WO2001029095A1 - Polymeres greffes contenant des amines, procedes de fabrication et d'utilisation associes - Google Patents

Polymeres greffes contenant des amines, procedes de fabrication et d'utilisation associes Download PDF

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WO2001029095A1
WO2001029095A1 PCT/US2000/028789 US0028789W WO0129095A1 WO 2001029095 A1 WO2001029095 A1 WO 2001029095A1 US 0028789 W US0028789 W US 0028789W WO 0129095 A1 WO0129095 A1 WO 0129095A1
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group
polymer
amine
groups
primary amine
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PCT/US2000/028789
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English (en)
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Jean-Roch Schauder
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Exxon Chemical Patents Inc.
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Priority to EP00973632A priority Critical patent/EP1237946A1/fr
Priority to AU12126/01A priority patent/AU1212601A/en
Priority to MXPA02003941A priority patent/MXPA02003941A/es
Priority to CA002388037A priority patent/CA2388037A1/fr
Publication of WO2001029095A1 publication Critical patent/WO2001029095A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • This invention is related to graft polymers and to a method for their manufacture.
  • it relates to functional polymers grafted with certain amine compounds and further processed to produce a polymer having pendant primary amine functionality.
  • thermoplastics such as polyamides, polycarbonates, and polyesters have excellent physical properties such as strength, impact resistance and stiffness, but it is often desirable to blend or alloy these with other thermoplastics such as polyolefins to improve their toughness or to reduce their overall cost.
  • a compatibilizer which functions to improve the adhesion between the incompatible components and/or to modify the surface tension at phase boundaries.
  • a modifier may be blended with an engineering thermoplastic, such a modifier comprising, typically, a polyolefin carrying groupings compatible or reactive with the engineering thermoplastic and thus enhancing interphase adhesion.
  • U.S. Patent No. 4,987,200 discloses production of a functionalized ethylene-propylene copolymer through incorporation, during polymerization, of monomers containing one functional group in which the functionality is protected by a non-halogenated metallic organic compound.
  • the functional groups are protected to prevent poisoning of Ziegler-Natta catalysts used in the polymerization.
  • amine is listed among the functional groups, only metal-based protecting groups are used. The method is costly in that it involves numerous processing steps in part due to the sensitivity to moisture content, and it is not applicable to post-polymerization functionalization reactions.
  • PCT Publication WO 94/13763 describes the preparation of graft polymers containing reactive tertiary amine functionality by melt reacting a maleinized polyolefmic polymer containing at least one electrophilic functionality sufficient to react with primary amine groups with a chemical compound comprising one primary amine and one tertiary amine.
  • PCT Publication WO 93/02113 discloses grafting a di-amine having one primary and one secondary amine functionality on to a maleinized polyolefmic polymer containing at least one electrophilic functionality sufficient to react with primary but not secondary amine groups.
  • Use of the method of either of these PCT publications with a di-amine having two primary functional groups would result in undesirable crosslinking, gelling and hardening.
  • the present invention provides graft polymers having pendant primary amine functionality distributed along the polymer chain and methods for making same.
  • Such graft polymers are produced by reacting an amine-containing compound, having two or more amine groups, with an initial polymer containing electrophilic functionality. Prior to the reaction, all but one of the amine groups on the amine compound are protected to reduce their reactivity such that the unprotected amine group is reactive with the electrophilic groups of the initial polymer and the protected amine groups are not. After the reaction producing the graft polymer having pendant protected primary amine functionality, the protecting group is removed from the appended amine groups to reactivate the primary amine functionality.
  • Preferred protected amine-containing compounds are particularly suitable for effective grafting under melt processing conditions with no or no significant cross-link formation.
  • An initial graft polymer is produced by reacting an initial polymer containing electrophilic functional groups reactive with primary amines with an amine compound having one primary amine group and one or more protected primary amine groups, wherein all the amine groups of the amine compound are held together by a connecting group or a direct nitrogen-to-nitrogen bond of two amine groups.
  • protection of a primary amine group means replacement of one or more of the hydrogen atoms of a primary amine group with a protecting group.
  • Preferred protecting groups reduce the reactivity of the protected amine group to a level that is unreactive or substantially unreactive with the electrophilic functional groups of the initial polymer.
  • Suitable protecting groups are those that can be easily removed when the protected amine group is pendant from a polymer backbone without damaging or substantially altering: (1) the polymer structure (e.g., by chain scission or crosslinking); (2) the bond between the electrophilic functional group of the initial polymer and the primary amine; or (3) the bonds connecting the amine groups of the amine compound to the connecting group or to each other.
  • the electrophilic functional groups of the initial polyolefmic polymer preferentially react with the primary amine groups.
  • the preferential reaction of the primary amine group to leave the protected amine groups unreacted and pendant from the thermoplastic polymer chain may be determined by selecting a protecting group such that the protected amine group is less reactive with those groups than is a primary amine group, and preferably has no reactivity with the electrophilic groups of the initial polymer.
  • the invention also includes a composition comprising a polymer having pendant primary amine functional groups, wherein each said pendant primary amine functional group is attached to the polymer chain by an organic group containing at least one nitrogen linkage.
  • the initial polymer contains anhydride functionality, in which case this nitrogen linkage will be an imide group.
  • Nitrogen linkage for purposes of this invention means a connection through a nitrogen atom such that removal of the nitrogen atom would cause separation of an organic group containing such a linkage into two smaller groups.
  • the protected amine-containing compound prior to reaction with the initial polymer can be any amine of the formula H 2 N-R-[-N(H) x (R 1 ) y ] z , where R is an organic connecting group between amine groups, R 1 is a protecting group which is a further organic group, x is 0 or 1, y is 1 or 2, x+y ⁇ 2, and z is an integer from 1 to 100, preferably 1 or 2. In the case where z is 2 or greater, x, y, and R 1 can be the same or different among the protected amine groups on a single molecule.
  • x+y can be less than 2 where double bonds with the nitrogen atom of the amine group are involved, such as in the case where a Schiff base group is formed after reaction with an aldehyde or a ketone.
  • polyamines meeting the formulaic structure given above can further contain substantially unreactive amine groups, for example, in intermediate positions between the reactive primary and the protected amine group.
