -SO2-, -SO-, -CyH2y- (y being an mteger from 1 to 20), and halogenated derivatives thereof, mcludmg perfluoroalkylene groups In some embodiments the tetravalent linker V is free of halogens In some embodiments groups free of benzylic protons are used as the resulting pre-polymer (as well as the polymer blend) can have superior melt stability
[0025] In one embodiment, the dianhydride compnses an aromatic bis(ether
anhydnde) Examples of specific aromatic bis(ether anhydnde)s are disclosed, for
example, m U S Patent Nos 3,972,902 and 4,455,410 Illustrative examples of aromatic
bis(ether anhydnde)s mclude 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride (bisphenol-A dianhydride), 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether
dianhydnde, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydnde, 4,4'-bis(3,4-
dicarboxyphenoxy)benzophenone dianhydnde, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl
sulfone dianhydnde, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydnde, 4,4'-
bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydnde, 4,4'-bis(2,3-
dicarboxyphenoxy)diphenyl sulfide dianhydnde, 4,4'-bis(2,3-
dicarboxyphenoxy)benzophenone dianhydnde, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl
sulfone dianhydnde, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-
propane dianhydnde, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl
ether dianhydnde, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide
dianhydnde, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone
dianhydnde and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydnde, as well as mixtures comprising at least two of the foregoing In one embodiment the dianhydnde is selected from the group consisting of oxydiphthahc anhydndes, bisphenol-A dianhydndes and combinations thereof
[0026] The bis(ether anhydnde)s can be prepared by the hydrolysis, followed by dehydration, of the reaction product of a nitro substituted phenyl dinitnle with a metal salt of dihydnc phenol compound m the presence of a dipolar, aprotic solvent
[0027] A chemical equivalent to a dianhydnde may also be used Examples of dianhydnde chemical equivalents mclude tetra-functional carboxylic acids capable of forming a dianhydnde and ester or partial ester denvatives of the tetra functional carboxylic acids Mixed anhydnde acids or anhydnde esters may also be used as an equivalent to the dianhydnde As used throughout the specification and claims "dianhydnde" will refer to dianhydndes and their chemical equivalents
[0028] Useful diamines have the formula
(Formula Removed)
wherein R10 is a substituted or unsubstituted divalent organic moiety such as an aromatic hydrocarbon moiety havmg 6 to 20 carbons and halogenated derivatives thereof, straight or branched cham alkylene moiety havmg 2 to 20 carbons, cycloalkylene moiety havmg 3 to 20 carbon atom, or divalent moieties of the general formula (V)
(Formula Removed)
wherein Q is defined as above Examples of specific organic diamines are disclosed, for
example, m US Patent Nos 3,972,902 and 4,455,410 Exemplary diamines include
ethylenediamine, propylenediamine, tnmethylenediamine, diethylenetnamine,
triethylenetetramine, hexamethylenediamine, heptamethylenediamine,
octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-
dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-
dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-
methylnonamethylenediamme, 2,5-dimethylhexamethylenediamine 2,5-
dimethylheptamethylenediamme, 2, 2-dimethylpropylenediamme, N-methyl-bis (3-ammopropyl) amine, 3-methoxyhexamethylenediamme, l,2-bis(3-ammopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamme, bis-(4-ammocyclohexyl) methane, m-phenylenediamine, p-phenylenediamme, 2,4-diaminotoluene, 2,6-diammotoluene, m-xylylenediamine, p-xylylenediamme, 2-methyl-4,6-diethyl-l,3-phenylene-diamme, 5-methyl-4,6-diethyl-l,3-phenylene-diamine, benzidme, 3,3'-dimethylbenzidme, 3,3'-dimethoxybenzidme, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-ammo-3, 5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(p-amino-t-butyl) toluene, bis(p-ammo-t-butylphenyl) ether, bis(p-methyl-o-ammophenyl) benzene, bis(p-methyl-o-aminopentyl) benzene, 1, 3-diammo-4-isopropylbenzene, bis(4-ammophenyl) sulfide, bis (4-ammophenyl) sulfone, bis(4-aminophenyl) ether and 1,3-
bis(3-aminopropyl) tetramethyldisiloxane Mixtures of these compounds may also be used In one embodiment the diamine is an aromatic diamine, or, more specifically, m-phenylenediamine, p-phenylenediamine, sulfonyl dianiline and mixtures thereof In one embodiment the diamine is selected from the group consisting of diamino diaryl sulfones, metaphenylene diamines, paraphenylene diamines, and combinations thereof
[0029] In some embodiments the pre-polymer is a polyethenmide pre-polymer comprising structural units denved from oxydiphthalic anhydride (ODPA) and diamino diaryl sulfone (DAS) Oxydiphthalic anhydnde has the general formula (VI)
(Formula Removed)
and denvatives thereof as further defined below
[0030] The oxydiphthalic anhydrides of formula (VI) includes 4,4'-oxybisphthahc anhydnde, 3,4'-oxybisphthahc anhydnde, 3,3'-oxybisphthahc anhydnde, and any mixtures thereof For example, the oxydiphthalic anhydnde of formula (VI) may be 4,4'-oxybisphthahc anhydnde having the following formula (VII)
(Formula Removed)
[0031] The term oxydiphthalic anhydndes includes denvatives of oxydiphthalic anhydrides which may also be used to make the pre-polymer Examples of oxydiphthalic anhydnde derivatives which can function as a chemical equivalent for the oxydiphthalic anhydnde in polyethenmide formmg reactions include oxydiphthalic anhydnde derivatives of the formula (VIII)
(Formula Removed)
wherein R1 and R2 of formula VIII can be, independently at each occurrence, any of the following hydrogen, a C1-C8 alkyl group, an aryl group R1 and R2 can be the same or different to produce an oxydiphthahc anhydride acid, an oxydiphthalic anhydride ester, and an oxydiphthahc anhydride acid ester
[0032] Derivatives of oxydiphthahc anhydrides may also be of the following formula (IX)
(Formula Removed)
wherein R1, R2, R3, and R4 of formula (IX) can be, independently at each occurrence, any of the following hydrogen, a C1-C8 alkyl group, an aryl group R1, R2, R3, and R4 can be the same or different to produce an oxydiphthahc acid, an oxydiphthahc ester, and an oxydiphthahc acid ester
[0033] Diamino diaryl sulfones (DAS) have the general formula (X)
(Formula Removed)
