GRAFT POLYMERS THAT CONTAIN AMINE, A METHOD TO MAKE THEM, AND ITS USE
Field of the Invention The present invention relates to graft polymers and to a method for their manufacture. In particular, it relates to functional polymers grafted with certain amine compounds and further processed to produce a polymer having pendant primary amine functionality. BACKGROUND Engineering thermoplastics, such as polyamides, polycarbonates, and polyesters have excellent physical properties such as strength, impact resistance and stiffness, but it is often desirable to physically mix or alloy these with other thermoplastics, such as polyolefins, to improve its tenacity or to reduce its overall cost. However, the components of such physical mixtures are rarely compatible; it is thus common practice to include a compatibilizing agent that functions to improve adhesion between the incompatible components and / or to modify the surface tension in phase boundaries. Alternatively, a modifier can be physically mixed with an engineering thermoplastic, such as a modifier which typically comprises a polyolefin carrying groupings compatible or reactive with the engineering thermoplastic and thereby enhancing the inter-phase adhesion. Additionally, it is well known that certain nitrogen-containing polymeric compounds find significant use as modifiers for lubricating oil compositions, and that certain such polymeric compounds have such molecular weight characteristics that a reaction by or during processing in the melted state is possible. possible preparation method, if not preferable. In this way there is a requirement to provide functional groups in a wide range of polymers, which functional groups can contribute to or by subsequent reaction binding to the polymer compatibilizing or modifying fractions. This has been commonly attempted by grafting or copolymerizing active clusters in the polymers. US Patent 4,987,200 discloses the production of an ethylene-propylene copolymer functionalized by incorporating, during the polymerization, monomers containing a functional group in which the functionality is protected by a non-halogenated metal organic compound. The functional groups are protected to prevent poisoning of the Ziegler-Natta catalysts used in the polymerization. Although amine is listed among the functional groups, only metal-based protecting groups are used. The method is expensive because it involves numerous processing steps, partly due to the sensitivity to moisture content, and 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 reacting in the melted state a maleinized polyolefin polymer containing at least one electrophilic functionality sufficient to react with primary amine groups with a chemical compound comprising a primary amine and a tertiary amine. PCT publication WO 93/02113 discloses grafting a diamine having a primary amine functionality and a secondary amine functionality into a maleinized polyolefin polymer containing at least one electrophilic functionality sufficient to react with primary but not secondary amine groups. The use of the method of any of these PCT publications with a di-amine having two primary functional groups would result in undesirable crosslinking, gelation and hardening. It would be desirable to economically produce graft polymers having pendant amine functionality with increased reactivity of primary amine groups while still preventing undesirable crosslinking of the base polymer. The primary amine functionality would promote more "complete" reactions and would require a shorter reaction time where the functional group is included for subsequent reactions such as, but not limited to, crosslinking or reactions with other polymers in physical mixtures. SUMMARY OF THE INVENTION 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 in the amine compound are protected to reduce their reactivity such that the unprotected amine group is reactive with the electrophile groups of the initial polymer and the protected amine groups are not. After the reaction that produces the graft polymer having pendant, protected primary amine functionality, the protecting group is removed from the bound amine groups to reactivate the primary amine functionality. The preferred protected amine-containing compounds are particularly suitable for effective grafting under processing conditions in the melted state without or without significant cross-linking formation. Detailed Description An initial graft polymer is produced by reacting an initial polymer containing electrophilic functional groups reactive with primary amines with an amine compound having a primary amine group and one or more protected primary amine groups, wherein all the amine groups of the compound of amine are held together by a linking group or a direct nitrogen to nitrogen bond of two amine groups. For purposes of this description and the appended claims, the protection of a primary amine group means the re-placement of one or more 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 non-reactive or substantially unreactive with the electrophilic functional groups of the initial polymer. Suitable protecting groups are those which can be easily removed when the protected amine group is pendant from a polymer backbone without damaging or substantially altering: (1) the structure of the polymer (e.g., by chain cleavage or cross-linking); (2) the link between the electrophilic functional group of the initial polymer and the primary amine; or (3) the linkages connecting the amine groups of the amine compound with the linking group or with each other. The electrophilic functional groups of the initial polyolefin polymer react preferably with the primary amine groups. The preferential reaction of the primary amine group to leave the unreacted protected amine groups and pendants of the thermoplastic polymer chain can be determined by selecting a protective 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 of said pendant primary amine functional groups is attached to the polymer chain by an organic group containing at least one nitrogen link. In a preferred embodiment, the initial polymer contains anhydride functionality, in which case this nitrogen link will be an imide group. The nitrogen link for purposes of this invention means a connection through a nitrogen atom such that the removal of the nitrogen atom would cause the separation of an organic group containing such a link into two smaller groups. Amine Containing Compound The amine-containing compound protected prior to reaction with the initial polymer can be any amine of the formula H2N-R- [-N (H) x (R1) y] z, where R is an organic linking group between the amine groups, R1 is a protecting group which is an additional organic group, is O ol, and 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 R1 may be the same or different among the protected amine groups in a single molecule. For clarification, 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. Optionally, the polyamines satisfying the structure of the formula given above may further contain substantially non-reactive amine groups, for example, at intermediate positions between the reactive primary amine group and the protected amine group. The term "organic group", as used herein, means essentially hydrocarbon, but optionally containing one or more