  • organic group as used herein means essentially hydrocarbon, but optionally containing one or more heteroatoms selected from the group consisting of O, N, and S, wherein the number of such heteroatoms does not exceed the number of carbon atoms.
  • the amine compound is a di-amine, i. e. , with only the two amine groupings specified above (one primary amine group and one protected primary amine group).
  • the amine compound may thus be represented by the formula H 2 N-N(H) x (R') y or H 2 N-R-N(H) x (R') y where R is an organic connecting group between amine groups, R 1 is a protecting group which is a further organic group, x is 0 or 1, y is 1 or 2, and x+y ⁇ 2 such that the valence of N is satisfied.
  • the groups R and R 1 are different in that the bond strength between nitrogen and R 1 or another nitrogen must be less than the bond strength between nitrogen and R, at least under certain process conditions.
  • the critical aspect of this bond strength difference is to permit removal of the protecting group by heat or chemical reaction, as discussed later, with little or no disruption of the nitrogen bond to the connecting group or the nitrogen-to-nitrogen bond where no connecting group is present.
  • the R group can be an alkyl group, an alicyclic group, an aralkyl group, an aryl group, or an oligomeric or polymeric group having a weight average molecular weight of 3000 or less.
  • Preferred alkyl, alicyclic, aralkyl, and aryl groups have 30 carbon atoms or fewer, preferably 20 or fewer, more preferably 12 or fewer.
  • Such R groups may also have one or more carbon atoms substituted with a heteroatom or heteroatom-containing group, such as but not limited to, oxygen, nitrogen, sulfur, 2-hydroxyethyl, pyridine, pyrimidine, and triazole groups.
  • Typical di-amines, before protecting, for use in accordance with the invention include aliphatic di-amines, alicyclic di-amines, aromatic di-amines, and heteroaromatic di-amines.
  • exemplary aliphatic di-amines include but are not limited to 1,2-di-aminoefhane, 1,3-di-aminopropane, 1,4-di-aminobutane, 1,5-di- aminopentane, 1,6-di-aminohexane, 1,7-di-aminoheptane, 1 ,9-di-aminononane, 1 , 10-di-aminodecane, 1 , 12-di-aminododecane, 1 ,3 -di-amino-2-hydroxypropane, 3,3'-di-amino-N-methyldipropylamine, and 1 ,2-di-amino-2-methylpropane.
  • Exemplary aliphatic di-amines with heteroatoms are: 4,5-di(aminomethyl)-2,2- dimethyldioxolane and l,5-diamino-3-oxapentane.
  • Exemplary alicyclic di-amines include but are not limited to 1,4-di-aminocyclohexane.
  • Exemplary aromatic di- amines include but are not limited to 4-methoxy-l,3-phenylenedi-amine, 1,4-di- aminoanthraquinone, 1,5-di-aminoanthraquinone, 2,6-di-aminoanthraquinone, 3,5- di-aminobenzoic acid, 3,7-di-amino-2-methoxyfluorene, 1,5-di-aminonaphthalene, 1,8-di-aminonaphthalene, 2,7-di-aminofluorene, 2,4-di-aminotoluene, and 2,6-di- aminotoluene.
  • Exemplary heteroaromatic di-amines include but are not limited to 2,4-di-amino-6-(hydroxymethyl)pteridine, 3,4-di-amino-6-hydroxypyrimidine, 3,8-di-amino-6-phenylphenanthridine, 2,6-di-aminopyridine, and 3,5-di-amino- 1,2,4-triazole.
  • An exemplary polymeric di-amine is amino-terminated polyoxyethylene-polyoxypropylene copolymer known as JeffamineTM, available from Huntsman Corporation. Further description of such polymeric di-amines can be found in U.S. Patent No. 5,777,033, which is incorporated by reference herein for purposes of U.S. patent practice.
  • the protecting group R 1 can be a benzyloxycarbonyl group, a tertio- butyloxycarbonyl group, a phenylthiocarbonyl group, a Schiff base precursor (e.g., aldehydes, ketones, or mixtures thereof), a trifluoroacetyl group, a chloroacetyl group, a phthalyl group, an acetoacetyl group, a benzyl group, a diphenyl methyl group, a triphenylmethyl group, an enamine precursor, a para-toluenesulfonyl group, an arylsulfonyl group, a triphenylsulfonyl group, or a trialkyl silyl group.
  • a Schiff base precursor e.g., aldehydes, ketones, or mixtures thereof
  • a trifluoroacetyl group e.g., aldehydes, ketones
  • the protecting group R 1 can also be any of the above named groups wherein one or more hydrogen atoms are replaced with an aliphatic group, e.g., an alkyl group having 1 to 6 carbon atoms, an alicyclic group with 6 to 12 carbon atoms, an aralkyl group with 6 to 12 carbon atoms, or an aryl group with 6 to 12 carbon atoms, e.g., benzyl or phenyl.
  • Such hydrocarbon groups can be linear, branched, cyclic, aryl, or a combination of such structures, provided that these substitutions do not prevent or substantially hinder the protection and deprotection processes.
  • the mono-protected di-amine is recovered after filtration to remove the di-protected di-amine, and solvent extraction and a water wash to remove the excess di-amine.
  • the different constituents i.e., polyamines having different numbers of amine groups protected
  • the different separation techniques such as chromatography.
  • protecting groups and protection/deprotection processes are selected such that these processes can be carried out with substantially no effect on the bonds between the electrophilic functional groups of the initial polymer and the single primary amine groups of the protected amine compound or on the chemical structure of the unprotected amine compound.
  • the amine-reactive functional groups on the functional group-containing polyolefin being reacted with the amine compound will in general be electrophilic groups such as carboxyl, esterified carboxyl, acid chloride, acid anhydride, aldehyde, ketone, silane, epoxy, halogen, isocyanate or oxazoline groups.
  • Anhydride groups are particularly useful in that they react with primary amine groups to form stable cyclic imido groupings.
  • the initial functional group-containing polymer can, for example, be based on a base polymer such as those formed from one or more C 2 -C 20 alpha-olefins, optionally containing copolymerizable non-conjugated diolefms and/or vinyl monomers.