wherein Ar1 and Ar2 independently are an aryl group containing a single or multiple rings Several aryl rings may be linked together, for example through ether linkages, sulfone linkages or more than one sulfone linkages The aryl rmgs may also be fused In one embodiment Ar1 and Ar2 mdependently compnse 5 to 12 carbons In one embodiment Ar1 and Ar2 are both phenyl groups
[0034] In one embodiment, the pre-polymer is an ODPA/DAS polyethenmide comprising more than 1, specifically 10 to 1000, or, more specifically, 30 to 500 structural units of formula (XI)
(Formula Removed)
wherein Ar1 and Ar2 are defined as above
[0035] In one embodiment, the pre-polymer has a total reactive end group concentration of 0 5 to 20 mole% resin Reactive end groups are defined as anhydrides and their chemical equivalents and amines In some embodiments, a pre-polymer has a weight average molecular weight of 1,000 to 100,000 grams per mole (g/mole) as measured by gel permeation chromatography (GPC)
[0036] The pre-polymer can have different ratios of carbon (C) atoms to non-carbon atoms such as nitrogen (N), oxygen (O), and sulfur (S) For instance, in one embodiment, the pre-polymer can have a ratio of C atoms/N+O+S atoms of 2 8 to 4 2 In one embodiment, the number of oxygen atoms is greater than or equal to 2 5 times the number of nitrogen atoms In another embodiment, the number of oxygen atoms is 2 5 to 5 0 times more than the number of nitrogen atoms In another embodiment, the number of
oxygen atoms is greater than or equal to 7 tunes the number of sulfur atoms In another embodiment, the number of oxygen atoms is 7 to 10 times the number of sulfur atoms
[0037] The pre-polymer may be made by any suitable process, such as the process descnbed inUS Patent Number 4,835,249 In this method, reactant monomers are dissolved in a solvent and then polymerized to an extent where the polymer precipitates from solution and can eventually be isolated by filtration or other related separation technique
[0038] When the pre-polymer is an ODPA/DAS pre-polymer the pre-polymer is made usmg a slurry/precipitation method comprising stirring a diamine and a dianhydride m a solvent to form a slurry, heatmg the slurry to a temperature sufficient for the diamine and dianhydride to react wherem the temperature is below the meltmg point of the dianhydride, below the meltmg pomt of the diamine, or below the meltmg points of the dianhydride and diamine, and reacting the diamine and dianhydride to form a polyethenmide having sufficient molecular weight to precipitate from the solvent
[0039] In the above process, it is important that the reaction temperature is kept below the meltmg pomt of the minimally soluble monomers so that the polymers precipitate as fine powder from the slurry that is easily stirred It can be useful to remove water, or other volatile by-products from the reaction mixture by distillation or other means In one embodiment azeotropic distillation of water is employed In some embodiments water can be removed by chemical absorption using, for example, molecular sieves In other instances water can be removed usmg a stream of a gas, for example nitrogen, passing over or through the reaction mixture In addition, a combination of two or more water removal methods may be employed
[0040] In one embodiment, the polymerization is conducted entirely below the melting point of the minimally soluble monomer(s) This may be useful when the boiling point temperature of the solvent and the meltmg pomt of the minimally soluble monomer(s) are greater than 100 °C, to allow removal of water from the polymerization
reaction at atmospheric pressure
[0041] It can be useful to conduct the polymerization under pressure, for example at 1 to 300 pounds per square inch (psi) (21 1 kilograms force per square centimeter (kgf/cm2)), or, more specifically, 1 psi (0 070 kgf/cm2) to 100 psi (7 0 kgf/cm2) This can be done for a variety of reasons, one bemg to raise reaction temperature and mcrease the rate of imidization In order to prevent sticking or clumping of the precipitated polymer it is still important to maintain temperature below the melting point of the mmimally soluble monomer(s) even when pressure is increased In some embodiments, it may be useful to remove water from the reaction while pressure is maintained at atmospheric pressure In some embodiments it can be useful to remove water in a multi step process employing pressures greater than or equal to atmospheric pressure
[0042] After the consumption of equal to or greater than 50 weight percent (wt%) of the initial charge of the monomers it can be useful m some embodiments to isolate the precipitated polymer In other embodiments the precipitated polymer may be isolated when equal to or greater than 90 wt% of the initial charge of monomers are consumed This can be done usmg a variety of methods, for example, filtration, centnfugation, floatation, freeze-drying, and combinations compnsmg one or more of the foregoing methods In some embodiments equal to or greater than 95 wt% of the isolated precipitated polyethenmide, based on the total weight of the isolated precipitated polyethenmide, passes through a 2 millimeter (mm) mesh screen In some embodiments the isolated precipitated polyethenmide is a free flowing powder with an average particle size of 10 to 5000 micrometers
[0043] The solvent used to form the slurry is chosen such that one or more of the initial monomers is minimally soluble "Minimally soluble" is defined as 1 to 50 wt% of the monomer is undissolved at the start of the reaction (at the initial reaction conditions) In addition, the solvent should be chosen such that the resultant polymer is largely insoluble, that is to have a polymer solubility of less than or equal to 10 wt %, or, even more specifically, less than or equal to 5 wt%, or, even more specifically, less than or
equal to 1 wt % In some embodiments the solvent compnses an aprotic polar solvent In some embodiments, the solvent is insoluble in water, that is less than or equal to 5 wt%, or, more specifically, less than or equal to 1 wt%, based on the total amount of solvent, of the solvent dissolves in an equal amount of water at room temperature In some embodiments, the solvent has a high auto ignition temperature, for example greater than or equal to 70 °C, to reduce the potential fire hazard during the process and during any subsequent isolation
[0044] In addition, a solvent free of nitrogen atoms, phosphorus atoms, sulfur atoms or a combmation comprising two or more of the foregomg may be useful m some embodiments Solvents without these more polar atoms may be easier to remove from the polymer and being less effective solvents are more likely to have monomers and polymers that are minimally soluble or insoluble