heteroatoms selected from the group consisting of 0, N, and S, where the number of such heteroatoms does not exceed the number of carbon atoms. carbon In a preferred embodiment, the amine compound is a diamine, ie with only the two amine groupings previously taught (a primary amine group and a protected primary amine group). The amine compound can thus be represented by the formula H2N-N (H) x (R1) and H2N-RN (H) x (R1) and, where R is an organic linking group between amine groups, R1 is a protective group which is an additional organic group, x is O ol, and is the 2, and x + y < 2, such that the valence of? be satisfied. The groups R and R1 are different insofar as the intensity of the bond between nitrogen and R1 or another nitrogen must be less than the intensity of the bond between nitrogen and R, at least under certain process conditions. The critical aspect of this difference in bond strength is to allow the removal of the protective group by heat or chemical reaction, as discussed below, with little or no disturbance of the nitrogen bond with the linking group or the nitrogen- nitrogen where a linking group is not present. The group R 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 3., 000 or less. Preferred alkyl, alicyclic, aralkyl and aryl groups have 30 carbon atoms or less, preferably 20 or less, more preferably 12 or less. Such R groups may also have one or more carbon atoms substituted with a heteroatom or a heteroatom-containing group, such as, but not limited to oxygen, nitrogen, sulfur, 2-hydroxyethyl, pyridine, pyrimidine and triazole groups. Typical diamines, before protection, for use in accordance with the invention, include aliphatic diamines, alicyclic diamines, aromatic diamines, and heteroaromatic diamines. Exemplary aliphatic diamines include, but are not limited to, 1, 2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 12-diaminododecane, 1,3-diamino-2-hydroxypropane, 3'3'-diamino-N-methyldipropylamine, and 1, 2-diamino-2-methylpropane. Exemplary aliphatic diamines with heteroatoms are: 4,5-di (aminomethyl) -2,2-dimethyldioxolane and 1,5-diamino-3-oxapentane. Exemplary alicyclic diamines include, but are not limited to, 1,4-diaminocyclohexane. Exemplary aromatic diamines include, but are not limited to, 4-methoxy-1,3-phenylene diamine, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,6-diaminoanthraquinone, 3,5-diaminobenzoic acid, 3,7 -diamino-2-methoxyfluorene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,7-diaminofluorene, 2,4-diaminotoluene, and 2,6-diaminotoluene. Exemplary heteroaromatic diamines include, but are not limited to, 2,4-diamino-6- (hydroxymethyl) pteridine, 3,4-diamino-6-hydroxy-rimidine, 3,8-diamino-6-phenylphenanthridine, 2,6-diaminopyridine. , and 3, 5-diamino-1, 2,4-triazole. An exemplary polymeric diamine is amino-terminated polyoxyethylene-polyoxypropylene copolymer, known as Jeffamine, available from Huntsman Corporation. A further description of such polymeric diamines can be found in US Patent 5,777,033, which is incorporated herein by reference. The protecting group R 1 can be a benzyloxycarbonyl group, a t-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. This list is exemplary only, and other known protecting groups for deactivating primary amines according to this invention are equally suitable. The protecting group R1 can also be any of the named groups where one or more hydrogen atoms are replaced with an aliphatic group, eg, an alkyl group having 1 to 6 carbon atoms, an alicyclic group with 6 to 12 atoms of carbon, 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 impede or substantially hinder the processes of protection and deprotection. Methods of protecting all, except an amine group, of a polyamine compound, particularly mono-protection of a diamine, are disclosed in Peptide Synthesis, Bodansky, Klausner &; Ondetti, second edition, Wiley-Interscien-ce, John Wiley and Sons (1976), in particular chapter 4, which is incorporated herein by reference. In the case of polyamines where two or more identical sites can react, special methods known to those skilled in the art can be applied. For example, in the case of a diamine, the protecting group is added progressively to a solution containing an excess of the diamine. In this case, there is always an excess of amine in the medium and the formation of the di-protected diamine is minimized. See, Krapcho & Kuell, "Mono-protected Diamines, N-tert-Butoxycarbonyl-a,? -Alkanediamines from a,? - Alkanediamines", Synthetic Communications, 20 (16), pp. 2559-2564 (1990), which is incorporated herein by reference. In one embodiment, the mono-protected diamine is recovered after filtration to remove the di-protected diamine, and extraction with solvent and a wash with water to remove the excess diamine. In other embodiments, the different constituents (i.e., polyamines having different numbers of protected amine groups) having different molecular weights and hence different boiling points can be separated by distillation fractionation or different separation techniques, such as chromatography. These methods of producing mono-active amines (ie, amine compounds having only one primary amine group and one or more protected primary amine groups) are known to those skilled in the art. In general, protecting groups and protection / deprotection processes are selected such that these processes can be carried out substantially without effect on the bonds between the electrophilic functional groups of the initial polymer and the simple primary amine groups of the protected amine compound or on the chemical structure of the unprotected amine compound. Initial Polymer Amine-reactive functional groups in the polyolefin containing functional group that is being reacted with the amine compound in general will be electrophilic groups such as carboxyl groups, esterified carboxyl, acid anhydride acid chloride, aldehyde, ketone, silane, epoxy, halogen, isocyanate or oxazoline. The anhydride groups are particularly useful as they react with primary amine groups to form stable, cyclic imido clusters. The polymer containing an initial functional group may, for example, be based on a base polymer, such as those formed from one or more C2-C20 alpha-olefins, optionally containing unconjugated diolefins and / or vinyl monomers copolymerizable. Such polyolefins can be crystalline, partially crystalline, or amorphous. In this way, suitable polyolefins are polypropylene, polyethylene, ethylene-propylene copolymers, ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer rubber (EPDM), and ethylene or propylene polymers with one or more alpha higher olefins (particularly ethylene / alpha-olefin copolymers) such as l-butene, l-hexene, 1-octene, etc. Additionally included are the polyethylene copolymer resins comprising one or more copolymerizable vinyl esters, acids, epoxies, carbon monoxide, etc. Throughout the description and the claims, the term "copolymer" is used in its definition accepted by the ASTM of a polymer formed from two or more types of monomers. As used in the description and claims, the term "polypropylene" (PP) includes propylene homopolymers as well as polypropylene reactor copolymers (RCPP) which may contain 1 to 20% by weight of ethylene or an alpha co-monomer -olefin of 4 to 20 carbon atoms. The polypropylene can