  • Such polyolefins may be crystalline, partially crystalline, or amorphous.
  • polypropylene, polyethylene, ethylene-propylene copolymers, ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer rubber (EPDM), and polymers of ethylene or propylene with one more higher alpha olefins (particularly ethylene/alpha-olefm copolymers) such as 1-butene, 1- hexene, 1-octene, etc. are suitable polyolefins.
  • the polyethylene copolymer resins comprising one or more copolymerizable vinyl esters, acids, epoxides, carbon monoxide, etc.
  • copolymer is used in its ASTM accepted definition of a polymer formed from two or more types of monomers.
  • polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene (RCPP) which can contain 1 to 20 wt % ethylene or an alpha-olefin comonomer of 4 to 20 carbon atoms.
  • the polypropylene can be isotactic, syndiotactic or atactic polypropylene.
  • the RCPP can be either a random or block copolymer.
  • the density of the PP or RCPP can be 0.85 to 0.9 g/cm 3 .
  • Polypropylene containing copolymerized non-conjugated diolefins will also be particularly useful.
  • High density polyethylene useful as a polyolefin resin, has a density of about 0.941 to about 0.965 g/cm 3 .
  • High density polyethylene is an established product of commerce and its manufacture and general properties are well known in the art.
  • Polyethylene copolymer resins which can optionally be used in the compositions of this invention include polybutylene, low density polyethylene (LDPE), VLDPE and linear low density polyethylene (LLDPE) as well as copolymers of ethylene with unsaturated esters of carboxylic acids.
  • LDPE low density polyethylene
  • VLDPE linear low density polyethylene
  • LLDPE linear low density polyethylene
  • polybutylene generally refers to thermoplastic resins of both poly(l-butene) homopolymer and the copolymer with, for example, ethylene, propylene, 1-pentene, etc.
  • Polybutylene is manufactured via a stereo-specific Ziegler-Natta polymerization of monomer(s).
  • Commercially useful products are of high molecular weight and isotacticity.
  • a variety of commercial grades of both homopolymer and ethylene copolymer are available with melt indices that range from about 0.3 to about 20 g/10 min.
  • low density polyethylene or "LDPE” as used in the specification and claims means both low and medium density polyethylene having densities of about 0.91 to about 0.94 g/cm 3 .
  • the term includes linear polyethylene as well as copolymers of ethylene which are thermoplastic resins.
  • Linear low density polyethylene (LLDPE) is a low density polyethylene characterized by little, if any, long chain branching, in contrast to conventional LDPE.
  • LLDPE Linear low density polyethylene
  • the processes for producing LLDPE are well known in the art and commercial grades of this polyolefin resin are available. Generally, it is produced in gas phase fluidized bed reactors or liquid phase solution process reactors. The former process can be carried out at pressures of about 100 to 300 psi (0.7 to 2.1 MPa) and temperatures as low as 100°C.
  • a polyethylene copolymer includes as a comonomer one or more linear, branched, or ring-containing C 3 to C 30 olefms, capable of insertion polymerization, or combinations thereof.
  • Preferred olefmic comonomers are C 3 to C 20 linear or branched ⁇ -olefins, more preferably C 3 to C 8 ⁇ -olefins, even more preferably propylene, 1-butene, 1-hexene, and 1-octene, even more preferably propylene or 1-butene.
  • Preferred branched ⁇ -olefins include 4-methyl-l-pentene, 3-methyl-l-pentene, and 3,5,5-trimethyl-l-hexene.
  • Preferred ring-containing olefmic comonomers include as a ring structure at least one aromatic group.
  • Preferred aromatic group-containing monomers contain up to 30 carbon atoms.
  • Suitable aromatic group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety.
  • the aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone.
  • Preferred aromatic group-containing comonomers contain at least one aromatic structure appended to a polymerizable olefmic moiety.
  • the polymerizable olefmic moiety can be linear, branched, cyclic-containing, or a mixture of these structures.
  • the cyclic structure and the aromatic structure can share 0, 1 , or 2 carbons.
  • the polymerizable olefmic moiety and/or the aromatic group can also have from one to all of the hydrogen atoms substituted with linear or branched alkyl groups containing from 1 to 4 carbon atoms.
  • Particularly preferred aromatic comonomers include styrene, alpha-methylstyrene, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene and allyl benzene.
  • the polyethylene copolymer is a semicrystalline, thermoplastic, preferably random copolymer, of ethylene and at least one ⁇ -olefin, most preferably C 3 -C 8 linear or branched, has a melting point of from 60°C to 125°C, preferably from 65°C to 110°C, more preferably from 70°C to 100°C.
  • the average ethylene content is at least 84 mole %, preferably from 87 to 98 mole %, and more preferably from 89 to 96 mole %.
  • the balance of the copolymer is one or more minor olefmic monomers, capable of insertion polymerization, more preferably one or more ⁇ -olefins as specified above and optionally minor amounts of one or more diene monomers.
  • Density of the polyethylene copolymer, in g/cm 3 is preferably in the range of from 0.865 to 0.915, more preferably from 0.865 to 0.900, even more preferably from 0.870 to 0.890.
  • Weight average molecular weight (M w ) of the polyethylene copolymer can range from 30,000 to 500,000, more preferably from 50,000 to 300,000, even more preferably from 80,000 to 200,000.
  • Particularly preferred polyethylene copolymers are produced with metallocene catalysis and display narrow molecular weight distribution, meaning that the ratio of the weight average molecular weight to the number average molecular weight will be equal to or below 4, most typically in the range of from 1.7 to 4.0, preferably from 1.8 to 2.
  • Such polyethylene materials are commercially available from ExxonMobil Chemical Company of Houston, Texas under the trade name ExactTM. These materials may be made in a variety of processes (including slurry, solution, high pressure and gas phase) employing metallocene catalysts.
  • polyethylene copolymers suitable as the base polymer of this invention include copolymers of ethylene and polar comonomers such as unsaturated esters of carboxylic acids as well as the carboxylic acids per se.
  • copolymers of ethylene with vinylacetate or alkyl acrylates, for example methyl acrylate and ethyl acrylate can be used.