[0045] Examples of useful solvents for forming the pre-polymer include halogenated aromatics, such as chlorobenzene, dichlorobenzene, trichlorobenzene and bromobenzene, aryl ethers such as phenetole, anisole and veratrole, alkylaromatics such as xylenes and toluene, nitro aromatics such as nitrobenzene, polyaryl species such as naphthylene and alkyl substituted fused aromatic systems, aryl sulfone, high molecular weight alkane compounds such as mineral oils, and combinations comprising one or more of the foregomg solvents In some embodiments the solvent or combmation of solvents has an atmospheric boiling pomt of 150 to 250 °C
[0046] The reaction to form the pre-polymer may be run at any level of reactants versus solvent In some mstances the weight % solids can be 5 to 50 % by weight of reactants to solvent at the start of the polymerization reaction In other mstances, concentrations of 15 to 40% by weight may be useful In still other instances higher concentrations of reactants to solvent may be used to gam reactor efficiency
[0047] Polyethenmide pre-polymer may be made usmg the precipitative process by reaction of more or less equal molar amounts of dianhydnde (or chemical equivalent of a dianhydnde) with a diamine In some embodiments the amount of dianhydnde and diamine differ by less than 5 mole%, this helps to give polymers of sufficient molecular weight (Mw), for example greater than or equal to 1,000 g/mol, to precipitate from the reaction medium and have useful mechanical properties such as stiffness, impact strength and resistance to tearing or cracking
[0048] Polyethenmide polymers and polyethenmide pre-polymers may have varying levels of amme and anhydnde end groups depending on the amounts of diamine and dianhydnde used in the polymenzation reaction and the degree of completeness of the polymerization reaction A vanety of amine, anhydnde, and anhydride denvatives such as carboxyhc acids, carboxylate salts, amide-acids and amide-carboxylate salts are examples of possible end groups As used herein it will be understood that the term "amme end groups" compnses end groups that are amines, and any related end groups that are denved from amine end groups As used herein it will also be understood that the term "anhydnde end groups" comprises end groups which are anhydndes and anhydnde derivatives such as carboxyhc acid, carboxylate salts, amide-acids and amide-carboxylate salts All types, more than one type or essentially one type of these end groups may be present In general, total reactive end group concentrations of a polyethenmide can be 0 05 to 0 3 mole% resin In contrast, the total reactive end group concentrations of a pre-polymer can be 0 5 to 20 mole% As used herein, the term "reactive end group" refers to any of the vanous possible end groups that can give nse to volatile species dunng melt processmg Most reactive end groups will be amme or anhydride In one embodiment, the pre-polymer has a total reactive end group content of 1 to 10 mole%, or, more specifically, 5 to 10 mole%
[0049] The concentration of amine, anhydnde, and related end groups can be analyzed by vanous titration and spectroscopic methods well known in the art Spectroscopic methods include infrared, nuclear magnetic resonance, Raman
spectroscopy, and fluorescence Examples of infrared methods are descnbed in J A Kreuz, et al, and J Poly Sci Part A-1, vol 4, pp 2067-2616 (1966) Examples of titration methods are descnbed in Y J Kim, et al, Macromolecules, vol 26, pp 1344-1358 (1993) It may be advantageous to make derivatives of polymer end groups to enhance measurement sensitivity usmg, for example, variations of methods as described in K P Chan et al, Macromolecules, vol 27, p 6731 (1994) and J S Chao, Polymer Bull, vol 17, p 397 (1987)
[0050] The molecular weight of pre-polymer can be measured by gel permeation chromatography (GPC) The molecular weights as used here refer to the weight average molecular weight (Mw) In one embodiment, the pre-polymer has a weight average molecular weight of 1,000 to 100,000 grams per mole (g/mole) as measured by gel permeation chromatography (GPC) In some embodiments the Mw can be 2,000 to 20,000
[0051] The polymer compnses end groups reactive with anhydride, amine or a combination thereof under melt mixmg conditions Exemplary endgroups include and are not limited to amine, anhydnde, hydroxyl, alcohol, amide, epoxide, ester, thiol, acid and activated aromatic hahde, and combmations thereof Exemplary polymers include polyimides, polyethenmides, polyamideimides, polyaryl ether ketones, polyaryl ketones, polyether ketones, polyether ether ketones, polyaryl sulfones, liquid crystal polymers, polyamides, polyesters, polysulfones, polyphenylene sulfides, polybenzimidazoles, polyphenylenes, and combmations thereof The foregoing exemplary polymers are commercially available e g, Aurum polyimides (Mitsui), ULTEM polyethenmides (GE), PEEK (Victrex), Radel polysulfones (Solvay) and Fortran PPS (Ticona)
[0052] The polymer may be a polyethenmide denved from the dianhydndes and diamines descnbed above In some embodiments, the polymer is a polyethenmide compnsing structural units denved from bisphenol-A dianhydnde (BPADA) and diamino diarylsulfone (DAS) Bisphenol-A dianhydnde has the following formula (XII)
(Formula Removed)
[0053] Similar to the discussion above with regard to oxydiphthalic anhydnde, the term "bisphenol-A dianhydnde" is inclusive of chemical denvatives of the anhydnde functionality which can function as a chemical equivalent for the bisphenol-A dianhydnde in polyetherunide forming reactions
[0054] In one embodiment the diamino diaryl sulfone is diamino diphenyl sulfone
[0055] In one embodiment, the polymer is a BPADA/DAS polyetherunide compnsmg more than 1, or, specifically 10 to 1000, or, more specifically, 30 to 500 structural units of the formula (XIII)
(Formula Removed)
The polyetherunide can have a weight average molecular weight (Mw) of 5,000 to 100,000 grams per mole (g/mole) as measured by gel permeation chromatography (GPC) In some embodiments the Mw can be 10,000 to 80,000
[0056] In some embodiments the polymer is a polyetherunide denved from bisphenol-A dianhydnde (BPADA) and phenylene diamine (PD) (a BPADA/PD polyetherunide) More specifically, the structural units can be denved from bisphenol-A dianhydnde (BPADA) and meta-phenylene diamine (MPD), BPADA and para-phenylene diamine (PPD), or combinations thereof
[0057] Meta-phenylene diamine (MPD) has the following formula (IX)