be isotactic, syndiotactic or atactic polypropylene. The RCPP can be a random or block copolymer. The density of the PP or RCPP can be from 0.85 to 0.9 g / cm3. Polypropylene containing copolymerized unconjugated diolefins will also be particularly useful. High density polyethylene (HDPE), useful as a polyolefin resin, has a density of about 0.941 to about 0.965 g / cm3. High density polyethylene is an established trade product and its manufacturing and general properties are well known in the art. Polyethylene copolymer resins that can be optionally used in the compositions of this invention include polybutylene, low density polyethylene (LDP), very low density polyethylene (VLDPE) and linear low density polyethylene (LLDPE), as well as copolymers of ethylene with unsaturated esters of carboxylic acids. The term "polybutylene" generally refers to thermoplastic resins of both poly (l-butene) homopolymer and copolymer with, for example, ethylene, propylene, 1-pentene, etc. Polybutylene is manufactured via stereo-specific Ziegler-Natta polymerization of monomer (s). Commercially useful products are of high molecular weight and high isotacticity. A variety of commercial grades of both homopolymer and ethylene copolymer are available, with melt rates ranging from about 0.3 to about 20 g / 10 minutes. The term "low density polyethylene" or "LDPE", as used in the description and claims, means both low and medium density polyethylene having densities of about 0.91 to about 0.94 g / cm3. The term includes linear polyethylene as well as ethylene copolymers which are thermoplastic resins. "Linear low density polyethylene" (LLDPE) is a low density polyethylene characterized by little, if any, branching of long chains, in contrast to conventional LDPE. Processes for producing LLDPE are well known in the art and commercial grades of this polyolefin resin are available. Generally, it is produced in fluidized-bed, gas-phase reactors, or liquid-phase solution process reactors. The first process can be carried out at pressures of around 100 to 300 psi (0.7 to 2.1 MPa) and temperatures as low as 100 ° C. In one embodiment, an ethylene copolymer includes as co-monomer one or more C3 to C30 olefins, linear, branched, or ring-containing, capable of insertion polymerization, or combinations thereof. Preferred olefinic co-monomers with linear or branched C3 to C20 alpha-olefins, more preferably C3 to C8 alpha-olefins, even more preferably propylene, l-butene, l-hexene, and 1-ketene, even more preferably propylene or l-butene. Preferred branched alpha-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene. Preferred ring-containing olefinic monomers include at least one aromatic group as a ring structure. Preferred aromatic-containing monomers contain up to 30 carbon atoms. Suitable aromatic group-containing monomers comprise at least one aromatic structure, preferably one to three, more preferably a phenyl, indenyl, fluorenyl or naphthyl moiety. The monomer containing an aromatic group further comprises at least one polymerizable double bond, such that after polymerization, the aromatic structure is suspended from the polymeric backbone. The preferred aromatic group-containing co-monomers contain at least one aromatic structure attached to a polymerizable olefinic fraction. The polymerizable olefinic fraction can be linear, branched, containing cyclic structure, or a mixture of these structures. When the polymerizable olefinic fraction contains a cyclic structure, the cyclic structure and the aromatic structure can share 0, 1 or 2 carbons. The polymerizable olefinic fraction and / or the aromatic group may also have from one to all hydrogen atoms substituted with linear or branched alkyl groups containing from 1 to 4 carbon atoms. Particularly preferred aromatic co-monomers include styrene, alpha-methylstyrene, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene and allyl benzene. In this embodiment, the polyethylene copolymer is a semi-crystalline, preferably random, thermoplastic copolymer of ethylene and at least one alpha-olefin, more preferably C3 to C8, linear or branched, having a melting point of 60 to 125 ° C, preferably 65 to 110 ° C, more preferably 70 to 100 ° C. In a particularly preferred embodiment with polyethylene as the base polymer, the average ethylene content is at least 84 mol%, preferably from 87 to 98 mol%, and more preferably from 89 to 96 mol%. The remainder of the copolymer is from one or more lower olefinic monomers, capable of insertion polymerization, more preferably one or more alpha-olefins, as noted above, and optionally minor amounts of one or more diene monomers. The density of the polyethylene copolymer, in g / cm 3, is preferably in the range from 0.865 to 0.915, more preferably from 0.865 to 0.900, even more preferably from 0.870 to 0.890. The heavy average molecular weight (Mw) of the polyethylene copolymer can vary 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 catalysts and exhibit a narrow molecular weight distribution, meaning that the ratio of the heavy average molecular weight to the number average molecular weight will be equal to or less than 4, most typically in the range of 1.7 to 4.0, preferably 1.8 to 2. Such polyethylene materials are commercially available from ExxonMobil Chemical Company of Houston, Texas, United States, under the trade designation Exact. These materials can be made in a variety of processes (including slurry, solution, high pressure and gaseous phase), which employ metallocene catalysts. The processes for making a variety of polyethylene materials with metallocene catalyst systems are well known. See, for example, US Pat. Nos. 5,017,714; 5,026,798; 5,055,438; 5,057,475; 5,096,867 5,153,157; 5,198,401; 5,240,894; 5,264,405; 5,278,119; 5,281,679 5,324,800; 5,391,629; 5,402,217; 5,504,169; 5,547,675; 5,621,126 5,643,847; 5,767,208; 5,801,113; 5,861,945; and 6,100,214; patent applications US 08 / 877,390 and 08 / 473,693; European patent application EP 0 277 004; and the international publications WO 92/00333 and WO 94/03506, each being incorporated herein in its entirety. The production of ethylene and cyclic olefin copolymers is described in U.S. Patent Nos. 5,635,573 and 5,837,787, and of copolymers of ethylene and geminally di-substituted monomers, such as isobutylene, in U.S. Patent 5,763,556, all of which are incorporated herein in their entirety. . Other polyethylene copolymers suitable as the base polymer of this invention include copolymers of ethylene and polar co-monomers, such as unsaturated esters of carboxylic acids as well as carboxylic acids by themselves. In particular, copolymers of ethylene with vinyl acetate or alkyl acrylates, for example methyl acrylate and ethyl acrylate, can be used. These ethylene copolymers typically comprise 60 to 98% by weight of ethylene, preferably 70 to 95% by weight of ethylene, more preferably 75 to 90% by weight of ethylene. The term "ethylene copolymer resin", as used in the description and claims, generally means copolymers of ethylene with unsaturated esters of lower monocarboxylic acids C - ^ - C ^ and the acids themselves; e.g., acrylic acid, vinyl esters or alkyl acrylates. It is also intended to include both "EVA" and "EVOH", which refer to ethylene-vinyl acetate copolymers, and their hydrolyzed counterpart, ethylene-vinyl