  • These ethylene copolymers typically comprise 60 to 98 wt % ethylene, preferably 70 to 95 wt % ethylene, more preferably 75 to 90 wt % ethylene.
  • ethylene copolymer resin means, generally, copolymers of ethylene with unsaturated esters of lower (C r C 4 ) monocarboxylic acids and the acids themselves; e.g., acrylic acid, vinyl esters or alkyl acrylates. It is also meant to include both “EVA” and “EVOH”, which refer to ethylene-vinyl acetate copolymers, and their hydrolyzed counterpart ethylene-vinyl alcohols.
  • acrylates which can be utilized are methyl acrylate, ethyl acrylate, glycidyl methacrylate, and alkylacrylate (where alkyl means any alkyl between and including propyl and dodecenyl).
  • polyethylene copolymers include ethylene-acrylic acid, ethylene-methyl-acrylate, ethylene- methyl-acrylate-acrylic acid, ethylene-methacrylic acid, etc. Terpolymers of ethylene and any of those polar monomers above mentioned will also be included. Similarly, those having acid groups only partially neutralized with metal cations to form those products known as ionomers will be suitable herein.
  • ethylene- alpha-olefm elastomers which are defined to include ethylene-alpha-olefin copolymers, optionally with one or more non-conjugated diolefins.
  • Such polymers are well-known, as are their methods of preparation, as described in U.S. Patent Nos. 4,895,897 and 4,749,505, which are fully incorporated herein by reference for purposes of U.S. patent practice.
  • Particularly preferred ethylene-alpha-olefin elastomers are prepared from ethylene and ethylenically unsaturated hydrocarbons including cyclic, alicyclic and acyclic, containing from 3 to 28 carbons, preferably 2 to 18 carbons.
  • These ethylene copolymers may contain from 15 to 90 wt % ethylene, preferably 30 to 80 wt % of ethylene and 10 to 85 wt %, preferably 20 to 70 wt %, of one or more C 3 to C 28 , preferably C 3 to C, g , more preferably C 3 to C 8 , alpha-olefins.
  • copolymers preferably have a degree of crystallinity of less than 25 wt %, as determined by X-ray and differential scanning calorimetry.
  • Copolymers of ethylene and propylene are most preferred.
  • Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene to form a terpolymer, tetrapolymer, etc. include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; branched- chain alpha-olefins, such as 4-methyl- 1-pentene, 4-methyl- 1-hexene, 5-methyl-l- pentene, 4,4-dimethyl- 1-pentene, 6-methyl- 1-heptene, etc., and mixtures thereof.
  • copolymer as used herein, unless otherwise indicated, includes terpolymers, tetrapolymers, etc., of ethylene, said C 3 -C 28 alpha-olefin and/or a non-conjugated diolefm or mixtures of such diolefins which may also be used.
  • the amount of the non-conjugated diolefm will generally range from 0.5 to 20 mole percent, preferably 1 to 7 mole percent, based on the total amount of ethylene and alpha-olefin present.
  • non-conjugated dienes that may be used as the third monomer in the terpolymer include:
  • Multi-single-ring alicyclic dienes such as 4,4'-dicyclopentenyl and 4,4'-dicyclohexenyl dienes
  • Multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene; bicyclo(2.2.1)hepta 2,5-diene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as ethyl norbornene; 5-methylene-6-methyl-2- norbornene; 5-methylene-6,6-dimethyl-2 -norbornene; 5-propenyl-2 -norbornene; 5-(3-cyclopentenyl)-2-norbornene and 5-cyclohexylidene-2 -norbornene; norbornadiene; etc.
  • the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2- norbornene.
  • Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene.
  • ENB 5-ethylidene-2-norbornene
  • the non-conjugated diene is incorporated into the polymer in an amount of from 0.1 to 15 wt %; more preferably, from 0.5 to 10 wt %, most preferably from 1 to 10 wt %.
  • the ethylene-alpha-olefin elastomers of this invention can be prepared by procedures known in the art.
  • various examples of such commercially available copolymers are VISTALONTM, elastomeric copolymers of ethylene and propylene alone or with 5-ethylidene-2-norbornene, marketed by ExxonMobil Chemical Company, Houston, Texas, and Nordel®, a copolymer of ethylene, propylene and 1,4-hexadiene, marketed by E. I. duPont de Nemours & Company, Wilmington, Del.
  • elastomeric butyl rubber and halogenated butyl rubber are suitable as the initial polyolefmic polymer when containing, or modified to contain, functional groups reactive with primary amine groups.
  • Butyl rubber and halogenated butyl rubber are well known articles of commerce and any such polymer product, suitably functionalized, will be effective in accordance with the invention.
  • These polymers are based upon cationic polymerization of isobutylene, optionally with one or more monomers (such as isoprene or a para-alkylstyrene, particularly para-methylstyrene) copolymerizable therewith, all as is well known.
  • elastomeric butyl rubber is the class of compositions making up polyisobutylene rubber, which strictly speaking is not butyl rubber, but is instead an elastomeric homopolymer of isobutylene.
  • Polyisobutylene rubber is also a well known article of commerce manufactured in accordance with known methods. Its use in lubricating oils, when modified with succinic acid/anhydride groups, optionally aminated, is particularly well suited for this invention.
  • a preferred polypropylene copolymer used in the present invention includes one or more comonomers selected from ethylene and C 4 -C 20 alpha olefins and having crystallinity resulting from stereoregular polypropylene sequences.
  • Such polypropylene copolymers are described in detail as the "Second Polymer Component (SPC)" in co-pending U.S. application serial nos.
  • the low levels of crystallinity in the polypropylene copolymer are derived from isotactic or syndiotactic polypropylene sequences, preferably isotactic polypropylene sequences, obtained by incorporating minor olefmic monomers as described above, as comonomers.
  • Preferred polypropylene copolymers have an average propylene content on a molar basis of from 49% to 92%, more preferably from 59% to 91%), even more preferably from 65% to 88%, even more preferably from 72% to 86%o, most preferably from 18% to 85%.
  • the balance of the copolymer is one or more linear or branched ⁇ -olefins as specified above and optionally minor amounts of one or more diene monomers.
