CA2270333A1 - Gels derived from extending grafted-a-olefin maleimide centipede polymers and copolymers - Google Patents

Abstract

The present invention teaches a method for enabling the formation of a high damping, soft polymer gel. The method includes: reacting a poly(.alpha.-olefin-co-maleimide) polymer with a maleated polyalkylene and an alkyl diamine under substantially dry conditions sufficient to form a polyalkylene grafted poly(.alpha.-olefin-co-maleimide) polymer product; and, dispersing the polyalkylene grafted poly(.alpha.-olefin-co-maleimide) polymer product with an extender oil sufficient to form the gel. The present invention also contemplates a polymer gel composition, a polymer composition and an article manufactured from the polymer gel composition.

Description

' CA 02270333 1999-04-28 2 This invention relates to oil or low molecular weight component extended grafted 3 "centipede" polymer of a maleated polypropylene and a poly(a-olefin-(co)-(maleimide)) that is 4 useful in producing high damping, soft materials BACKGROUND OF THE INVENTION
6 The polymerization of olefins such as octadene and malefic anhydride by free radical 7 initiation is well known in the prior art. As disclosed in United States Patent 5,066,742, to Gupta;
8 Vijai P., as the first step, malefic anhydride and a C, - C8 olefin are typically polymerized in the 9 presence of a free radical initiator in a blend of a reaction solvent selected from the group consisting of esters of acetic acid, formic acid, and propionic acid and a C6 -C1, hydrocarbon I I diluent. Further, imidization between a malefic anhydride and an alkyl amine group is a commonly 12 known chemical reaction. Patent publications which have recognized these reactions include:
13 German Patent DE 4241538, assigned to Leuna-Werke A.-G; Japanese Patent JP
94248017, 14 assigned to Monsanto Kasel Kk.; and, Italian Patent EP 322905 A2, assigned to Montedipe S.p.A. Various other non-patent publications have also recognized these reactions. Included 16 among them are: L.E. Colleman, Jr., J.F. Bork, and H. Donn, Jr., J. Org.
Chem., 24, 185(1959);
17 A. Matsumoto, Y. Oki, and T. Otsu, Polymer J., 23(3), 201 ( 1991 ); L.
Haeussler, U. Wienhold, V.
18 Albricht, and S. Zschoche, Themochim. Acta, 277, 14(1966); W. Kim, and K.
Seo, Macromol.
19 Rapid Commun., 17, 835(1996); W. Lee, and G. Hwong, J. Appl. Polym. Sci., 59, 599(1996); I.
Vermeesch and G. Groeninckx, J. Appl. Polym. Sci., 53, 13 56( 1994); Y. Kita, K. Kishino, and K.
21 Nakagawa, J. Appl. Polymer. Sci. 63, 1055 (1997).
22 The synthesis of various monofunctional N-alkyl and N-aryl maleimides are also well 1 known in the prior art. These maleimides have been extensively used to improve the heat stability 2 of homo- and especially copolymers such as AB S (poly(acrylonitrile-butadiene-styrene)) or a 3 polyblend of poly(acrylonitrile-butadiene) and poly-(styrene-acrylonitrile);
PVC (poly(vinyl 4 chloride)); SAN (polystyrene-co-acrylonitrile)); PMMA (poly(methyl methacrylate)); and the S like. These maleimides may be copolymerized with other monomers such as acrylonitrile, 6 butadiene, styrene, methyl methacr5~late, vinyl chloride, vinyl acetate and many other 7 comonomers. A more preferred practice in the industry is to produce copolymers of maleimides 8 with other monomers and optionally with acrylonitrile and to blend the resultant copolymer with 9 ABS and SAN resins. In any event, the copolymer compositions are adjusted to be fully compatible with the bulk resins (e.g., ABS and/or SAN) as shown by the presence of a single 11 glass transition point (T~) as determined by differential scanning calorimetry (DSC).
12 Maleimide-containing vinyl resins and their use in the manufacture of parts for automobiles, I 3 electrical and electronic machinery and appliances, because of their good heat resistance, impact 14 resistance and moldability, are generally described, for example, in U.S
Pat. No. 3,652,726, U.S.
Pat. No. 3,676,404, U. S. Pat. No. 3,766,142, U. S. Pat. No. 4,039,734, U. S.
Pat. No. 4,374,951, 16 U.S. Pat. No. 4,381,373, U.S. Pat. No. 4,605,700, U.S. Pat. No. 4,683,275, U.S. Pat. No.
17 4,874,829, U.S. Pat. No. 4,879,343, U.S. Pat. No. 4,914,138, U.S. Pat. No.
4,954,571, U.S. Pat.
18 No. 4,983,669, U.S. Pat. No. 5,028,651, U.S. Pat. No. 5,091,470 and U.S.
Pat. No. 5,136,052.
19 As noted above, United States Patent 5,066,742, to Gupta; Vijai P., discloses copolymer suspensions of malefic anhydride and C, - Cg olefins used in the manufacture of synthetic fibers.
21 United States Patent 5,424,380, to Doi, relates to a resin composition comprising an 22 N-alkyl-substituted maleimide/olefin copolymer and a specified resin, which has excellent heat I resistance, rigidity, izod impact strength, weather resistance and dimensional resistance. United 2 States Patent 4,919,925, to Ueda, et. al., disclose Diels-Alder reaction-type adduct of an alpha, 3 beta-unsaturated dicarboxylic acid anhydride and an olefin or a derivative of the adduct as an 4 active ingredient in deodorants. All of the above are incorporated by reference herein for all purposes as if fully set forth.
6 It has long been recognized that two or more polymers may be blended together to form a 7 wide variety of random or structured morphologies to obtain products that potentially offer 8 desirable combinations of characteristics. However, it may be difficult or even impossible in 9 practice to achieve many potential combinations through simple blending because of some inherent and fundamental problem. Frequently, the two polymers are thermodynamically I 1 immiscible, which precludes generating a truly homogeneous product. This immiscibility may not 12 be a problem per se since often it is desirable to have a two-phase structure. However, the 13 situation at the interface between these two phases very often does lead to problems. The typical 14 case is one of high interfacial tension and poor adhesion between the two phases. This interfacial tension contributes, along with high viscosities, to the inherent difficulty of imparting the desired 16 degree of dispersion to random mixtures and to their subsequent lack of stability, giving rise to 17 gross separation or stratification during later processing or use. Poor adhesion leads, in part, to 18 the very weak and brittle mechanical behavior often observed in dispersed blends and may render 19 some highly structured morphologies impossible.
As a general rule, it is particularly desirable to prepare a grafted polymer having the 21 impact strength of polypropylene and the elastomeric properties of a block copolymer and to 22 extend the resultant copolymer with a high oil or low molecular weight component content to 1 obtain a soft material having a low Shore A hardness. Similarly in the case of the present 2 invention it is particularly desirable to prepare a grafted poly[a-olefin-(co)-(maleimide)J, so as to 3 obtain a soft material having a low Shore A hardness.
4 Thus, the oil or low molecular weight component extended grafted polymers of this S invention, comprising the grafting of a poly[a-olefin-(co)-(maleimide)] to a maleated 6 polypropylene by the use of a difunctional grafting agent reactive with the anhydride groups on 7 the centipede polymer and the maleate groups of the maleated polypropylene, are not currently 8 known to the prior art.