alcohols. Illustrative of the acrylates that may be used are methyl acrylate, ethyl acrylate, glycidyl methacrylate, and alkyl acrylate (where alkyl means any alkyl between and including propyl and dodecenyl). Examples of such polyethylene copolymers include ethylene-acrylic acid, ethylene-methyl acrylate, ethyl-methyl acrylate-acrylic acid, ethylene-methacrylic acid, etc. Also included are the terpolymers of ethylene and any of those polar monomers mentioned above. Similarly, those having acid groups only partially neutralized with metal cations to form those products known as isomers will be suitable herein. Particularly suitable according to this invention are the ethylene / alpha-olefin elastomers, which are defined to include ethylene / alpha-olefin copolymers, optionally with one or more unconjugated diolefins. Such polymers are well known, as are their methods of preparation, as described in US patents 4,895,897 and 4,749,505, which are incorporated herein in their entirety. Particularly preferred ethylene / alpha-olefin elastomers are prepared from ethylene and ethylenically unsaturated hydrocarbons, including cyclics, alicyclic and acyclic, containing from 3 to 28 carbons, preferably 2 to 18 carbons. These ethylene copolymers can contain from 15 to 90% by weight of ethylene, preferably 30 to 80% by weight of ethylene and 10 to 85% by weight, preferably 20 to 70% by weight, of one or more alpha-olefins C3 to C2B, preferably C3 to C18, more preferably C3 to C8. Although not essential, such copolymers preferably have a degree of crystallinity of less than 25% by weight, as determined by X-ray and differential scanning calorimetry. Ethylene and propylene copolymers are most preferred. Other suitable alpha-olefins 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 l-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-1-pentene, 4,4-dimethyl-1-pentene, 6-methyl-1-heptene , etc., and their mixtures. The term "copolymer", as used herein, unless otherwise indicated, includes terpolymers, tetrapolymers, etc. of ethylene, said C3-C28 alpha-olefin and / or an unconjugated diolefin or mixtures of such diolefins, which may also be used. The amount of unconjugated diolefin will generally vary from 0.5 to 20 mol%, preferably 1 to 7 mol%, based on the total amount of ethylene and alpha-olefin present. Representative examples of non-conjugated dienes that can be used as the third monomer in the terpolymer include: (a) straight chain acyclic dienes, such as 1,4-hexadiene; 1,5-heptadiene; and 1, 6-octadiene; (b) branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene; 3, 6-dimethyl-1,6-octadiene; 3, 7-dimethyl-1, 7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1, 5-cyclo-octadiene; 1, 5-cyclo-dodecadiene; 4-vinylcyclohexene; l-allyl-4-isopropylidene cyclohexane; 3-allyl-cyclopentene; 4 -allyl-cyclohexane; and 1-isopropenyl-4- (4-butenyl) -hexane; (d) single multi-ring alicyclic dienes, such as 4,4'-dicyclopentenyl and 4,4'-dicyclohexenyl diene; and (e) multi-ring, fused and ring-bridged alicyclic 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. Of the non-conjugated dienes typically used, 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, -hexadiene. The unconjugated diene is incorporated into the polymer in an amount of about 0.1 to 15% by weight; more preferably, from 0.5 to 10% by weight, most preferably from 1 to 10% by weight. The ethylene / alpha-olefin elastomers of this invention can be prepared by methods well known in the art. In fact, various examples of such commercially available copolymers are Vistalon, ethylene and propylene elastomeric copolymers alone or with 5-ethylidene-2-norbornene, marketed by ExxonMobil Chemical Company of Houston, Texas, United States, and Nordel®, a copolymer of ethylene, propylene and 1,4-hexadiene, marketed by El duPont de Nemours & Company, of Wilmington, Delaware, United States. These copolymers of ethylene, terpolymers, tetrapolymers, etc., are readily prepared using soluble Ziegler-Natta catalyst compositions. For a review of the literature and patents see: "Polyolefin Elastomers Based on Ethylene and Propylene", F.P. Baldwin and G. See Strate, Rubber Chem. & Tech. , vol. 45, No. 3, 709-881 (1972), and Polymer Chemistry of Synthetic Elastomers, Kennedy and Tornqvist, editors, Interscience, New York (1969). For more recent reviews, see: "Elastomers, Synthetic (Ethylene-Propylene)", E.L. Borg, in Encyclopedia of Chemical Technology, third edition, vol. 8, 492-500, Kirk-Othmer (1979) and "Ethylene-Propylene Elastomers", G. Ver Strate, in Encyclopedia of Polymer Science and Engineering, vol. 6, second edition, 522-564, J. Wiley & Sons (1986). The disclosure of each of these references is incorporated herein by reference. Additionally, the elastomeric butyl rubber and the halogenated butyl rubber are suitable as the initial polyolefin polymer when they contain, or are modified to contain, functional groups reactive with primary amine groups. Butyl rubber and halogenated butyl rubber are well-known commodities and any polymeric product such, functionalized in an appropriate manner, will be effective according to the invention. These polymers are based on the cationic polymerization of isobutylene, optionally with one or more monomers (such as isoprene or a para-alkylstyrene, particularly para-methyl-tyne) copolymerizable therewith, all as is well known. Included for the purposes of this invention within the term elastomeric butyl rubber is the case of polyisobutylene rubber compositions, which strictly speaking is not butyl rubber, but instead an elastomeric isobutylene homopolymer. The polyisobutylene rubber is also a well-known merchandise, manufactured according to known methods. Its use in lubricating oils, when modified with acidic / succinic anhydride groups, optionally aminated, is particularly suitable for this invention. A preferred polypropylene copolymer used in the present invention includes one or more co-monomers selected from ethylene and C4-C20 alpha-olefins and having crystallinity that is a result of stereo-regular polypropylene sequences. Such polypropylene copolymers are described in detail as the "second polymeric component (SPC)" in patent applications US 09 / 569,362, filed on May 11, 2000, 09 / 342,854, filed on June 29, 1999, and 08 / 910,001, filed August 12, 1997 (published as WO 99/07788), and described in greater detail as the "propylene-olefin copolymer" in the patent application US 09 / 346,460, filed July 2, 1999 , all incorporated herein by reference. The low levels of crystallinity in the polypropylene copolymer are derivatives of isotactic or syndiotactic polypropylene sequences, preferably isotactic polypropylene sequences, obtained by incorporating minor olefinic monomers, as described above, as co-monomers. Preferred polypropylene copolymers have an average content of propylene, on a molar basis, from 49 to 92%, more preferably from 59 to 91%, even more preferably from 65 to 88%, even more preferably from 72 to 86% , with the greater preference of 78 to 85%. The remainder of the copolymer is one or more linear or branched alpha-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 of 9 to 76 J / g, more preferably 11 to 57 J / g, more preferably 15 to 47 J / g, even more preferably 17 at 38 J / g. The crystallinity of the polypropylene