  • the semi-crystalline polypropylene copolymer preferably has a heat of fusion from 9 J/g to 76 J/g, more preferably from 11 J/g to 57 J/g, more preferably from 15 J/g to 47 J/g, even more preferably from 17 J/g to 38 J/g.
  • the crystallinity of the polypropylene copolymer arises from crystallizable stereoregular propylene sequences.
  • the electrophilic groups are provided most preferably by ethylenically unsaturated electrophilic group-containing compounds, which are either copolymerized during the preparation of the thermoplastic polymers or are grafted onto a previously prepared polymer or by halogenation such as in halobutyl. Copolymerization including the compound providing the electrophilic groups will be possible when all the monomers of the polymers are polymerizable by either conventional free radical catalysis or Ziegler coordination catalysis. Copolymerizable monomers incorporated by free-radical catalysis include such comonomers as alkyl acrylates, vinyl esters, acrylic acids, methacrylic acid, glycidyl methacrylate and the like.
  • thermoplastic polymers are known in the art, as is their method of preparation. Illustrative of this knowledge is U.S. Patent No. 4,017,557, or WO 96/23010, which are fully incorporated by reference herein for purposes of U.S. patent practice. Thus, copolymerizable monomers permitting the incorporation of these reactive electrophilic groups into the polyolefins will be useful in accordance with this invention. Such compounds, and methods both of preparation and of incorporation with polyolefins, are also well known. Descriptions for Ziegler copolymerization are to be found, inter alia, in U.S. Patent Nos.
  • copolymerization for the purpose of this invention, are those chain terminating reactions wherein the appropriate functional groups are added to a forming thermoplastic polymer and simultaneously terminate the polymerization reaction. Such reactions are sometimes termed end- capping reactions and are generally known.
  • end- capping reactions the carbonation of polymers prepared by anionic polymerization through the introduction of gaseous CO 2 into the living polymerization reaction and termination of that reaction will be suitable for this invention.
  • Description appears in the art see, for example, the teachings of U.S. Patent No. 4,950,721, which is fully incorporated herein by reference for purposes of U.S. patent practice.
  • graft addition of ethylenically unsaturated electrophilic group- containing compounds suitable in this invention is conveniently accomplished by heating a blend of the polyolefin and the unsaturated electrophilic group-containing compounds within a range of 150- 400°C, often in the presence of free-radical initiators such as organic peroxides.
  • free-radical initiators such as organic peroxides.
  • Isocyanate groups can also be grafted onto polyolefmic backbones through the reaction for example of TMITM (META) [benzene, 1 -( 1 -isocyanato- 1 -methylethyl)-3 -( 1 -methylethenyl), produced by American Cyanamid Company] in the presence of a peroxide.
  • Oxazoline functionality can also be introduced onto a polyolefin according to methods described in reactive modifiers for polymers. (See S. Al-Malaika, Blackie Academic & Professional (1997), Chapter 4.)
  • the amount of electrophilic group-containing compound incorporated in the functionalized polymer will be that sufficient to provide at least one site reactive per chain with the primary amine group-containing compound, that is monomers containing electrophilic groups should make up at least 0.01 wt % of the functional group-containing thermoplastic polymer component. Most typically, the electrophilic group-containing monomer will make up from 0.01 to 15 wt %, preferably 0.05 to 5.0 wt % ⁇ .
  • the amount of functional moieties present, whether contributed by functional group-containing monomers, or by direct functionalization, will thus be that equivalent to this level of monomer incorporation.
  • Other functionalized polymers include any that can be similarly grafted or otherwise contain the described electrophilic groups, particularly, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, or epoxy groups, for example styrene-based polymers and copolymers, or ethylene-acrylic ester-maleic anhydride or ethylene-acrylic ester-glicidyl methacrylate terpolymers, such as LotaderTM, available from Atochem.
  • electrophilic groups particularly, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, or epoxy groups, for example styrene-based polymers and copolymers, or ethylene-acrylic ester-maleic anhydride or ethylene-acrylic ester-glicidyl methacrylate terpolymers, such as LotaderTM, available from Atochem.
  • Styrene-based polymers suitable for graft incorporation of one or more electrophilic group-containing compounds and well known in the art include those which may be described as hydrogenated or partially hydrogenated homopolymers, and random, tapered, or block polymers (copolymers, including terpolymers, tetrapolymers, etc.) of conjugated dienes and or monovinyl aromatic compounds with, optionally, alpha-olefins or lower alkenes, e.g., C 3 to C ]8 alpha- olefins or lower alkenes.
  • the conjugated dienes include isoprene, butadiene, 2,3- dimethyl-butadiene, piperylene and or mixtures thereof, such as isoprene and butadiene.
  • the monovinyl aromatic compounds include any of the following or mixtures thereof: vinyl di- or polyaromatic compounds, e.g., vinyl naphthalene, but are preferably monovinyl monoaromatic compounds, such as.
  • styrene or alkylated styrenes substituted at the alpha-carbon atoms of the styrene such as alpha-methylstyrene, or at ring carbons, such as o-, m-, or p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, isobutylstyrene, and tertiobutylstyrene (e.g., p-tertiobutylstyrene).
  • alpha-carbon atoms of the styrene such as alpha-methylstyrene, or at ring carbons, such as o-, m-, or p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butyl
  • Alpha-olefins and lower alkenes optionally included in these random, tapered and block copolymers preferably include ethylene, propylene, butene, ethylene-propylene copolymers, isobutylene, and polymers and copolymers thereof.
  • these random, tapered and block copolymers may include relatively small amounts, that is less than 5 mole %, of other copolymerizable monomers such as vinyl pyridines, vinyl lactams, methacrylates, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl stearate, and the like.
  • specific examples include random polymers of butadiene and/or isoprene and polymers of isoprene and/or butadiene and styrene.
  • Typical block copolymers include polystyrene-polyisoprene, polystyrene-polybutadiene, polystyrene-polyethylene, polystyrene-ethylene propylene copolymer, polystyrene-ethylene butene copolymer, polyvinyl-cyclohexane-hydrogenated polyisoprene, and polyvinyl cyclohexane-hydrogenated polybutadiene.