Accordingly, it is an object of this invention to provide an oil or low molecular weight 11 component extended grafted "centipede" polymer of a maleated polypropylene and a poly(a-12 olefin-(co)-(maleimide)) that is useful in producing high damping, soft materials.
13 More specifically, it is an object of this invention to provide a grafted centipede polymer 14 formed by reacting maleated polypropylene and a poly(a-olefin-(co)-(maleimide)) with a diamine.
1 S Another object of the invention is to provide oil or low molecular weight component 16 extended grafted centipede polymers that exhibit improved properties, including low Shore A
17 hardness less than 30, high damping properties and a service temperature of about 100°C.

19 The present invention is directed to an oi( or low molecular weight component extended grafted poly(a-olefin-(co)-(maleimide))-polypropylene polymer soft gel composition having 21 damping properties useful in producing molded products having heat resistance and a high 22 elasticity and damping property.

1 The present invention is broadly directed to grafted polymer compositions of a maleated 2 polypropylene and a poly(a-olefin-(co)-(maleimide)) reacted with a diamine.
It is further directed 3 to a process for preparing an oil extended grafted polymer compositions broadly comprising a 4 maleated polypropylene grafted to a functionalized thermoplastic elastomer, namely, a poly(a-olefin-(co)-(maleimide)) under conditions sufficient to permit grafting of the functionalized 6 polypropylene with the functionalized thermoplastic elastomer.

8 The extended grafted polymer gels of the present invention contain: 100 parts by weight 9 of a grafted polymer of a poly(a-olefin-(co)-(maleimide)) having at least one maleated polypropylene segments grafted thereto through the at least one functional linkage formed by a 11 crosslinking reaction with a diamine grafting agent; and at least 30, preferably 30 to 1000, parts 12 by weight of an extender such as an oil or a low molecular weight component.
13 The poly(a-olefin-(co)-(maleimide)) is a "centipede" polymer formed by imidizing a 14 poly(a-olefin-co-malefic anhydride) with a primary amine. The "centipede"
polymer has a high 1 S molecular weight spine connected with many relatively short side chains formed from the addition 16 of the primary amines. The length of the main chain usually equals or is longer than the 17 entanglement length, which is herein defined theoretically as an order of magnitude of 100 18 repeating units, while the length of the side chains is much smaller than the entanglement length.
19 The a-olefin contributed monomer units of the poly(a-olefin-(co)-(maleimide)) "centipede" polymer contain 3 to about 50 carbon atoms. Examples of these a-olefins are 21 propylene, 1-butene, 1-pentene, 1-octadene, 2-ethyl-1-hexene, 1-dodecene, and the like.