copolymer arises from stereo-regular, crystallizable propylene sequences. The electrophilic groups are most preferably provided with compounds containing ethylenically unsaturated electrophilic groups, which are either copolymerized during the preparation of the thermoplastic polymers or are grafted into a previously prepared polymer or by halogenation, such as in halobutyl. Copolymerization including the compound providing the electrophilic groups will be possible when all monomers of the polymers are polymerizable by either conventional free radical catalysis or Ziegler coordination catalysis. Copolymerizable monomers incorporated by free radical catalysis include co-monomers such as alkyl acrylates, vinyl esters, acrylic acids, methacrylic acid, glycidyl methacrylate, and the like. Such thermoplastic polymers are known in the art, as is their method of preparation. Illustrative of this knowledge are US Patent 4,017,557 or WO 96/23010, which are incorporated herein by reference in their entirety. In this manner, copolymerizable monomers that allow the incorporation of these reactive electrophilic groups into the polyolefins will be useful in accordance with this invention. Such compounds, and methods of both preparation and incorporation with polyolefinsThey are also well known. Ziegler copolymerization descriptions are found, inter alia, in US Patents 3,492,227; 3,761,458; 3,796,687; 4,017,669; 4,139,417; 4,423,196; and 4,987,200, the disclosures of which are incorporated herein by reference in their entirety. These patents teach the preparation of polyolefins, particularly random terpolymers of ethylene, tetrapolymers, etc., from alpha-olefins, non-conjugated dienes and unsaturated functional monomers, by direct Ziegler-Natta polymerization of the monomers, usually in solvent, using systems catalysts consisting of trivalent and higher vanadium compounds, organoaluminium compounds and, for some, halogenated reactivating compounds. These polymerization reactions are run in the absence of moisture in an inert atmosphere and in a preferred temperature range of 0 to 65 ° C. Both continuous and batch reactions are taught. Included within the term "copolymerization", for the purposes of this invention, are those reactions that terminate chains where the appropriate functional groups are added to a thermoplastic polymer in formation and simultaneously terminate the polymerization reaction. Such reactions are sometimes called end-cap reactions and are generally known. In particular, carbonation of polymers prepared by anionic polymerization by the introduction of CO 2 gas into the living polymerization reaction and the termination of that reaction will be suitable for this invention. A description appears in the subject; see, for example, the teachings of US Patent 4,950,721, which is incorporated herein by reference in its entirety. The end cap of polyolefins prepared by means of Ziegler-Natta copolymerization is known, in particular an effective use of hydroxy compounds can be made in accordance with the disclosure contained in US Pat. No. 4,999,403, which refers to the disclosure contained in the patent. US 5,030,695, both of which are hereby incorporated by reference in their entirety. By using compounds containing functional groups that terminate chains, the graft copolymers prepared by subsequent reaction with the amine compounds of the invention are extremely grafted with those amino compounds. The graft addition of compounds containing ethylenically unsaturated electrophilic groups, suitable in this invention, e.g. Maleic anhydride is conveniently achieved by heating a physical mixture of the polyolefin and the compounds containing unsaturated electrophilic groups within a range of 150 to 400 ° C, often in the presence of free radical initiators, such as organic peroxides. Methods of preparing these graft polymers are well known in the art, as illustrated in US Patents 4,017,557 (above); 3,862,265; 3,884,882; 4,160,739; 4,161,452; 4,144,181; 4,506,056; and 4,749,505, the disclosures of which are incorporated herein by reference in their entirety. The use of heat and / or physical shear stress, optionally with free radical initiators, in equipment such as extruders or chewers, to achieve the free radical grafting of compounds containing electrophilic, ethylenically unsaturated groups, all as it is known in the matter, it will be particularly useful in accordance with this invention. The graft addition to polyolefins of monomers containing carboxylic acid groups, and monomers containing epoxy groups, is also known. The description appears in, inter alia, US Pat. Nos. 3,862,265; 4,026,967; 4,068,057; 4,388,202; and 4,749,505, the disclosures of which are incorporated herein by reference in their entirety. As noted, these grafting methods are parallel to those useful for the grafting of maleic anhydride described more fully in the foregoing. The compounds containing epoxy groups effective in such grafting reactions are represented by glycidyl acrylate, glycidyl methacrylate, and similar. One or more electrophilic groups useful in accordance with this invention are thus easily incorporated into the functionalized polymers of this invention by the use of the knowledge of the art. Isocyanate groups can also be grafted onto polyolefin backbones by the reaction, for example, of TMI (META) [benzene, 1- (1-isocyanato-1-methylethyl) -3- (1-methylethyl), produced by American Cyanamid Company] in the presence of a peroxide. Oxazoline functionality can also be introduced into a polyolefin, according to methods described in reactive modifiers for polymers. (See, S. Al-Malaika, Blackie Academic & Professional (1997), chapter 4.) Although the description herein of the incorporation of electrophilic groups is directed to conventional methods of copolymerization and grafting, it will be apparent to those skilled in the art that any additional methods for such incorporation will be effective for achieve the objectives of this invention. For example, the preparation of polymeric compounds containing epoxy groups by direct epoxidation of polymers containing unsaturation either spinal or pendant is known. U.S. Patent 3,330,794; 3,448,174, and 3,551,518, describe the use of epoxidizing agents, such as perbenzoic acid, to directly oxidize the unsaturation in elastomeric compounds containing ethylene, to obtain incorporated epoxy, or oxirane groups. The disclosures of these patents are incorporated herein by reference in their entirety. The amount of compound containing electrophilic groups, incorporated in the functionalized polymer, will be sufficient to provide at least one reactive site per chain with the primary amine group-containing compound, ie the monomers containing electrophilic groups must constitute at least 0.01% by weight of the thermoplastic polymer component containing functional groups. In the most typical manner, the monomer containing electrophilic groups will constitute 0.01 to 15% by weight, preferably 0.05 to 5.0% by weight. The amount of functional fractions present, whether contributed by monomers containing functional groups, or by direct functionalization, will thus be 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 polymers and copolymers styrene base, or terpolymers of ethylene-acrylic ester-maleic anhydride or ethylene-acrylic