(Formula Removed)
[0058] Para-phenylene diamme (PPD) has the following formula (XI)


(Formula Removed)
[0059] The BPADA/PD polyethenmide compnses more than 1, or, specifically 10 to 1000, or, more specifically, 30 to 500 structural units of the formula (X), formula (XII) or a combination thereof

(Formula Removed)
[0060] In embodiments where the polymer is a polyethenmide, the polyethenmide may be made usmg any suitable method known in the art In one embodiment, a method usmg a highly polar solvent that dissolves both the reactant monomers and the resultant polymers can be used Solvents such as dimethyl formamide (DMF), dimethyl acetamide (DMAC), N-methyl pyrrohdinone (NMP), hexamethyl phosphoramide (HMPA) and dimethyl sulfoxide (DMSO) can be used m this method The resultant polymers are totally dissolved and can be isolated from solution by removal of solvent as part of a film castmg or other evaporative process or by precipitation using an anti-solvent such as methanol
[0061] The compositions described herein may further contain fillers, reinforcements, additives, and combinations thereof Exemplary fillers and reinforcements include fiber glass, milled glass, glass beads, flake and the like Minerals such as talc, wollastonite, mica, kaolm or montmonllonite clay, silica, quartz, bante, and combinations of two or more of the foregoing may be added The compositions can comprise inorganic fillers, such as, for example, carbon fibers and nanotubes, metal fibers, metal powders, conductive carbon, and other additives including nano-scale reinforcements as well as combinations of inorganic fillers
[0062] Other additives include, UV absorbers, stabilizers such as light stabilizers and others, lubricants, plasticizers, pigments, dyes, colorants, anti-static agents, foaming agents, blowmg agents, metal deactivators, and combinations compnsmg one or more of the foregomg additives Antioxidants can be compounds such as phosphites, phosphonites and hindered phenols or mixtures thereof Phosphorus containing stabilizers mcludmg tnaryl phosphite and aryl phosphonates are of note as useful additives Difunctional phosphorus containing compounds can also be employed Stabilizers may have a molecular weight greater than or equal to 300 In some embodiments, phosphorus containing stabilizers with a molecular weight greater than or equal to 500 are useful Phosphorus contaming stabilizers are typically present in the composition at 0 05-0 5% by weight of the formulation Flow aids and mold release compounds are also contemplated
[0063] In some embodiments, the compositions may further mclude second polymer Examples of such polymers include and are not limited to PPSU (polyphenylene sulfone), PEI (poly(ether lmide)), PSU (polysulfone), PC (polycarbonate), PPE (polyphenylene ether), PMMA (poly methyl methacrylate), ABS (acrylonitrile butadiene styrene), PS (polystyrene), PVC (polyvmylchlonde), PFA (per fluoro alkoxy alkane), MFA (co-polymer of TFE tetra fluoro ethylene and PFVE perfluonnated vinyl ether), FEP (Fluonnated ethylene propylene polymers), PPS (poly(phenylene sulfide), PEK (poly(ether ketone), PEEK (poly(ether-ether ketone),
ECTFE (ethylene chloro tnfluoro ethylene), PVDF (polyvmyhdene fluonde), PTFE (polytetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polyamide), UHMW-PE (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene), PBI (polybenzimidizole), PAI (poly(amide-imide), poly(ether sulfone), poly(aryl sulfone), polyphenylenes, polybenzoxazoles, polybenzthiazoles, as well as blends and co-polymers thereof
[0064] Compositions may be made by any suitable method For instance, compositions can be made by melt mixing (compounding) the pre-polymer, the polymer and, optionally, additives, in a suitable device such as twin screw extruder at a suitable temperature, e g, 250°C to 450°C Melt mixing is performed by mixing the composition components at a temperature sufficient to maintain the pre-polymer and the polymer in a molten state The temperature is less than the degradation temperatures of the pre-polymer and the polymer In some embodiments an extruder is used for melt mixing Optionally, the extruder may have a vacuum vent In some embodiments the pre-polymer and the polymer are melt mixed to form the polymer blend and additional components are added to the polymer blend The polymer blend may be pelletized and then the polymer blend pellets melt mixed with additional components, or the additional components may be added to the polymer blend without a pelletizing step
[0065] The pre-polymer may be present m an amount of 1 weight percent (wt%) to 99 wt%, or, more specifically, 10 wt% to 90 wt%, or, even more specifically, 20 wt% to 80 wt%, based on the combmed weight of the pre-polymer and the polymer The polymer may be present m an amount of 1 wt% to 99 wt%, or, more specifically, 10 wt% to 90 wt%, or, even more specifically, 20wt% to 80 wt%, based on the combmed weight of the pre-polymer and the polymer
[0066] The compositions of the mvention can be formed into articles by any number of methods Preferred methods mclude, for example, mjection moldmg, blow moldmg, compression moldmg, profile extrusion, sheet or film extrusion, sintering, gas
assist molding, structural foam molding and thermoforming Film and sheet extrusion processes may mclude and are not limited to melt casting, blown film extrusion and calendaring Examples of such articles include, but are not limited to, films, membranes, tubing, composites, semi-conductor process tools, wire coatings and jacketing, fluid handling components, cookware, food service items, medical devices, trays, plates, handles, helmets, animal cages, electrical connectors, enclosures for electrical equipment, engine parts, automotive engine parts, bearings, lighting sockets and reflectors, electric motor parts, power distribution equipment, communication equipment, computers and the like, including devices that have molded in snap fit connectors The blends can also be used as fibers In addition the blends can be used as coatings, for example powder coatings
[0067] Films may have a thickness of 0 1 to 1000 micrometers m some instances Co-extrusion and lamination processes may be employed to form composite multi-layer films or sheets Smgle or multiple layers of coatings may further be applied to the smgle or multi-layer substrates to impart additional properties such as scratch resistance, ultra violet light resistance, aesthetic appeal, etc Coatmgs may be applied through standard application techniques such as rolling, spraying, dipping, brushing, or flow coatmg Film and sheet may alternatively be prepared by castmg a solution or suspension of the composition in a suitable solvent onto a substrate, belt or roll followed by removal of the solvent Films may also be metallized using standard processes such as sputtering, vacuum deposition and lamination with foil
[0068] Oriented films may be prepared through blown film extrusion or by stretching cast or calendared films m the vicinity of the thermal deformation temperature using conventional stretching techniques For instance, a radial stretching pantograph may be employed for multi-axial simultaneous stretching, an x-y direction stretching pantograph can be used to simultaneously or sequentially stretch in the planar x-y directions Equipment with sequential uniaxial stretching sections can also be used to achieve uniaxial and biaxial stretching, such as a machine equipped with a section of
differential speed rolls for stretching m the machine direction and a tenter frame section for stretching in the transverse direction
[0069] Compositions discussed herem may be converted to multiwall sheet compnsmg a first sheet having a first side and a second side, wherem the first sheet comprises a thermoplastic polymer, and wherem the first side of the first sheet is disposed upon a first side of a plurality of nbs, and a second sheet havmg a first side and a second side, wherein the second sheet comprises a thermoplastic polymer, wherem the first side of the second sheet is disposed upon a second side of the plurality of nbs, and wherein the first side of the plurality of ribs is opposed to the second side of the plurality of nbs
[0070] The films and sheets descnbed above may further be thermoplastically processed mto shaped articles via formmg and moldmg processes mcluding but not limited to thermoforming, vacuum formmg, pressure forming, injection molding and compression moldmg Multi-layered shaped articles may also be formed by injection molding a thermoplastic resm onto a single or multi-layer film or sheet substrate as descnbed below
1) Providing a single or multi-layer thermoplastic substrate having optionally one or more colors on the surface, for instance, using screen pnnting of a transfer dye
2) Conforming the substrate to a mold configuration such as by formmg and trimming a substrate mto a three dimensional shape and fittmg the substrate mto a mold havmg a surface which matches the three dimensional shape of the substrate