1 The poly(a-olefin-co-maleimide) described herein are subsequently graft-reacted through a 2 difunctional linking or grafting agent to a maleated polypropylene to yield a grafted polymer 3 having at least one polypropylene segment grafted thereto through the at least one functional 4 linkages thus formed.
The maleated polypropylene may be any of the conventionally known polypropylene 6 compounds that are subsequently maleated by methods known in the art. The polypropylene 7 grafted segment or segments have molecular weights "M,~" of about 10,000 up to about 8 10,000,000, or higher, preferably about 20,000 to about 300,000.
9 The crystallinity, or tacticity, of the polypropylene may vary from being substantially amorphous to being completely crystalline, that is from about 10-100%
crystallinity. Most 11 typically, because of the extensive commercial use of isotactic polypropylene, the grafted 12 polypropylene will be substantially crystalline, e.g., greater than about 90%. Generally, the 13 polypropylene is substantially free of ethylene. However, under certain circumstances small 14 amounts of ethylene, on the order of less than about 5% by weight, may be incorporated.
Furthermore, in certain instances the polypropylene contain small amounts of ethylene in 16 copolymers known as "reactor copolymers". Thus, it is within the scope of the invention that the 17 grafted polypropylene contain minor amounts of ethylene, both as part of ethylene-propylene 18 segments and as polyethylene segments.
19 Polymerization conditions for the preparation of polypropylene are well known in the art.
Propylene can be polymerized into isotactic polypropylene in the presence of stereo-specific 21 Ziegler-Natta catalyst systems comprising compounds of the transition metals of Groups 4 to 6 22 and 8 of the Periodic Table of elements, preferably titanium compounds, most preferably I titanium halides, and organometallic compounds of elements of groups 1 to 3 of the Periodic 2 Table, especially aluminum alkyls or aluminum alkyl halides. Illustrative examples include titanium 3 trichloride, titanium tetrachloride as catalysts and triethylaluminum and diethyl aluminum chloride 4 as cocatalysts. These transition metal catalyst systems can be non-supported or supported, for example, silica gel, or metal oxides and dihalides, such as MgO, MgCI,, ZnCI,, etc. Such systems 6 can be reacted together and can be complexed with a variety of Lewis-base electron donors.
7 Molecular weight control is typically achieved by the incorporation of hydrogen via a feed 8 stream into the polymerization reactor. The hydrogen is added at about 0 to 30 mole % based on 9 the total monomer. The polymerization reaction is preferably conducted according to the slurry method employing an inert hydrocarbon diluent or liquid propylene as the vehicle. The 11 polymerization temperature can be in the range of about 50° C to about 100°C and is preferably at 12 a range or about 60°C to about 80° C. Polymerization pressure can also vary over a wide 13 range and is not particularly limited. The polymerization pressure can for example be in the range 14 from between atmospheric pressure to 37,000 KPa. Such procedures and components are only 1 S illustrative of the knowledge in the art with respect to polypropylene polymerization, any are 16 contemplated as useful within the scope of the invention. For general review of literature and 17 patents in the art see "Olefin Polymers (Polypropylene)" in the Kirk-Othmer Encyclopedia of 18 Chemical Technology, 3rd Edition v. 16, 453-469 (J. Wiley & Sons, 1981 ).
19 The maleinization of the polypropylene compound to maleated polypropylene is conveniently accomplished by heating a blend of polypropylene and ethylenically unsaturated 21 carboxyl group-containing compounds, e.g.) malefic anhydride, within a range of about 150° to 22 400° C., often in the presence of free-radical initiators such as organic peroxides that are 1 well-known in the art. Free-radical grafting of the carboxyl group-containing compounds onto 2 the polypropylene readily results. Methods of preparing these grafted polymers are well-known in 3 the art as illustrated, inter alia, in U.S. Pat. Nos. 3,480,580, 3,481,910, 3,577,365, 3,862,265, 4 4,506,056, and 3,414,551 the disclosures of which are incorporated herein by reference. Such processes are well-known in the art, for example, an independent source of the description of the 6 process is found in Y. Minoura, M. Ueda, S. Mizinuma and M. Oba, J. Applied Polymer Sci. 1625 7 ( 1969). The use of heat and/or physical shearing optionally with the free-radical initiators, in such 8 equipment as extruders, masticators, and the like, to simultaneously accomplish controlled 9 degradation in molecular weight of the polypropylene along with the free-radical grafting of the malefic anhydride, as is known in the art, will be useful in accordance with this invention.
11 In particular, it is preferable to conduct the maleinization with such amounts of malefic 12 anhydride and free-radical initiators, and under conditions of temperature and shearing such that 13 free-radical sites on the polypropylene are formed substantially at the time of scission of the 14 polypropylene chains and are formed at the point of such scission. The malefic anhydride is then grafted onto the scissioned end of one side of such broken chains. In this manner the anhydride 16 groups are located principally at the ends of the maleated polypropylene chains, and the 17 substantial majority of such maleated polypropylene chains contain one site of maleinization. This 18 procedure permits grafting of the maleated polypropylene at its maleated end to the maleated 19 block copolymer though the use of a difunctional linking or grafting agents having two functional groups each functional group being reactive with a maleate group on the polypropylene and block 21 copolymer. Multiple sites of maleinization can lead to grafting of the maleated polypropylene to 22 more than one maleated block copolymer polymer chain or at more than one site of one or more 1 maleated block copolymer. The same substantial chemistry applies to the centipede polymers of 2 the present invention.
3 In accordance with the above, the free-radical initiator is preferably used and will typically 4 be utilized in an amount of from about 0.01 to 1.0 wt. %, preferably from about 0.02 to 0. S wt.
%, and most preferably from about 0.04 to 0.3 wt. % of the total polypropylene. The mixture is 6 then heated to a temperature at or about the known decomposition temperature of the selected 7 free-radical initiator, concurrently with any optional mechanical shearing.
The malefic anhydride is 8 subsequently added in an amount typically from about 0.01 to 10.0 wt. %, preferably from about 9 0.1 to 5 wt. %, and most preferably about 0.75 to 2 wt. % of the total polypropylene.
The maleated polypropylene of this invention contain from about 0.01 wt. %
incorporated 11 malefic anhydride, based upon the weight of the maleated polypropylene, up to about 5 wt. %.
12 Preferably the malefic anhydride content will be from about 0.01 to about 2 wt. %, most preferably 13 about 0.03 to about 0.2 wt. %. As will be apparent, unreacted polypropylene will also be present 14 in the reaction mix as will minor amounts of reaction by-products, such as decomposed 1 S free-radical initiator compounds and low molecular weight free-radical products. These 16 by-products are substantially removed, by methods known in the art, e.g., sparging with nitrogen 17 or washing with water. Malefic anhydride may not be left in substantial amounts in the polymer 18 without detrimental affects on the subsequent reaction of the present poly(a-olefin-co-19 maleimide) with the maleated polypropylene.
The poly(a-olefin-co-maleimide) of the present invention is formed by reacting a poly(a-21 olefin-(co)-(malefic anhydride)] at from about 120 °C to about 250 °C and from about slightly 22 above vacuum to about 20 atmospheres, under substantially dry conditions in the presence of a 1 primary amine. The present invention is preferably directed to a polymer compositions of a 2 poly(1-octadene-co-maleimide) formed by reacting a poly(1-octadene-co-malefic anhydride) with a 3 primary amine.
4 For the purposes of this invention, poly(a-olefin-co-maleimide) is defined to encompass random and stereo-specific copolymers, including copolymers having alternating and maleimide or 6 malefic anhydride contributed monomer units along the polymer backbone. Such alternating 7 structure are typically described as poly(a-olefin-alt-maleimide) and poly(a-olefin-alt-malefic 8 anhydride); however, these polymers are encompassed herein within the descriptions poly(a-9 olefin-co-maleimide) and poly(a-olefin-co-malefic anhydride).
Processes for forming poly(a-olefin-co-malefic anhydride) polymers are well known to 11 those skilled in the art. The preparation of the copolymers from electron donor monomers, such 12 as styrene, and electron acceptor monomers, such as malefic anhydride, as a result of complexation 13 of the electron acceptor monomers may be carried out in the absence as well as in the presence of 14 an organic free radical initiator in bulk, or in an inert hydrocarbon or halogenated hydrocarbon solvent such as benzene, toluene, hexane, carbon tetrachloride, chloroform, etc. (N.G. Gaylord 16 and H. Antropiusova, Journal of Polymer Science, Part B, 7, 145 ( 1969) and Macromolecules, 2, 17 442 ( 1969); A. Takahashi and N. G. Gaylord, Journal of Macromolecular Science (Chemistry), 18 A4, 127 ( 1970).
19 Poly(a-olefin-co-malefic anhydride) polymers are prepared by reacting monomers of an a-olefin containing from 3 to about 20 carbon atoms with malefic anhydride.
The preferred a-21 olefin monomers used for forming the poly(alkyl benzene-co-malefic anhydride) polymer 22 contains 6 to about 16 carbon atoms.