ester-glycidyl methacrylate, such as Lotader, available from Atochem. Styrene-based polymers, suitable for incorporation by grafting of one or more compounds containing electrophilic groups, and well known in the art, include those that can be described as hydrogenated or partially hydrogenated homopolymers, and random, tapered or block polymers (copolymers, including terpolymers, tetrapolymers, etc.) of conjugated dienes and / or mono-vinyl aromatic compounds with, optionally, lower alpha-olefins or alkenes, eg, alpha-olefins or lower alkenes C3 to C18. Conjugated dienes include isoprene, butadiene, 2,3-dimethyl-butadiene, piperylene and / or mixtures thereof, such as isoprene and butadiene. The mono-vinyl aromatic compounds include any of the following, or their mixtures: di or poly-aromatic vinyl compounds, e.g., vinyl naphthalene, but are preferably mono-aromatic mono-vinyl compounds, such as styrene or substituted alkynes on the alpha carbon atoms of styrene, such as alpha-methylstyrene, or on ring carbons, such as o, p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, butylstyrene, isobutylstyrene, and t-butyl-styrene (e.g., pt-butyl styrene). Also included are vinylxilenes, methylethylstyrenes, and ethylvinylstyrenes. The alpha-olefins and the lower alkenes optionally included in these random, tapered and block copolymers of preference include ethylene, propylene, butene, ethylene / propylene copolymers, isobutylene, and their polymers and copolymers. As is also known in the art, these random, tapered and block copolymers may include relatively small amounts, ie less than 5 mol%, 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, hydrogenated polyvinyl-cyclohexane-polyisoprene, and hydrogenated polyvinyl-cyclohexane-polybutadiene. The tapered polymers include those of the above monomers, prepared by methods known in the art. Other suitable 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 0 416 815 A2, which is incorporated herein by reference in its entirety. Suitable styrene-based polymers having electrophilic functionality incorporated in accordance with the invention include those comprising styrene and maleic anhydride, optionally containing copolymerizable monomers, as disclosed in US Pat. No. 4,742,116, the disclosure of which is incorporated herein by reference. reference in its entirety. Graft Reaction Process The reaction of the functionalized initial polymer with the amine compound can be carried out either in solution or by heating the mixture. In a preferred embodiment, an important aspect of this invention is the ease of conducting the reaction process to a large extent in accordance with the melt-state processing reaction conditions well known to those skilled in the art. The reaction temperature will preferably be in the range of 160 to 200 ° C, more preferably 1-70 to 195 ° C, even more preferably 180 to 190 ° C. Such a reaction can easily be achieved in a mixing device such as a Brabender or Banbury mixer or an extruder, e.g., a single screw extruder or twin screws. The reaction time can be a few seconds (eg, 30 seconds) to a few minutes, or even longer, to optimize the efficiency of the reaction and the possible side effects of the reaction temperature, such as degradation. of molecular weight of the thermoplastic polymer. The amine must be present in an amount equal to or exceeding the number of functionally available reactive sites. The amine functionality can be assayed by solvent titration, and residual groups such as anhydride can be assayed by Fourier transform infrared spectroscopy (FTIR). In another embodiment, the grafting reaction of the amine compound protected with the initial polymer is carried out in solution. Preferred solutions include aliphatic, aromatic, alicyclic, alkane, 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 a mixture of a polar solvent and a non-polar solvent). The preferred pressure range for the solution process is atmospheric pressure at 10 bar (1 MPa) or less, more preferably up to 5 bar (0.5 MPa) or less. The preferred temperature range for the solution process is 100 to 220 ° C, more preferably 150 to 200 ° C, even more preferably 180 to 195 ° C. Deprotection Process Deprotection, or removal of protective groups, can be achieved in a process in solution or in a process in the melted state. In a deprotection process either in solution or in the melted state, it is essential that the process conditions that facilitate the removal of the protecting groups have no substantial effect on the bonds between the functional electrophile groups of the initial polymer and the simple primary amine groups. of the polyfunctional amine compound, masked or the chemical structure of the unprotected amine compound. Almost all combinations of polymer, amine compound, and protecting group can be unprotected in solution. Only one potion of these combinations can be unprotected via heat, due to the failure of one or more of the other chemical bonds before the separation of the protecting group. Technicians in the various polymer materials and in amine chemistry would be able to select an appropriate deprotection process for a given combination of polymer, amine compound, and protecting group. In a process in the melted state, the protective group can be removed either thermally or in the presence of acid catalysts. In one embodiment, a polymer containing primary amines protected with a t-butoxycarbonyl group can be deprotected by heating the polymer. Isobutylene and carbon dioxide are released when the protecting group is removed and replaced by hydrogen atoms. A temperature above 250 ° C is preferred in order to reach activation energies that allow the removal of the protective group within short residence times by a hydrogen atom. For a deprotection process in solution, the removal of the protecting group is carried out according to methods known to those skilled in the art and described, for example, in Peptide Synthesis, Bodansky, Klausner &; Ondetti, second edition, Wiley-Interscience Publication, John Wiley and Sons (1976), in particular chapter 4, which is incorporated herein by reference. Generally, it is required that the selected deprotection process involves only process conditions that do not substantially alter the polymer structure (e.g., chain cut or crosslink), the link between the functional electrophilic group of the starting polymer and the amine primary, or the bonds that connect the amine groups of the amine compound with the linking group or with each other. For example, Table 1 shows specific protective groups and appropriate methods for their removal.
Table 1