3) Injecting a thermoplastic resm mto the mold cavity behrnd the substrate to (l) produce a one-piece permanently bonded three-dimensional product or (n) transfer a pattern or aesthetic effect from a printed substrate to the mjected resm and remove the pnnted substrate, thus imparting the aesthetic effect to the molded resm
[0071] Those skilled in the art will also appreciate that common curing and surface modification processes including and not limited to heat-setting, texturing, embossing, corona treatment, flame treatment, plasma treatment and vacuum deposition may further be applied to the above articles to alter surface appearances and impart additional functionalities to the articles Accordingly, another embodiment of the invention relates to articles, sheets and films prepared from the compositions above
[0072] The physical properties of the compositions, and articles derived from the compositions, are useful and can vary For instance, in embodiments where the pre-polymer and the polymer comprise a common diamine, the polymer blend can have a single resm glass transition temperature
[0073] When the polymer blend has a single glass transition temperature, the glass transition temperature can be greater than or equal to 100°C, or, more specifically, greater than or equal to 125°C, or, even more specifically, greater than or equal to 150°C The glass transition temperature can be less than or equal to 600°C
[0074] In embodiments where the pre-polymer and the polymer do not have a common monomer the compatible polymer blend has greater than one glass transition temperature In some embodiments the composition has two glass transition temperatures In some embodiments the lowest glass transition temperature is greater than or equal to 50°C, or, more specifically, greater than or equal to 75°C, or, even more specifically, greater than or equal to 100°C The lowest glass transition temperature can be less than or equal to 600°C
[0075] In some embodunents the polymer blend has a melt viscosity of 50 to 20,000 Pascal-seconds at 380°C as measured by ASTM method D3835 usmg a capillary rheometer with a shear rate of 100 to 10,000 1/sec Within this range the melt viscosity can be greater than or equal to 100, or, more specifically, greater than or equal to 200 Also within this range the melt viscosity can be less than or equal to 15,000, or, more specifically, less than or equal to 10,000 Pascal-seconds
[0076] In another embodiment, the composition (and articles made from the composition) can have heat deflection temperature (HDT) of greater than or equal to 100°C, according to ASTM D648 In one embodiment, compositions can have an HDT of 100°C to 400°C, according to ASTM D648 In another embodiment, the compositions, and articles denved from the compositions, can have a tensile strength of greater than or equal to 70 megaPascals (MPa) according to ASTM D638 In one embodiment, the compositions and articles can have a tensile strength of 70 MPa to 500 MPa The coefficient of thermal expansion of the compositions can vary In one embodiment, the coefficient of thermal expansion is less than 100 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute In another embodiment, the coefficient of thermal expansion is 5 to 100 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute
[0077] Compositions and articles derived from the compositions can also exhibit advantageous heat aging performance properties For mstance, in one embodiment, a composition (and articles denved from the composition) can have a continuous use temperature of greater than or equal to 150°C, or above A composition can have a continuous use temperature of 150°C to 400°C
[0078] Advantageously, the compositions described herem now provide previously unavailable compositions and articles For mstance, the compositions can overcome the problem of delamination in an immiscible, incompatible blends and exhibit immiscible, but compatible blend features having highly useful applications The compositions can provide a much wider range of miscible blend compositions Compositions of the invention can exhibit an improved visual transparent appearance Extendmg the range of miscibihty in such blends has significant practical importance It is now possible to make a wide vanety of blend compositions with a single glass transition temperature (Tg) and pre-determined transparency
[0079] The following examples are included to provide additional guidance to those skilled in the art The examples provided are merely representative and are not intended to limit the invention, as defined in the appended claims, in any manner
EXAMPLES
[0080] Matenals used in the Examples are listed Table 1 Amounts listed m the Examples are in weight percent based on the combined weight of the first and second polymers used
Table 1
(Table Removed)
Examples 1-9
[0081] The purpose of these examples is to show that blending with a reactive pre-polymer can overcome the problem of delamraation m an immiscible, mcompatible
blend These examples also show that blending with a reactive pre-polymer can improve the irascibility in an immiscible, but compatible blend and result in a much wider range of miscible blend compositions The examples also show how visual appearance can also improve
Preparation Techniques
[0082] The compositions shown m Table 2 were prepared by melt mixmg the components in a twin screw extruder at temperatures of 300°C to 430°C with vacuum venting The screw speed typically varied from 100 to 350 rotations per minute (RPM)
Testing Techniques
[0083] The compositions were tested for glass transition temperature usmg differential scanning calonmetry (DSC) Morphology was determined by visual mspection usmg mjection molded ASTM tensile bars The tensile bars were aged at 280°C for 240 hours and checked for delammation by visual mspection Visual inspection was determined by normal vision (e g, 20/20 vision m the absence of any magnifying device with the exception of corrective lenses necessary for normal eyesight) at a distance of one half (1/2) meter Results are shown in Tables 2 and 3
Results
Table 2 (Table Removed)
"■Comparative example
Table 3 (Table Removed)
♦Comparative examples
Discussion
[0084] Examples 1-3 (which are based on pre-polymers) when compared to Comparative Example 4 (which is not based on a pre-polymer) show the unexpected behavior of polyethenmide blends when a pre-polymer was used to make the blends Blends of PEI 1 and PEI 3 exhibited two phase morphology and delammation even at low levels of PEI 3 (15 weight %) In contrast, despite the two phase resm morphology, blends of pre-polymer and PEI 3, even at 40 weight %, did not show delammation after heat aging at 280°C for 240 hours Surprisingly, melt mixmg with a reactive pre-polymer overcame the problem of delammation in an immiscible, incompatible blend and resulted m an immiscible, but compatible blend of practical importance
[0085] Examples 5-7 (which are based on pre-polymers) when compared to Comparative Examples 8 and 9 (which are not based on pre-polymers) illustrated the unexpected behavior of polyethenmide blends when a pre-polymer was used to make the blends Blends of PEI 1 and PEI 2 showed two phase morphology at low levels of PEI 2
(15 weight %) Despite the multiphasic resin morphology, the blends of PEI1 and PEI2 did not show any delamination In contrast, blends of pre-polymer and PEI 2 showed a monophasic morphology with a single Tg at the same levels of PEI 2 (15 weight%) and even at a high level of PEI 2 (40 weight%) No delamination after heat aging at 280°C for 240 hours was observed in any of these blends
[0086] The blend of Example 7 also demonstrated excellent properties More particularly, the blend of Example 7 exhibited tensile strength of 120 MPa, flexural strength of 170 MPa, HDT of 240°C under a load of 1 8MPa, and a coefficient of thermal expansion of 45 ppm/°C from 30-200°C
[0087] Thus, Examples 5-7 showed that blending with a reactive pre-polymer improved the miscibihty in an immiscible, but compatible blend and resulted m a much wider range of miscible blend compositions The visual appearance also improved from translucent to transparent Extendmg the range of miscibihty m such a blend has significant practical importance since a wide variety of blend compositions with a smgle Tg and transparency could now be designed
[0088] While the mvention has been described with reference to several embodiments, it will be understood by those skilled in the art that vanous changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention In addition, many modifications may be made to adapt a particular situation or material to the teachmgs of the mvention without departing from essential scope thereof Therefore, it is intended that the mvention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this mvention, but that the mvention will mclude all embodiments falling within the scope of the appended claims All patents identified by number herem are incorporated by reference in their entirety