1 The poly(a-olefin-co-malefic anhydride) for use in the present invention is a polymer 2 containing from about 5 to 99 mole percent of malefic anhydride monomer with the remainder 3 being a-olefin monomer. The preferred poly(a-olefin-co-malefic anhydride) contains from 20 to 4 50 mole percent of malefic anhydride monomer with the remainder being a-olefin monomer. The most preferred poly (a-olefin-co-malefic anhydride) for use in the present invention contains 50 6 mole percent of malefic anhydride monomer and SO mole percent of a-olefin monomer. The 7 comonomers, malefic anhydride and a-olefin, can be randomly or alternatingly distributed in the 8 chain, however, it is preferred to have these comonomers alternating along the polymer backbone 9 chain.
The poly(a-olefin- co-malefic anhydride) has a molecular weight range between about 11 1,000 and up to about 500,000 or higher, more typically between about 10,000 and 500,000, and 12 even more typically between about 150,000 and 450,000, where the molecular weight is 13 weight-average ("M,~. ") 14 The poly(a-olefin-co- maleimide) of the present invention is formed by reacting a poly(a-olefin-co-malefic anhydride) in the presence of a mono-primary amine at a temperature from about 16 100°C to about 300°C and at a pressure from about slightly above vacuum to about 20 17 atmospheres, under substantially dry conditions. The reactants are preferably dry mixed in the 18 absence of solvents in a suitable mixing apparatus such as a Brabender mixer. It is preferable to 19 purge the mixer with nitrogen prior to the charging of the reactants. The primary amine may be added in a singular charge or in sequential partial charges into a reactor containing a charge of 21 poly(a-olefin-co-malefic anhydride). Preferably the primary amine is charged in ratio between 0.8 22 to 1.0 of moles of amine per monomer contributed units of malefic anhydride in the poly(a-olefin-1 co-malefic anhydride).
2 Suitable primary amine include but are not limited to: alkyl amines; alkyl benzyl amines;
3 alkyl phenyl amines; alkoxybenzyl amines; alkyl aminobenzoates; alkoxy aniline; and other linear 4 primary amines containing from 1 to 50 carbon atoms, preferably 6 to 30 carbon atoms, in the alkyl and alkoxy substituents in these primary amines. It is understood that the alkyl and alkoxy 6 substituents on the above discussed primary amines can be linear or branched, preferably linear, 7 and saturated or unsaturated, preferably saturated. Exemplary, but not exclusive of such amines 8 are: hexylamine, octylamine, dodecylamine and the like.
9 The poly(a-olefin-co-maleimide), prior to grafting with maleated polypropylene, preferably has a molecular weight range between about 1,000 and up to about 500,000 or higher, 11 more typically between about 10,000 and 500,000, and even more typically between about 12 150,000 and 450,000, where the molecular weight is weight-average ("Mw. ") 13 The centipede polymer of the present invention may be prepared by any means well known 14 in the art for combining such ingredients, such as blending, milling or internal batch mixing. A
rapid and convenient method of preparation comprises heating a mixture of the components to a 16 temperature of about SO°C. to about 300°C.
17 The centipede polymers of this invention are preferably manufactured by mixing and 18 dynamically heat-treating the components described above, namely, by melt-mixing. As for the 19 mixing equipment, any conventional, generally known equipment such as an open-type mixing roll, closed-type Banbury mixer, closed type Brabender mixer, extruding machine, kneader, 21 continuous mixer, etc., is acceptable. The closed-type Brabender mixer is preferable, and mixing 22 in an inactive gas environment, such as nitrogen or carbon dioxide, is also preferable.