* protective group attached to the amine (or group formed by reaction of a protecting group precursor and the amine group) after replacement of one or two hydrogen atoms of the amine The list of methods is only exemplary and other methods for removing groups Primary amine protectants according to this invention are suitable. Methods of protecting and deprotecting primary amine groups are well known to those skilled in the art. Details of such methods can be found in Peptide Synthesis, Bodansky, Klausner & Ondetti, second edition, Wiley-Interscience Publication, John Wiley and Sons (1976), in particular chapter 4, which is incorporated herein by reference. Description of Uses As indicated above, the amino-modified polymers according to the invention can be used directly as compatibilizing or modifying agents for thermoplastic polymer compositions. For example, US Patent 4,742,116 suggests the use of EPR or NDMP grafted with nitrogen as an effective modifier for styrene-maleic anhydride copolymers. Similarly, European patent application EP 0 321 293 A discloses the use of EPR or functionalized EPDM, where the incorporated functionality can be amino, as an effective impact modifier for molding compositions of polybutylene terephthalate. US Patent 4,895,897 discloses the use of an intermediate functionalized elastomer, including amine-functionalized elastomer, reacted with oxazoline-functionalized polystyrene, to prepare effective graft polymers to modify the impact properties of aromatic polycarbonate (polycarbonate) compositions. EPR or amino-modified EPDM can also be used as compatibilizing agents between EPDM and nitrile rubbers, with the aim of improving the thermal resistance with a minimum punishment to the oil resistance. Thus, according to this invention, graft polymers are provided which can be used as modifying or compatibilizing agents with any thermoplastic polymer having molecular interaction with either the polymeric backbone of the graft polymer or the grafted amine functionality. In this way, physical mixtures of the graft polymer of the invention with one, two or more different polymers, particularly engineering thermoplastics, or in lubricating oil compositions, will be possible. The amine-functionalized polymer according to the invention can be reacted or physically mixed with a second polymer by reaction in the melted state, for example in a Brabender mixer or in an extruder. This reaction can be conducted in the same reactor as the deprotection reaction or, subsequently, in another reactor for reactions in the melted state. The time and the reaction temperature will depend on the polymers present. This reaction can be carried out in a subsequent, separate step, or it can be carried out in itself in a fusion of the polymer or the polymers to be compatibilized.
Basically, the polyolefin functionalized with primary amine can react with any of the polymers containing functional groups that are reactive to the 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 electrophilic site that contains a good leaving group. An extensive list can be found in "Reactive Polymers for Blend Compatibilization", Advances in Polymer Technology, vol. 11, 249 (1992), the disclosure of which is incorporated herein by reference. Thus, for example, polypropylene functionalized with amine (amino-PP) can be reacted in the melted / physically mixed state with a physical mixture of styrene-maleic anhydride polymer in polypropylene. In a similar way, physical blends of polypropylene containing other polymer systems, especially engineered thermoplastics that are reactive, or otherwise compatible, with the aminated polypropylene, can be prepared having an improved overall physical blend compatibility between the polypropylene, the other polymer, and the aminated polypropylene. Similar physical mixtures of (1) unmodified polymer with (2) functionalized, aminated polymers, equivalent thereto in the sense of being derivatives of the same polymer or its family, and (3) another polymer rendered at least partially miscible or compatible with ( 2) by the presence of the amine functionality, will now be possible in accordance with the teachings of this invention. Specifically, as shown in the cited state of the art, the use of EP rubber with polyester engineered plastics (e.g., polybutylene terephthalate, polycarbonate, etc.) or other styrene-anhydride based thermoplastics Maleic or the use of other ethylene-based copolymer resins may be increased by the inclusion of the ethylene-based, aminated polymers, and the copolymers of this invention. Also, amino-polyolefins according to this invention can be used to compatibilize otherwise incompatible polymeric physical blends of polyolefins and halogenated polymers, such as polyvinyl chloride (PVC), poly (divinyl chloride) (PVDC), poly (divinyl fluoride) (PVDF), chlorinated nitrile rubber, halobutyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, and the like. Such physical mixtures may be useful, for example, to improve the surface properties of polypropylene articles. Aminated polyethylene can advantageously be used as a tie layer in multi-layer films where it can promote adhesion between two otherwise incompatible polymer layers, such as polyethylene and PVDC. It will be apparent to those skilled in the art that the broad applicability of aminated polyolefins will be useful in improving the overall properties of polymer blends, and thus has the potential to recycle mixed plastics, particularly those containing a significant portion of the polyolefins. Amine-functionalized EPDM can be used to compatibilize physical mixtures of EPDM and Vamac (ethylene terpolymers, acrylic acid and acrylic esters, available from DuPont) or acrylate or epichlorohydrin rubbers or nitrile rubber or hydrogenated nitrile rubbers, for thermoformed applications where An increase in properties such as green strength, thermal resistance or cost reduction is desired. For lubricating oil compositions, 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 they react the amine compounds of this invention. In this manner, oil soluble polymers prepared according to the disclosure herein will be useful for lubricating oil compositions. More particularly, those polymers having a number average molecular weight of 500 to 10,000, preferably 800 to 3,000, will have utility in detergent and dispersant applications. Those having a number average molecular weight of 10,000 to 1,000,000, preferably 20,000 to 400,000, will have multi-functional utility as viscosity index improvers, as well as dispersants. Methods of preparation, and a further description of such lubricating oil compositions, are well known, as exemplified by US Patents 4,749,505; 4,670,173; and 4,520,171, which are incorporated herein by reference. Polymeric physical blends containing the primary amine functionalized polymers of this invention also have additional advantageous uses, including, but not limited to, improved properties such as: paint adhesion; adhesion to treated glass fibers or other fillers; reinforcement in EPDM compounds filled with carbon black through a better interaction between the carbon black and the 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 co-extruded tie-down resins (CTR) for film applications; co-extruded profiles for production of sealing of automotive bodies or manufacture of co-extruded hoses; plastic cover with polyolefins. Examples Description of experiments and tests The content of unsaturated acid or anhydride was measured by FTIR (Fourier transform infrared spectroscopy). The reaction products were compressed at a temperature of 165 ° C in thin films from which infrared spectra were taken using a Fourier transform infrared spectrometer Ma tson Polaris, at a resolution of 2 cm "1, with an accumulation of 100 scans The relative peak heights of the anhydride absorption band at 1790 cm4 and the absorption of acid (coming from hydrolysis of the anhydride in air) to 1.712 cm "1 were compared with a band at 4.328 cm" 1 serving as