  • Tapered polymers include those of the foregoing monomers prepared by methods known in the art.
  • styrene-based copolymers include pseudo-random ethylene- styrene (ES) copolymers prepared using constrained geometry catalysts. The synthesis of such ethylene-styrene copolymers is described in European Patent Application 416,815 A2, which is fully incorporated by reference herein for purposes of U.S. patent practice.
  • ES pseudo-random ethylene- styrene
  • Suitable styrene-based polymers having incorporated electrophilic functionality in accordance with the invention include those comprising styrene and maleic anhydride, optionally containing copolymerizable monomers as disclosed in U.S. Patent No. 4,742,116, the disclosure of which is fully incorporated by reference herein for purposes of U.S. patent practice.
  • the reaction of the functionalized initial polymer with the amine compound can be effected either in solution or by heating the mixture.
  • an important feature of this invention is the ease of conducting the reaction process largely in accordance with melt processing reaction conditions well-known by those skilled in the art.
  • the reaction temperature will preferably be in the range of from 160°C to 200°C, more preferably 170°C to 195°C, even more preferably 180°C to 190°C.
  • a mixing device such as a Brabender or Banbury mixer or an extruder, e.g., a single or twin screw extruder.
  • the reaction time may be a few seconds (e.g., 30 seconds) to a few minutes or even longer in optimizing reaction efficiency and possible reaction temperature side-effects such as molecular weight degradation of the thermoplastic polymer.
  • the amine should be present in an amount equal to or exceeding the amount of functionally available reactive sites. Amine functionality may be assayed by solvent titration, and residual groups such as anhydride may be assayed by Fourier Transform Infrared Spectroscopy (FTIR).
  • FTIR Fourier Transform Infrared Spectroscopy
  • the graft reaction of the protected amine compound with the initial polymer is performed in solution.
  • Preferred solutions include aliphatic, aromatic, alicyclic, alkanes, or any other solvent in which the initial polymer is soluble (i.e., in embodiments where the initial polymer contains polar groups, a polar solvent or mixture of a polar and non-polar solvent may be preferable).
  • the preferred solution process pressure range is from atmospheric pressure to 10 bar (1 MPa) or less, more preferably to 5 bar (0.5 MPa) or less.
  • the preferred solution process temperature range is from 100°C to 220°C, more preferably from 150°C to 200°C, even more preferably from 180°C to 195°C.
  • Deprotection, or removal of the protecting groups can be accomplished either in a solution process or in a melt process. In either a solution or a melt deprotection process, it is essential that the process conditions facilitating the removal of the protecting groups have substantially no effect on the bonds between the electrophilic functional groups of the initial polymer and the single primary amine groups of the masked polyfunctional amine compound or the chemical structure of the unprotected amine compound. Nearly all combinations of polymer, amine compound, and protecting group can be deprotected in solution. Only a portion of these combinations can be deprotected via heat, due to failure of one of more of the other chemical bonds prior to separation of the protecting group. Those skilled in the various polymer arts and in amine chemistry would be able to select an appropriate deprotection process for a given combination of polymer, amine compound, and protecting group.
  • the protecting group can be removed either thermally or in the presence of acid catalysts.
  • a polymer containing primary amines protected with a t-butoxycarbonyl group can be deprotected by heating the polymer. Isobutylene and carbon dioxide are liberated when the protecting group is removed and replaced by hydrogen atoms. A temperature above 250°C is preferred in order to achieve activation energies which allow the removal of the protecting group within short residence times by one hydrogen atom.
  • the removal of the protecting group is performed according to methods known to those skilled in the art and described, for example, in Peptide Synthesis, Bodansky, Klausner, & Ondetti, 2d ed., Wiley- Interscience Publication, John Wiley and Sons (1976), in particular Chapter 4, which is incorporated by reference herein for purposes of U.S. patent practice.
  • the deprotection process selected involves only process conditions that do not substantially alter the polymer structure (e.g., chain scission or crosslinking), the bond between the electrophilic functional group of the initial polymer and the primary amine, or the bonds connecting the amine groups of the amine compound to the connecting group or to each other.
  • Table 1 shows specific protecting groups and appropriate methods for their removal.
  • the amino-modified polymers according to the invention may be used directly as compatibilizers or modifiers for thermoplastic polymer compositions.
  • U.S. Patent No. 4,742,116 suggests the use of nitrogen-grafted EPR or EPDM as an effective modifier for styrene-maleic anhydride copolymers.
  • published European Patent Application EP-A-0 321 293 discloses the use of functionalized EPR or EPDM, wherein the incorporated functionality may be amino, as an effective impact modifier for polybutylene terephthalate molding compositions.
  • 4,895,897 discloses the use of an intermediate functionalized elastomer, including amine functionalized elastomer, reacted with oxazoline functionalized polystyrene, to prepare graft polymers effective for modifying the impact properties of aromatic polycarbonate compositions (polycarbonate).
  • Amino-modified EPR or EPDM can also be used as compatibilizers between EPDM and nitrile rubbers with the objective of improving heat resistance at minimum oil resistance penalty.
  • graft polymers are provided that can be used as modifiers or compatibilizers with any thermoplastic polymer having molecular interaction with either of the polymer backbone of the graft polymer or the grafted amine functionality.
  • any thermoplastic polymer having molecular interaction with either of the polymer backbone of the graft polymer or the grafted amine functionality can be used as modifiers or compatibilizers with any thermoplastic polymer having molecular interaction with either of the polymer backbone of the graft polymer or the grafted amine functionality.
  • blends of the graft polymer of the invention with one, two, or more other polymers, particularly engineering thermoplastics or in lubricating oil compositions will be possible.
  • the amine-functionalized polymer according to the invention may be reacted or blended with a second polymer by melt reaction, for example in a Brabender mixer or an extruder. This may be conducted in the same reactor as the de-protection reaction, or subsequently, in another melt reactor. The reaction time and temperature will depend on the polymers present. This reaction may be carried out in a separate subsequent step or may be effected in situ in a melt of the polymer or polymers to be compatibilized.