1 Grafting of maleated polypropylene and poly(a-olefin-co-maleimide) is performed by 2 addition of a grafting agent such as a polyamine, preferably an organic diamine, to a blend of 3 maleated polypropylene and poly(a-olefin-co-maleimide) to partially cross-link the polypropylene 4 to the poly(a-olefin-co-maleimide) through the maleate functional groups.
This grafting is performed by reacting from about 50 wt% to about 90 wt% of a poly(a-olefin-co-maleimide) and 6 about 10 wt% to about 50 wt% of a maleated polyalkylene and from about 0.01 to about 10 wt%
7 of a diamine under substantially dry conditions suff dent to form a polyalkylene grafted poly(a-8 olefin-co-maleimide) centipede polymer.
9 Suitable organic diamines or diamine mixtures containing two aliphatically or cycloaliphatically bound primary amino groups are used as grafting agents for the process 11 according to the present invention. Such diamines include, for example, aliphatic or cycloaliphatic 12 diamines _ _corresponding to the following general formula: R,(NH,), wherein R, represents an 13 aliphatic hydrocarbon group having from 2 to 20 carbon atoms, a cycloaliphatic hydrocarbon 14 group having from 4 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 20 carbon atoms or R1 represents an N-heterocyclic ring having from 4 to 20 carbon atoms, e.g., 16 ethylene diamine; 1,2- and 1,3- propylene diamine; 1,4-diaminobutane; 2,2-dimethyl-1,3-17 diaminopropane; 1,6-diaminohexane; 2, 5-dimethyl-2, 5-diaminohexane; 1,6-diamino-18 2,2,4-trimethyldiaminohexane; 1,8-diaminooctane; 1,10-diaminodecane; 1,11-diaminoundecane;
19 1,12-diaminododecane; 1-methyl-4-(aminoisopropyl)-cyclohexylamine; 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine; 1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-21 dimethylbenzene; 1, 2- and 1,4-diaminocyclohexane; 1, 2-; 1,4-; 1, 5- and I
, 8-diaminodecalin;
22 I-methyl-4-aminoisopropyl-cyclohexylamine; 4,4'-diamino-dicyclohexyl; 4,4'-diamino-1 dicyclohexyl methane; 2,2'-(bis-4-amino-cyclohexyl)-propane;
2 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane; 1,2-bis-(4-aminocyclohexyl)-ethane;
3 3,3',5,5'-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane; 1,4 -4 bis-(2-aminoethyl)-benzene; benzidine; 4,4'-thiodianiline, 3,3'-dimethoxybenzidine; 2,4-diaminotoluene, diaminoditolylsulfone; 2,6-diaminopyridine; 4-methoxy-6-methyl-m-6 phenylenediamine; diaminodiphenyl ether; 4,4'-bis(o-toluidine); o-phenylenediamine;
7 o-phenylenediamine, methylenebis(o-chloroaniline); bis(3,4-diaminophenyl)sulfone;
8 diaminodiphenylsulfone; 4-chloro-o-phenylenediamine; na-aminobenzylamine; m-9 phenylenediamine; 4,4'-C,-C6-dianiline such as 4,4'-methylenedianiline;
aniline-formaldehyde resin;
and trimethylene glycol di p-aminobenzoate. Mixtures of these diamines may also be used.
11 Other suitable polyamines for use as grafting agents in the process according to the 12 present invention include bis-(aminoalkyl)-amines, preferably those having a total of from 4 to 12 13 carbon atoms, e.g., bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine, 14 bis-(4-aminobutyl)-amine and bis-(6-aminohexyl)-amine, and isomeric mixtures of dipropylene triamine and dibutylene triamine. Hexamethylene diamine, tetramethylene diamine, and especially 16 1,12-diaminododecane are preferably used.
17 Thus in the preferred embodiment the process for preparing the grafted polymer of this 18 invention comprises the steps o~
19 (A) combining a commercially available poly(a-olefin-co-(malefic anhydride)) and a primary amine under substantially dry conditions sufficient to react substantially most of the acid anhydride 21 moieties to form the poly(a-olefin-co-maleimide); and, 22 (B) mixing a commercially available maleated polypropylene with the mass of step (A) under 1 substantially dry conditions of elevated temperature;
2 (C) adding a diamine to the reaction mass of step (B), under condition of agitation suffcient to 3 form the polypropylene grafted polymer and cooling the resultant polymer;
and, 4 (D) adding an extender oil to the final polymer of step (C) under conditions of agitation.
In broadest terms the process for preparing the grafted polymer of this invention 6 comprises cambining the poly(a-olefin-co-maleimide) with the maleated polypropylene and the 7 grafting agent under conditions sufficient to permit grafting of at least a minor portion of the 8 poly(a-olefin-co-maleimide) onto the polypropylene. Thus the grafted centipede polymer 9 composition of this invention will comprise the reaction product of the above described poly(a-olefin-co-maleimide), the grafting agent and the maleated polypropylene. The grafting reaction is 11 accomplished by contacting the grafting agent and the poly(a-olefin-co-maleimide) with the 12 maleated polypropylene whereupon interaction and cross linking take place.
Apparently, the 13 primary amino groups of the grafting agent react to form covalent chemical bonds (imide bonds) 14 with the malefic moieties of the maleated polypropylene and the poly(a-olefin-co-maleimide). The 1 S polypropylene is thus grafted to the poly(a-olefin-co-maleimide) through covalent chenucal 16 functional linkages.
17 For best results, a proportion of approximately one-half molar equivalent of grafting agent 18 per molar equivalent of malefic moiety can be employed due to the difunctionality of the grafting 19 agent. The contacting can be accomplished by combining solutions of the polymeric reactants in suitable solvents, such as benzene, toluene, xylene and other inert organic and 21 inorganic solvents, in a suitable reaction vessel under substantially anhydrous conditions. Heating 22 will accelerate the reaction and is generally preferred. However, the reaction is exothermic and 1 will occur at ambient temperatures. More preferably commercially, the contacting can be 2 accomplished by premixing pre-formed pellets of the neat functionalized polymers and adding the 3 grafting agent and melt processing in a physical blender or mixer, such as a Brabender mixer or an 4 extruder, at temperatures of from about ambient to about 350° C., preferably about 75° to about 300° C., and most preferably 120° C. to about 250° C. It is important that essentially all moisture 6 or water be removed by drying prior to contacting the polymer reactants in order to avoid 7 hydrolysis reactions which will compete with the sought cross linking and reduce the yield of the 8 grafted copolymer composition of this invention.
9 The amounts of poly(a-olefin-co-maleimide) and maleated polypropylene reacted into the grafted compositions of the invention may vary somewhat depending upon the properties desired 11 in the finished composition. In general, the amounts of maleated polypropylene included in the 12 grafted composition may range from about 1 to about SO percent by weight based on total weight 13 of composition. Preferred amounts of maleated polypropylene are from 1 to 30 percent by weight 14 with a particularly preferred amount being from 10 to 25 percent by weight.
The amounts of poly(a-olefin-co-maleimide) centipede polymer included in the grafted composition may range 16 from about 99 to about 50 percent by weight based on total weight of composition. Preferred 17 amounts of the centipede polymer are from 99 to 70 percent by weight with a particularly 18 preferred amount being from 99 to 75 percent by weight 19 The centipede polymer gels of the present invention have an extender added to the prepared grafted copolymers during final processing. Suitable extenders include extender oils and 21 low molecular weight compounds or components. Suitable extender oils include those well 22 known in the art such as naphthenic, aromatic and paraffinic petroleum oils and silicone oils.