WHAT IS CLAIMED:
1. A composition comprising a polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from a dianhydride and a diamine; and
(b) a polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof;
wherein the reactive member is reactive with the free anhydride groups, the free amine groups, or combinations thereof and wherein the polymer blend is non-delaminated.
2. The composition of claim 1, wherein the dianhydride is oxydiphthalic anhydride and the diamine is a diamino diaryl sulfone.
3. The composition of claim 1, wherein the polymer is selected from the group consisting of polyimides, polyetherimides, polyamideimides, polyaryl ether ketones, polyaryl ketones, polyether ketones, polyether ether ketones, polyaryl sulfones, liquid crystal polymers, polyamides, polyesters, polysulfones, polyphenylene sulfides, polybenzimidazoles, polyphenylenes, and combinations of two or more of the foregoing.
4. The composition of claim 1, wherein the polymer blend has two glass transition temperatures and an article molded from the composition exhibits no delamination after aging at 280°C for 240 hours.
5. The composition of claim 4, wherein the two glass transition temperatures are greater than or equal to 50°C.
6. The composition of claim 1, wherein the polymer blend has one glass transition temperature.
7. The composition of claim 6, wherein the one glass transition temperature is greater than or equal to 100°C.
8. The composition of claim 1, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer.
9. The composition of claim 8, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 10 weight percent to 90 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 10 weight percent to 90 weight percent, based on the combined weight of the pre-polymer and the polymer.
10. The composition of claim 9, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer.
11. The composition of Claim 1, wherein the polymer blend has a heat deflection temperature greater than or equal to 100°C according to ASTM D648.
12. The composition of Claim 1, wherein the polymer blend has a tensile strength above 70 MPa according to ASTM D638.
13. The composition of Claim 1, wherein the polymer blend has a coefficient of thermal expansion of less than or equal to 100 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute.
14. The composition of Claim 1, wherein the polymer blend has a continuous use temperature greater than or equal to 150°C.
15. The composition of Claim 1, wherein the pre-polymer is essentially free of benzylic protons.
16. The composition of Claim 1, wherein the composition further comprises a second polymer.
17. The composition of Claim 16 wherein the second polymer is selected from the group consisting of polyphenylene sulfone, polyetherimide, polysulfone, polycarbonate, polyphenylene ether, poly methyl methaciylate, acrylonitrile butadiene styrene, polystyrene, polyvinylchloride, perfluoroalkoxyalkane polymer, co-polymer of tetra fluoro ethylene and perfluorinated vinyl ether, fluorinated ethylene propylene polymer, poly(phenylene sulfide, poly(ether ketone), poly(ether-ether ketone), ethylene chloro trifluoro ethylene polymer, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyacetal, polyamide, ultra high molecular weight polyethylene, polypropylene, polyethylene, high density polyethylene, low density polyethylene, polybenzimidizole, poly(amide-imide), poly(ether sulfone), poly(aryl sulfone), polyphenylenes, polybenzoxazoles, polybenzthiazoles and blends and copolymers thereof.
18. The composition of claim 1, wherein the pre-polymer has a ratio of carbon atoms/(nitrogen atoms+oxygen atoms+sulfur atoms) of 2.8 to 4.2.