  • the primary amine functionalized polyolefin can react with any polymers containing functional groups which are reactive towards primary amines, such as carboxylic acids, carboxylic esters, anhydrides, carbonyl halides, ketones, aldehydes, epoxides, isocyanates, oxazolines, unsaturated carbonyl groups, alkyl, alkenyl, benzyl or aryl halides or any electrophylic site containing a good leaving group.
  • Any polymers containing functional groups which are reactive towards primary amines such as carboxylic acids, carboxylic esters, anhydrides, carbonyl halides, ketones, aldehydes, epoxides, isocyanates, oxazolines, unsaturated carbonyl groups, alkyl, alkenyl, benzyl or aryl halides or any electrophylic site containing a good leaving group.
  • amine functionalized polypropylene may be melt reacted/blended with a blend of styrene-maleic anhydride polymer in polypropylene.
  • polypropylene blends containing other polymer systems, especially engineering thermoplastics that are reactive with, or otherwise compatible with, the aminated polypropylene can be prepared having improved overall blend compatibility between the polypropylene, other polymer and aminated polypropylene.
  • amino-polyolefms in accordance with this invention may be utilized to compatibilize otherwise incompatible polymer blends of polyolefins and halogenated polymers, such as poly(vinyl chloride) (PVC), poly(di-vinyl chloride) (PVDC), poly(di-vinyl fluoride) (PVDF), chlorinated-nitrile rubber, halobutyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, and the like.
  • PVC poly(vinyl chloride)
  • PVDC poly(di-vinyl chloride)
  • PVDF poly(di-vinyl fluoride)
  • chlorinated-nitrile rubber halobutyl rubber
  • chlorinated polyethylene chlorosulfonated polyethylene, and the like.
  • Aminated-PE may be advantageously used as a tie layer in multilayer films where it can promote adhesion between two polymer layers otherwise incompatible, such as PE and PVDC.
  • aminated-polyolefins will be useful to improve overall properties of polymer mixes, and thus has potential for recycling of mixed plastics, particularly those containing a significant portion of polyolefins.
  • Amine functionalized EPDM can be used to compatibilize blends of EPDM and VamacTM (terpolymers of ethylene, acrylic acid and acrylic esters, available from DuPont) or acrylate rubbers or epichlorhydrin or nitrile rubber or hydrogenated nitrile rubbers for thermoset applications where increase of properties such as green strength, heat resistance or cost reduction are wanted.
  • VamacTM terpolymers of ethylene, acrylic acid and acrylic esters, available from DuPont
  • acrylate rubbers or epichlorhydrin or nitrile rubber or hydrogenated nitrile rubbers for thermoset applications where increase of properties such as green strength, heat resistance or cost reduction are wanted.
  • oil soluble polymers selected from the group consisting of ethylene-alpha-olefin elastomers, polyisobutylene rubber, and styrene-based polymers will be particularly suitable when functionalized to contain the necessary electrophilic functionality and reacted with the amine compounds of this invention.
  • the oil soluble polymers prepared in accordance with the disclosure herein will be useful in lubricating oil compositions. More particularly, those polymers having a number average molecular weight from 500 to 10,000, preferably 800 to 3,000 will have utility in detergent and dispersant applications.
  • Polymer blends containing the primary amine-functionalized polymers of this invention also have further advantageous uses, including but not limited to, improved: paint adhesion; adhesion to treated glass fibers or other fillers; reinforcement in carbon black filled EPDM compounds through better interaction between carbon black and polymer; adhesion to coatings, such as polyurethane; adhesion between polyolefins and other polymers, such as polyesters or any other polymers having reactive groups capable of reacting with an amine functionality; and coextruded tie resins (CTR) for film applications; coextruded profiles for automotive body sealing production or coextruded hoses manufacturing; plastic overmolding with polyolefins.
  • CTR coextruded tie resins
  • % MA (total MA content) k(A 1790 + A 1712 )/A 432g , k being determined after internal calibration with a series of standards and having a value of 0.258 in this case.
  • Mooney viscosity was measured according to ASTM method D-1646.
  • MI Melt Index
  • MFR Melt Flow Rate
  • ExactTM 4033 polymer is an ethylene-butene copolymer produced using metallocene catalyst and available from ExxonMobil Chemical Company, Baytown, Texas. This copolymer has a density of 0.880 g/cm 3 and a melt index (MI) of approximately 0.8 g/10 min at 190°C and 2.16 kg.
  • ExactTM 4049 polymer is an ethylene-butene copolymer produced using metallocene catalyst and available from ExxonMobil Chemical Company, Baytown, Texas. This copolymer has a density of 0.873 g/cm 3 and a MI of 4.5 g/10 min at 190°C and 2.16 kg.
  • IP Initial Polymer
  • IP1 Maleic Anhydride-grafted-Ethylene Butene Copolymer.
  • ExactTM 4033 polymer was modified on a twin screw extruder (Welding Engineer, 30mm, 48 L/D) with the following temperature profile: 170°C, 180°C, 210°C, 210°C, and 200°C. Modification was performed at a 7 kg/hr polymer feed rate and a 250 rpm screw speed. 0.6 weight percent maleic anhydride and 0.015 weight percent of peroxide (LuperoxTM 130 from Aatochem) were added.
  • the maleic anhydride modified polymer had a density of 0.880 g/cm 3 , a Mooney viscosity of ML(l+4) of 38 at 125°C and an anhydride content of 0.45 weight %> as measured by FTIR.
  • IP2 Maleic Anhydride-grafted-Ethylene Butene Copolymer.
  • ExactTM 4049 polymer was modified on a twin screw extruder (Welding Engineer, 30mm, 48 L/D) with the following temperature profile: 170°C, 180°C, 210°C, 210°C, and 200°C. Modification was performed at a 7 kg/hr polymer feed rate and a 250 rpm screw speed. 4 weight percent maleic anhydride and 0.18 weight percent of peroxide were added.
  • the maleic anhydride modified polymer had a density of 0.873 g/cm 3 , a MFR (230°C, 5 kg) of 3 g/10 min and an anhydride content of 3 weight %> as measured by FTIR.