1 Examples of low molecular weight organic compounds or components useful as extenders 2 in the compositions of the present invention are low molecular weight organic materials having a 3 number-average molecular weight of less than 20,000, preferable less than 10,000, and most 4 preferably less than 5,000. Although there is no particular limitation to the material which may be S employed, the following is a list of examples of appropriate materials:
6 ( 1 ) Softening agents, namely aromatic naphthenic and paraffinic softening agents for rubbers or 7 resins;
8 (2) Plasticizers, namely plasticizers composed of esters including phthalic, mixed phthalic, 9 aliphatic dibasic acid, glycol, fatty acid, phosphoric and stearic esters, epoxy plasticizers, other plasticizers for plastics, and phthalate, adipate, sebacate, phosphate, polyether and polyester 11 plasticizers for NBR;
12 (3) Tackifiers, namely coumarone resins, coumarone-indene resins, terpene phenol resins, 13 petroleum hydrocarbons and rosin derivative;
14 (4) Oligomers, namely crown ether, flourine-containing oligomers, polybutenes, xylene resins, chlorinated rubber, polyethylene wax, petroleum resins, rosin ester rubber, polyalkylene glycol 16 diacrylate, liduid rubber (polybutadiene, styrene/butadiene rubber, butadiene-acrylonitrile rubber, 17 polychloroprene, etc.), silicone oligomers, and poly-a-olefins;
18 (5) Lubricants, namely hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such 19 as higher fatty acid and hydroxy-fatty acid, fatty acid amide lubricants such as fatty acid amide and alkylene-bis-fatty acid amide, ester lubricants such as fatty acid-lower alcohol ester, fatty acid-21 polyhydric alcohol ester and fatty acid-polyglycol ester, alcoholic lubricants such as fatty alcohol, 22 polyhydric alcohol, polyglycol and polyglycerol, metallic soaps, and mixed lubricants; and, 1 (6) Petroleum hydrocarbons, namely synthetic terpene resins, aromatic hydrocarbon resins, 2 aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic or alicyclic petroleum 3 resins, aliphatic or aromatic petroleum resins, polymers of unsaturated hydrocarbons, and 4 hydrogenated hydrocarbon resins.
Other appropriate low-molecular weight organic materials include latexes, emulsions, 6 liquid crystals, bituminous compositions, and phosphazenes. One or more of these materials may 7 be used as extenders.
8 In accordance with the present invention, the grafted polymer containing gel composition 9 of the present invention may have added thereto at least about 1 to about 10,000, preferably 30 to I ,000, parts by weight of extender per 100 parts by weight of the grafted copolymers. Most 11 preferred amounts of added extender include from about 50 to about 500 parts of oil per 100 12 parts of grafted copolymer and ideally about 80 to about 300 parts of extender per 100 parts of 13 grafted copolymer. The weight percent ratio of the polyalkylene grafted poly(a-olefin-co-14 maleimide) to the extender is from about 100: I to about 1:100, preferably about 10:1 to about 1:100.
16 The polymer gels produced according to the present invention generally have high 17 damping properties having a tan b in the range of about 0. I to about 1.0, most preferably higher 18 than 0.2 over the temperature range of 30°C. to 100°C., and a Shore A hardness ranging from 0 19 to about 50, preferably about 0 to about 35, most preferably about 5 to 20 at about 20°C to 25°C
or at room temperature. The service temperature of the gels of the present invention is less than 21 or equal to 100°C. for most of the polymers of the present invention, e.g., 100°C compression set 22 of the gel is about 80. Some of the extended polymers of the present invention have a potential 1 use up to 140°C.
2 It is frequently desirable to include other additives well known in the rubber art to the 3 compositions of the present application. Stabilizers, antioxidants, conventional fillers, reinforcing 4 agents, reinforcing resins, pigments, fragrances and the like are examples of some such additives.
S Specific examples of useful antioxidants and stabilizers include 2-(2'-hydroxy-5'-methylphenyl) 6 benzotriazole, nickel dibutyldithiocarbamate, zinc dibutyl dithiocarbamate, tris(nonylphenyl) 7 phosphite, 2,6-di-t-butyl-4-methylphenol and the like. Exemplary conventional fillers and 8 pigments include silica, carbon black, titanium dioxide, iron oxide and the like. These 9 compounding ingredients are incorporated in suitable amounts depending upon the contemplated use of the product, preferably in the range of 1 to 3 50 parts of additives or compounding 11 ingredients per 100 parts of grafted copolymer.
12 A reinforcement may be defined as the material that is added to a resinous matrix to 13 improve the strength of the polymer. Most of these reinforcing materials are inorganic or organic 14 products of high molecular weight. Various examples include glass fibers, asbestos, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural 16 organic fibers, and synthetic organic fibers. Other elastomers and resins are also useful to enhance 17 specific properties like damping properties, adhesion and processability.
Examples of other 18 elastomers and resins include adhesive-like products including Reostomer (produced by Riken-19 Vinyl Inc.), hydrogenated polystyrene-(medium or high 3,4) polyisoprene-polystyrene block copolymers such as Hybler (produced by Kurare Inc.), polynorbornenes such as Norsorex 21 (produced by Nippon Zeon Inc.) and the like. In the present case, the foregoing materials are 22 equally applicable to the centipede polymer compositions.

1 The gels containing oil or low molecular weight component extended and polypropylene 2 compositions of the present invention may be prepared by any means well known in the art for 3 combining such ingredients, such as solution blending, milling, internal batch mixing, or 4 continuous extrusion of a solid form of the centipede polymer and polypropylene compositions and the other ingredients. A rapid and convenient method of preparation comprises heating a 6 mixture of the components to a temperature of about 50°C to about 300°C.
7 The gels containing oil extended grafted poly(a-olefin-co-maleimide)-polypropylene 8 compositions of the present invention can be manufactured by mixing and dynamically 9 heat-treating the components described above, namely, by melt-mixing. As for the mixing equipment, any conventional, generally known equipment such as an open-type mixing roll, 11 closed-type Banbury mixer, extruding machine, kneader, continuous mixer, etc., is acceptable.
12 The closed-type is preferable, and mixing in an inactive gas environment, such as nitrogen or 13 argon, is also preferable 14 The composition obtained using the manufacturing method of this invention can be molded with equipment conventionally used for molding thermoplastics. It is suitable for 16 extrusion molding, calendar molding, and particularly injection molding.
17 The composition of the present invention can be mixed in any conventional mixer such as 18 a Banbury mixer or roll mill or extruder normally conducted within the temperature range of 19 about 120 °C to about 300 °C, preferably maintaining the composition above its melting point for a few minutes up to several hours, preferably 10 to 40 minutes. A particularly useful technique is 21 to add any fillers in the beginning of the mixing cycle in order to take maximum advantage of 22 heating time and to prevent surface bleeding and overheating when forming the molded articles.