19. A composition comprising a polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from a first dianhydride and a first diamine;
(b) a polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof and further comprising structural units derived from a second dianhydride and a second diamine;
wherein the first dianhydride is the same as the second dianhydride or the first diamine is the same as the second diamine, and
wherein the polymer blend has a single glass transition temperature.
20. The composition of claim 19, wherein the single glass transition temperature is greater than or equal to 100°C.
21. The composition of claim 19, wherein the first dianhydride or the second anhydride is selected from the group consisting of oxydiphthalic anhydrides, bisphenol-A dianhydrides, and combinations thereof.
22. The composition of claim 19, wherein the first diamine or the second diamine is selected from the group consisting of diamino diaryl sulfones, metaphenylene diamines, paraphenylene diamines, and combinations thereof.
23. The composition of claim 19, wherein the pre-polymer is essentially free of benzylic protons.
24. The composition of Claim 19, wherein the polymer blend has a heat deflection temperature greater than or equal to 100°C according to ASTM D648.
25. The composition of Claim 19, wherein the polymer blend has a tensile strength above 70 MPa according to ASTM D638.
26. The composition of Claim 19, wherein the polymer blend has a coefficient of thermal expansion of less than or equal to 100 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis wim a thermal ramp rate of 5°C/minute.
27. The composition of Claim 19, wherein the polymer blend has a continuous use temperature greater than or equal to 150°C.
28. The composition of claim 19, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer.
29. The composition of claim 28, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 10 weight percent to 90 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 10 weight percent to 90 weight percent, based on the combined weight of the pre-polymer and the polymer.
30. The composition of claim 28, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer.
31. The composition of claim 19, wherein the pre-polymer has a ratio of carbon atoms/(nitrogen atoms+oxygen atoms+sulfur atoms) of 2.8 to 4.2.
32. A composition comprising a polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from a first dianhydride and a first diamine;
(b) a polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof and further comprising structural units derived from a second dianhydride and a second diamine; and
wherein the first dianhydride is different from the second dianhydride and the first diamine is different from the second diamine, and
wherein the polymer blend has greater than one glass transition temperature and an article molded from the composition is essentially free from delamination after aging at 280°C for 240 hours.
33. The composition of claim 32, wherein the glass transition temperatures are greater man or equal to 50°C.
34. The composition of claim 32, wherein the first dianhydride, second dianhydride, or both the first and the second dianhydride is selected from the group consisting of oxydiphthalic anhydrides, bisphenol-A dianhydrides, and combinations thereof.
35. The composition of claim 32, wherein the first diamine, second diamine or both the first and the second diamine is selected from the group consisting of diamino diaryl sulfones, metaphenylene diamines, paraphenylene diamines, and combinations thereof.
36. The composition of claim 32 wherein the pre-polymer is essentially free of benzylic protons.
37. The composition of claim 32, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 1 weight percent to 99 weight percent, based on the combined weight of the pre-polymer and the polymer.
38. The composition of claim 32, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 10 weight percent to 90 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 10 weight percent to 9o weight percent, based on the combined weight of the pre-polymer and the polymer.
39. The composition of claim 32, wherein prior to forming the polymer blend the pre-polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer and the polymer is present in an amount of 20 weight percent to 80 weight percent, based on the combined weight of the pre-polymer and the polymer.
40. The composition of Claim 32, wherein the polymer blend has a heat deflection temperature greater than or equal to 100°C according to ASTM D648.
41. The composition of Claim 32, wherein the polymer blend has a tensile strength above 70 MPa according to ASTM D638.
42. The composition of Claim 32, wherein the polymer blend has a coefficient of thermal expansion of less than or equal to 100 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute.
43. The composition of Claim 32, wherein the polymer blend has a continuous use temperature greater than or equal to 150°C.
44. A composition comprising a polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from oxydiphthalic anhydrides and diamino diaryl sulfones;
(b) a polyetherimide polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof and further comprising structural units derived from bisphenol-A dianhydrides and diamino diaryl sulfones;
wherein the polymer blend has a single glass transition temperature.
45. A composition comprising a polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from oxydiphthalic anhydrides and diamino diaryl sulfones;
(b) a polyedierimide polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof and further comprising structural units derived from bisphenol-A dianhydrides and diamino diaryl sulfones;
wherein the polymer blend has greater than one glass transition temperature and an article molded from the composition is essentially free from delamination after aging at 280°C for 240 hours.
46. A composition comprising polymer blend derived from:
(a) a pre-polymer comprising a component selected from the group consisting of free amine groups, free anhydride groups, and combinations thereof and further comprising structural units derived from oxydiphthalic anhydride and diamino diaryl sulfone; and
(b) a poiyetherimide polymer comprising a reactive member selected from the group consisting of structural groups, end groups, and combinations thereof and further comprising structural units derived from bisphenol -A dianhydride and diamino diaryl sulfone; and further comprising
a stabilizer selected from the group consisting of antioxidants, phosphites, and combinations thereof;
wherein the polymer blend has a heat deflection temperature greater than or equal to 200°C according to ASTM D648; a tensile strength greater than or equal to 90 megaPascals according to ASTM D638; a coefficient of thermal expansion of less than or equal to 60 ppm/°C from 30°C-200°C as measured by thermal mechanical analysis with a thermal ramp rate of 5°C/minute;
wherein prior to the formation of the polymer blend the pre-polymer is present an amount of 50 to 95 weight percent and the poiyetherimide polymer is present in an amount of 5 to 50 weight percent, based on the combined weight of the pre-polymer and the polymer.
47. A composition of matter comprising an article derived from Claim 1.
48. A composition of matter comprising an article derived from Claim 32.
49. A composition of matter comprising an article derived from Claim 42.
50. A composition of matter comprising an article derived from Claim 43.
51. A composition of matter comprising an article derived from Claim 44.
52. The composition of matter of Claim 45, wherein the article is selected from the group consisting of films, membranes, tubing, composites, semi-conductor process tools, wire coatings and jacketing, fluid handling components, cookware, food service items, medical devices, trays, plates, handles, helmets, animal cages, electrical connectors, enclosures for electrical equipment, engine parts, automotive engine parts, bearings, lighting sockets and reflectors, electric motor parts, power distribution equipment, communication equipment, computers, devices have molded in snap fit connectors and fibers.