  • IP3 Maleic Anhydride-grafted-Ethylene Butene Copolymer. ExactTM
  • 4049 polymer was modified on a twin screw extruder with the following temperature profile: 170°C, 180°C, 210°C, 210°C, and 200°C. Modification was performed at a 7 kg/hr polymer feed rate and a 250 rpm screw speed. 1 weight percent maleic anhydride and 0.04 weight percent of peroxide (LuperoxTM 130 from Aatochem) were added. The maleic anhydride modified polymer had a density of 0.873 g/cm 3 , a Mooney viscosity of ML(l+4) of 44 at 125°C and an anhydride content of 0.8 weight % as measured by FTIR.
  • N-terbutoxy carbonyl- 1 ,6-hexanediamine was produced by condensation of 1 ,6-hexanediamine with di-terbutyl-dicarbonate as described in Krapcho & Kuell, "Mono-protected Diamines. N-tert-Butoxycarbonyl- ⁇ , ⁇ - Alkanediamines from ⁇ , ⁇ -Alkanediamines," Synthetic Communications, 20(16), pp. 2559-2564 (1990).
  • Example 1 Production of polymer with pendant protected amine groups in solution.
  • IP2 20 grams of IP2 were dissolved in 500 mL of xylene and 2.6 grams of the protected amine were added. The solution was heated at refluxing xylene temperature for 2 hours. The solution was cooled down to 70°C and poured into 1 L of acetone. The precipitated polymer was recovered by filtration and dried in a vacuum oven at 50°C for 2 hours, then analyzed by FTIR.
  • Example 2 Production of polymer with pendant protected amine groups in an extruder.
  • a dry blend was prepared by dry blending 1 kg of IP3 with 30 grams of mono-protected amine on an open mill at room temperature for 10 minutes. From the final sheet, strips were cut and fed to a Haake RheocordTM 90 extruder (25 L/D, 3/1 compression ratio) at different temperatures from 160°C to 220°C at 25 rpm. The Mooney viscosity of the polymers obtained after animation is given for each temperature in Table 2.
  • Example 3 Production of polymer with pendant protected amine groups in an extruder.
  • Polymer IP1 was fed at 3 kg per hour to a twin screw extruder (Welding Engineer, 3 mm, 48 L/D), heated at 180°C. Screw speed was set at 200 ⁇ m and the monoprotected amine was fed at a rate of 0.84 mL/min. Nitrogen stripping and vacuum (700 mbar (70 kPa)) were applied to the vent barrel in order to remove the protected amine in excess. The recovered protected amino-grafted-IPl had a Mooney viscosity [ML(l+4), 125°C] of 27. Extrusion conditions:
  • Vacuum on vent barrel 700 mbar (70 kPa) Feeding conditions:
  • Example 4 Deprotection of protected amine groups of "protected" amine grafted polymer in solution. Two grams of the mono-protected amine functionalized polymer produced in Example 3 were dissolved in 40 mL of xylene, and 4 mL of a 5 M HC1 aqueous solution were added. The solution was heated at refluxing xylene temperature for 2 hours. The solution was cooled down to 70°C and poured into 100 mL of acetone. The precipitated polymer was recovered by filtration and dried in a vacuum oven at 50°C for 2 hours, then analyzed by FTIR.
  • Example 5 Deprotection of protected amine groups of "protected” amine grafted polymer by heat.
  • Example 3 42 grams of the mono-protected amine functionalized polymer produced in Example 3 were mixed in a Haake RheocordTM mixer for 1 hour at a chamber temperature of 300°C with a rotor speed of 100 ⁇ m. The polymer was than recovered, cooled down and analyzed by FTIR.
  • Example 4 The Mooney viscosity of this polymer ML(l+4), 125°C was 20 indicating that there was essentially no cross-linking or chain extension taking place during the deprotection reaction as the polymer viscosity did not significantly increase.

Abstract

L'invention concerne des polymères greffés comprenant la fonction amine primaire. Ces polymères greffés sont fabriqués par réaction d'un polymère thermoplastique contenant au moins une fonction électrophile suffisante pour réagir avec des groupes amines primaires, avec un composé chimique comprenant un groupe d'amines primaires et au moins un groupe d'amines primaires protégées. L'utilisation des groupes de protection sélectionnés permet d'éviter sensiblement la réticulation. Après la greffe du composé contenant des amines, les groupes de protection sont retirés puis remplacés par des atomes d'hydrogène de manière à rétablir la fonction amine primaire dans le groupe d'amines en suspension. Grâce à l'utilisation de processus de protection, les liaisons chimiques contenues dans le composé d'amines et les liaisons chimiques liant l'amine au polymère sont sensiblement conservées.
PCT/US2000/028789 1999-10-19 2000-10-18 Polymeres greffes contenant des amines, procedes de fabrication et d'utilisation associes WO2001029095A1 (fr)

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EP00973632A EP1237946A1 (fr) 1999-10-19 2000-10-18 Polymeres greffes contenant des amines, procedes de fabrication et d'utilisation associes
AU12126/01A AU1212601A (en) 1999-10-19 2000-10-18 Amine-containing graft polymers, a method for making same, and their use
MXPA02003941A MXPA02003941A (es) 1999-10-19 2000-10-18 Polimeros de injerto que contienen amina, un metodo para hacer los mismos, y su uso.
CA002388037A CA2388037A1 (fr) 1999-10-19 2000-10-18 Polymeres greffes contenant des amines, procedes de fabrication et d'utilisation associes

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EP2527374A1 (fr) 2006-12-21 2012-11-28 Dow Global Technologies LLC Polymères d'oléfine fonctionnalisés, compositions et articles préparés à partir de ceux-ci et procédé de fabrication associés
US8981013B2 (en) 2006-12-21 2015-03-17 Dow Global Technologies Llc Functionalized olefin polymers, compositions and articles prepared therefrom, and methods for making the same
US9200103B2 (en) 2006-12-21 2015-12-01 Dow Global Technologies Llc Functionalized olefin polymers, compositions and articles prepared therefrom, and methods for making the same

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CN109722020B (zh) * 2018-12-27 2021-06-29 万华化学集团股份有限公司 一种胺基官能化聚烯烃弹性体增韧的尼龙复合材料及其制备方法
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