1 The resultant gel composition may be molded in appropriate press ovens and the like to 2 form products in the form of extruded pellets, cut dices, preferably as small as possible since 3 smaller pellets provide short heating times and better flow when utilized in flow molding. Ground 4 pellets may also be utilized.
S The extended grafted centipede polymers of the present invention can be used in high 6 temperature applications including uses in injection molding or in any other compositions typically 7 containing used for elastomeric properties.
8 In summary, the molded polymers produced from the gels containing extended grafted a 9 poly(a-olefin-co-maleimide) and polypropylene compositions of the present invention retain elastomeric characteristics and are useful in high temperature applications and/or high damping 11 applications.
12 Damping is the absorption of mechanical energy by a material in contact with the source 13 of that energy. It is desirable to damp or mitigate the transmission of mechanical energy from, 14 e.g., a motor, engine, or power source, to its surroundings. Elastomeric materials are often used for this purpose. It is desirable that such materials be highly effective in converting this mechanical 16 energy into heat rather than transmitting it to the surroundings. It is further desirable that this 17 damping or conversion is effective over a wide range of temperatures and frequencies commonly 18 found near motors, automobiles, trucks, trains, planes, and the like.
I 9 A convenient measurement of damping is the determination of a parameter called tan 8. A
forced oscillation is applied to a material at frequency f and the transmitted force and phase shift 21 are measured. The phase shift angle delta is recorded. The value of tan b is proportional to the 22 ratio of (energy dissipated)/(energy stored). The measurement can be made by any of several 1 commercial testing devices, and may be made by a sweep of frequencies at a fixed temperature, 2 then repeating that sweep at several other temperatures, followed by the development of a master 3 curve of tan b vs. frequency by curve alignment. An alternate method is to measure tan 8 at 4 constant frequency (such as at 10 hz) over a temperature range. We have defined a thermoplastic S unfilled material as useful for damping when tan b > ~ 0. 3 over at least a 4 decade range, 6 preferably a 6 decade range of frequency.
7 It is further important that this high degree of absorption of energy be accompanied by 8 good mechanical and thermal stability, as the part prepared from the subject polymers will be 9 cycled through various environments and repeatedly such to various forces of compression, tension, bending, and the like.
11 The compositions of the present invention are favorably used in the manufacturing of any 12 product in which the following properties are advantageous: a high degree of softness, heat 13 resistance, decent mechanical properties, elasticity and/or high damping.
The compositions of the 14 present invention can be used in all industry fields, in particular, in the fabrication of automotive parts, tire tread rubbers, household electrical appliances, industrial machinery, precision 16 instruments, transport machinery, constructions, engineering, and medical instruments.
17 Representative examples of the use of the extended graft polymers of the present invention 18 are in the manufacture of damping materials and vibration restraining materials. These uses 19 involve connecting materials such as sealing materials, packing, gaskets and grommets, supporting materials such as mounts, holders and insulators, and cushion materials such as stoppers, 21 cushions, and bumpers. These materials are also used in equipment producing vibration or noise 22 and household electrical appliances, such as in air-conditioners, laundry machines, refrigerators, 1 electric fans, vacuums, driers, printers and ventilator fans. Further, these materials are also 2 suitable for impact absorbing materials in audio equipment and electronic or electrical equipment, 3 sporting goods and shoes. Further, as super low hardness rubbers, these materials are applicable 4 for use in appliances, damping rubbers, and as low hardness plastics, and it is preferable for molding materials. Further, because the present compositions can be used to control the release 6 of internal low molecular weight materials out from the compositions, it is useful as a release 7 support to emit materials such as fragrance materials, medical materials and other functional 8 materials. The compositions of the present invention also possess utility in applications of use in 9 liquid crystals, adhesive materials and coating materials.
Specific examples of uses of the compositions of the present invention as damping 1 I materials are as follows:
12 ( 1 ) in audio equipment, such as in insulators for a portable CD or a CD
mounted on a vehicle, 13 mike holders for home video cassette recorder, radio cassette recorder, karaoke or handy mike, 14 etc., an edge cone of a speaker, a tape holder of a radio cassette, a holder of a portable mini-disk player, an optical disk holder of a digital video disk, etc.;
16 (2) in information relating equipment, such as in insulators for a hard disk, insulators for motors 17 such as a spindle motor for HHD and stepping motor, insulators for floppy disk drive, insulators 18 for CD-ROM of personal computer, and a holder for optical disk;
19 (3) in communication equipment, such as in a holder for compact high performance mike or speaker of a portable telephone, a pocket bell or PHS, a mike holder for a wireless equipment, 21 and a disk holder for portable note type electronic equipment;
22 (4) in home electronics equipment, such as in insulators for CD-ROM of home TV, insulators for 1 cassette holder or CD-ROM of cassette holder or game machine, a holder of high performance 2 mike, and cone edge of speaker; and 3 (5) in other applications, such as in damping materials for printer head of a wordprocessor, printer 4 of personal computer, small or middle handy type printer, or name printers, and insulators for CD-ROM used for measure equipment.
6 In the following, the present invention will be described in more detail with reference to 7 non-limitative examples. The following examples and tables are presented for purposes of 8 illustration only and are not to be construed in a limiting sense.
9 Example 1 Preparation of Centipede Polymers 11 A nitrogen purged Brabender mixer (55 g capacity) equipped with a roller blade was 12 initially set to 10 rpm and 40° C. The mixer was then charged with 32.90 g of poly(1-octadene-13 alt-malefic anhydride) (M" of about 40,000 obtained from Aldrich Chemical Company of 1001 14 West Saint Paul Avenue, Milwaukee) and 17.48 of dodecane amine (obtained from Aldrich, 99%
1 S purity). After 5 minutes, the mixture was allowed to heat up at a rate about 4°C/min to 200°C
16 and the agitation speed was set to be 60 rpm. The mixing was continued for 2 hours, then, the 17 heating element was turned off and the polymer was allowed to cool down at a rate of about 18 4°C/min. The polymer was removed from the mixer at 160°C.
19 IR characteristic absorption peaks of the polymer mass were noted at 705, 1701, 1770, 2855, 2926 cm 1. DSC characteristic Tg transition is broad, starting from -80 to 20°C. The Tg was 21 estimated to be about -30°C. The acid value of the polymer was 0.171 meq./g using the NaOH
22 titration method in a tetrahydrofuran solution.