Documents:

3144-delnp-2009-Abstract-(02-06-2014).pdf

3144-delnp-2009-abstract.pdf

3144-DELNP-2009-Assignment (17-11-2009).pdf

3144-delnp-2009-Assignment-(31-07-2013).pdf

3144-delnp-2009-Claims-(02-06-2014).pdf

3144-delnp-2009-Claims-(31-12-2014).pdf

3144-delnp-2009-claims.pdf

3144-delnp-2009-Correspondance Others-(31-12-2014).pdf

3144-delnp-2009-Correspondence Others-(02-06-2014).pdf

3144-delnp-2009-Correspondence Others-(05-12-2013).pdf

3144-delnp-2009-Correspondence Others-(31-07-2013).pdf

3144-DELNP-2009-Correspondence-Others (17-11-2009).pdf

3144-delnp-2009-correspondence-others.pdf

3144-delnp-2009-description (complete).pdf

3144-delnp-2009-Drawings-(02-06-2014).pdf

3144-delnp-2009-drawings.pdf

3144-delnp-2009-form-1.pdf

3144-delnp-2009-form-18.pdf

3144-delnp-2009-form-2.pdf

3144-DELNP-2009-Form-3 (17-11-2009).pdf

3144-delnp-2009-Form-3-(05-12-2013).pdf

3144-delnp-2009-form-3.pdf

3144-delnp-2009-form-5.pdf

3144-delnp-2009-GPA-(02-06-2014).pdf

3144-delnp-2009-Others-(31-12-2014).pdf

3144-delnp-2009-pct-210.pdf

3144-delnp-2009-pct-304.pdf

3144-delnp-2009-pct-306.pdf

Petition under rule 137.pdf


Patent Number 264674
Indian Patent Application Number 3144/DELNP/2009
PG Journal Number 03/2015
Publication Date 16-Jan-2015
Grant Date 14-Jan-2015
Date of Filing 14-May-2009
Name of Patentee SABIC INNOVATIVE PLASTICS IP B.V
Applicant Address PLASTICSLAAN 1, NL-4612 PX BERGEN OP ZOOM THE NETHERLANDS
Inventors:
# Inventor's Name Inventor's Address
1 GALLUCCI ROBERT RUSSELL 1109 TANGLEWOOD DRIVE MT. VERNON, IN 47620 U.S.A
2 MULLEN TARA 1911 WESTRIDGE DRIVE MT. VERNON, IN 47620 U.S.A
3 ODLE ROY 7401 SAUERKRAUT LANE NORTH MT. VERNON, IN 47620 U.S.A
4 SHETH KAPIL CHANDRAKANT 331 HOPE COURT EVANSVILLE, IN 47712 U.S.A
5 WHITE JAMES M 1566 VALENCIA ROAD NISKAYUNA, NY 12309 U.S.A
PCT International Classification Number C08G 73/00
PCT International Application Number PCT/US2007/075809
PCT International Filing date 2007-08-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/562,625 2006-11-22 U.S.A.