internal standard, were taken as a measurement of MA content, according to the following relationship:% MA (total MA content) = k (A1790 + A1712) / A4328, with 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-16 6. The melt index (MI) was measured according to ASTM method D-1238 (E). of flu melted jo (MFR) was measured according to ASTM method D-1238 (L). The density was measured according to the method ASTM 1238. Materials used in the examples The Exact 4033 polymer is an ethylene-butene copolymer produced using metallocene catalyst and available from ExxonMobil Chemical Company, of Baytown, Texas, United States. This copolymer has a density of 0.880 g / cm3 and a melt index (MI) of about 0.8 g / 10 min at 190 ° C and 2.16 kg. Initial Polymer (IP) IP1: ethylene-butene copolymer grafted with maleic anhydride. The Exact 4033 copolymer was modified in a twin screw extruder (Welding Engineer, 30 mm, 48 L / D) with the following temperature profile: 170, 180, 210, 210, and 200 ° C. The modification was carried out at 7 kg / hr of polymer feed rate and a screw speed of 250 rpm. 0.6% by weight of maleic anhydride and 0.015% by weight of peroxide (Luperox 130 from Atochem) were added. The maleic anhydride-modified polymer had a density of 0.880 g / cm3, a Mooney viscosity of ML (1-4) of 38 to 125 ° C, and an anhydride content of 0.45% by weight, as measured by FTIR. IP2: ethylene-butene copolymer grafted with maleic anhydride. The Exact 4049 polymer was modified in a twin screw extruder (Welding Engineer, 30 mm, 48 L / D) with the following temperature profile: 170, 180, 210, 210 and 200 ° C. The modification was carried out at a polymer feed rate of 7 kg / hr and a screw speed of 250 rpm. 4% by weight of maleic anhydride and 0.18% by weight of peroxide were added. The polymer modified with maleic anhydride had a density of 0.873 g / cm3, an MFR (230 ° C, 5 kg) of 3 g / 10 min and an anhydride content of 3% by weight, as measured by FTIR. IP3: ethylene-butene copolymer grafted with maleic anhydride. The Exact 4049 polymer was modified in a twin screw extruder with the following temperature profile: 170, 180, 210, 210 and 200 ° C. The modification was carried out at a polymer feed rate of 7 kg / hr and a screw speed of 250 rpm. 1% by weight of maleic anhydride and 0.04% by weight of peroxide (Luperox de Atochem) were added. The maleic anhydride modified polymer had a density of 0.873 g / cm3, a Mooney viscosity of ML (l + 4) of 44 to 125 ° C, and an anhydride content of 0.8% by weight, as measured by FTIR. Protected amine: N-t-butoxycarbonyl-1,6-hexanediamine was produced by condensation of 1,6-hexanediamine with di-t-butyl bicarbonate, as described in Krapcho & amp;; Kuell, "Mono-protected Diamines, N-tert-Butoxycarbonyl-a,? -Alkanediamines from a,? -Alkanediamines", Synthetic Communications, 20 (16), pp. 2559-2564 (1990). Example 1: Production of polymer with protected, pendant amine groups in solution 20 g of IP2 were dissolved in 500 ml of xylene and 2.6 g of the protected amine was added. The solution was heated to the reflux temperature of xylene for two hours. The solution was cooled to 70 ° C and poured into 1 1 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. The FTIR spectrum of the product indicated the disappearance of the maleic anhydride peak at 1,790 cm "1 and the peak formation at 1,705 cm" 1, typical of the imide functionality, as well as small peaks at 1,395, 1,150, and 1,120 cm "1 , specific for the protected amine groups Example 2: production of polymer with protected, pendant amine groups in an extruder A physical mixture was prepared by physically blending dry 1 kg of IP3 with 30 g of mono-protected amine in an open mill, at room temperature, for 10 minutes From the final sheet, strips were cut and fed to a Haake Rheocord 90 extruder (25 L / D, 3/1 compression ratio) at different temperatures from 160 to 220 ° C to 25 The Mooney viscosity of the polymers obtained after the amination is given for each temperature in Table 2. Table 2
From the table, it is clear that for temperatures lower than 200 ° C, there is no fundamental change in the viscosity of the polymer. This would indicate that the protective group is stable up to these temperatures, while above 200 ° C, cross-linking occurs as a result of deprotection of the protective group and competitive reactions. Example 3: Polymer production with protected, pendant amine groups in an extruder Polymer IP1 was fed at a rate of 3 kg per hour to a twin screw extruder (Welding Engineer, 3 mm, 48 L / D), heated to 180 ° C. The screw speed was set at 200 rpm and the mono-protected amine was fed at a rate of 0.84 ml / min. Nitrogen and vacuum stripping (700 mbar (70 kPa)) were applied to the ventilation barrel in order to remove the excess protected amine. Protected, recovered, amino-protected IP1 had a Mooney viscosity [ML (l + 4), 125 ° C] of 27. Extrusion conditions: Welding Engineer twin screw extruder, 25 mm D, 42 L / D Temperature: 180 ° C in the four zones Screw speed: 200 rpm Disposal with N2 Vacuum in the ventilation barrel: 700 mbar (70 kPa) Power conditions: IP1: 3 kg / hr Mono-protected amine: 0.84 ml / min Amino-protected, protected IP1: Mooney viscosity ML (l + 4), 125 ° C: 27 The FTIR spectrum is extremely similar to that of Example 1. There was essentially no cross-linking or extension of chains during the amination reaction , because the Mooney viscosity of the polymer was basically reduced after the reaction. This reduction would indicate some molecular weight breakdown due to the higher shear stress generated on the twin screw extruder versus the single screw experiment. Example 4: Deprotection of the protected amine groups of the "protected" amine-grafted polymer in solution 2 g of the mono-protected amine functionalized polymer, produced in Example 3, was dissolved in 40 ml of xylene, and 4 ml of a 5 M aqueous solution of HCl. The solution was heated to the reflux temperature of xylene for two hours. The solution was cooled 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 two hours, then analyzed by FTIR. The FTIR spectrum showed that the protective groups were removed as the peaks disappeared at 1,395, 1,150 and 1,120 cm "1, respectively, and the imide peak at 1,705 cm" 1 was expanded as a result of hydrogen bonding between the carbonyl group and the free amine group. Example 5: Deprotection of amine groups protected from graft polymer with "protected" amine by means of heat 42 g of the functionalized polymer with mono-protected amine in Example 3 was mixed in a Haake Rheocord mixer, for one hour, at a temperature of 300 ° C chamber, with a rotor speed of 100 rpm. The polymer was then recovered, cooled and analyzed by FTIR. The FTIR spectrum of the deprotected polymer was extremely similar to that of Example 4. The Mooney viscosity of this polymer., ML (l + 4), 125 ° C, was 20, indicating that there was essentially no cross-linking or extension of chains having place during the deprotection reaction, as the viscosity of the polymer did not increase significantly. It will be further evident to those skilled in the art that conventional additives can be used in conventional amounts, when added in accordance with the existing knowledge in the art. Such additives, amounts and conditions are illustrated in the patents incorporated by reference.