1 Example 2 2 Grafting of the Centipede Polymers with Polypropylene 3 A nitrogen purged Brabender mixer (55 g capacity) equipped with a roller blade was 4 initially set to 20 rpm and the temperature was set to 200°C. The mixer was initially charged with 12 g of commercial maleated polypropylene (from the Exxon Chemical Company, trade name 6 Exxelor PO 1015). After 3 minutes, a charge of 28 g of the product from Example 1 was added 7 into the mixture. After 3 minutes, the agitation speed was increased to 60 rpm. The mixing was 8 continued for another 12 minutes, and then a charge of 0.4 g dodecane diamine (from Aldrich, 9 purity of 98%) was added in the mixture. At the same time, the agitation speed was adjusted to 90 rpm. The torque of the mixing started to build. Thirty minutes Later, the agitation speed was 11 set back to 60 rpm and the heating element was turned off. The mixture was allowed to cool to 12 about 160°C at a rate of about 4°C/min. Finally, the agitation was turned off and the polymer was 13 removed from the mixer.
14 Example 3 The procedure of Example 2 were repeated with minor changes in the amounts of 16 materials. The mixer was charged with 24 g of the centipede polymer synthesized according to 17 the procedures of Example 1 and 16g of the commercial maleated polypropylene (from the Exxon 18 Chemical Company, trade name Exxelor PO 1015).
19 Example 4 The procedure of Example 2 were repeated with minor changes in the amounts of 21 materials used. The mixture was charged with 16 g of the centipede polymer synthesized 22 according to the procedures of Example 1 and 24 g of the commercial maleated polypropylene 1 (from the Exxon Chemical Company, trade name Exxelor PO 1015).
2 Example 5 3 Oil Extending the Grafted Polymer 4 A charge of 20 g of the product from Example 2 was added to a Brabender mixer (SS g capacity) equipped with a roller blade. The mixture was initially set to 25°C and 20 rpm, a charge 6 of 20 g of di(tridecyl)phthalate (DTDP) oil was slowly charged into the mixer. After 5 minutes, 7 the temperature of the mixer was then set to 160°C and the agitation speed was adjusted to 70 8 rpm. After 145 minutes continuously mixing, another charge of 1 Og of DTDP
oil was added into 9 the mixer. After an additional 50 minutes of mixing, another charge of Sg of DTDP oil was added into the mixer. The material was further mixed at 70 rpm for 70 minutes; then, the agitation was 11 turned off and the mixture was removed from the mixer.
12 These products from these examples were molded into sheets and cylinder buttons at 13 about 160°C. Ring samples were cut from these sheets for tensile measurement. The detail of 14 physical properties of the final materials are listed below in Table 1:

Oil TypePP Modulus Tb/Eb Tg/Tm ShoreComments (content)content (at 50%)(psi (f C/''C)A
/ %) 16 Example ---- 0% ---- ---- -32/-- 0 HV Fluid 17 Example ---- 20% 32 57/150 -32/142 55 TPE material 18 Example ----- 40% 432 519/83 -32/1:12 80 TPE material 19 Example ----- 60% 1156 1368/30-t-32/la2 95 TPE material Example DTDP 20% 2.34 8.11109 -32/142 3 Soft Gel 5 (64%) (tan b=0.4 at 25C) 1 As can be seen in Table 1, the octadene-alt-n-dodecylmaleimide centipede was a highly 2 viscous (HV) fluid with Tg of -32°C. When the octadene-alt-n-dodecylmaleimide centipede 3 polymers were grafted with polypropylene, the grafted copolymers (Examples 2-4) were thermal 4 plastic elastomers(TPE) and exhibited very well balanced tensile strength, modulus and elongation. Particularly, the grafted copolymers after extending with large amounts of oil (e.g., 6 64% oil content) can form soft and thermoreversible gels (Example 5).
However, if the 7 polypropylene and the centipede were simply (or physically) blended together, the physical blends 8 after oil extending were liquids rather than elastomers. Finally, all materials shown in Table 1 9 were thermally recyclable and had a service temperature up to 100°C.
Although the invention has been described with reference to particular means, materials 11 and embodiments it is to be understood that the invention is not limited to the particular disclosed 12 and extends to all equivalents within the scope of the claims.

Claims (23)

1. A method for the formation of a high damping centipede polymer, comprising:
reacting from about 50 wt% to about 99 wt% of a poly(.alpha.-olefin-co-maleimide) and about 1 wt% to about 50 wt% of a maleated polyalkylene and from about 0.01 to about 10 wt% of a diamine under substantially dry conditions sufficient to form a polyalkylene grafted poly(.alpha.-olefin-co-maleimide) centipede polymer.

2. The method of claim 1, further comprising the step of: mixing said polyalkylene grafted poly(.alpha.-olefin-co-maleimide) centipede polymer with an extender oil in an amount sufficient to from a gel.

3. The method of claim 1, further comprising the step of: mixing about 10 wt%
to about 90 wt%
of said polyalkylene grafted poly(.alpha.-olefin-co-maleimide) centipede polymer with about 10 wt%
to about 90 wt% of an extender oil.

4. The method of claim 1, wherein the a-olefin contributed monomer units of said poly(a-olefin-co-maleimide) is selected from the group consisting of a-olefins containing from 3 to about 50 carbon atoms.

5. The method of claim 1, wherein the alkylene contributed monomer units of said maleated polyalkylene is selected from the group consisting of ethylene, propylene and mixtures thereof.

6. The method of claim 1 wherein the maleimide contributed monomer units of the poly(.alpha.-olefin-co-maleimide) is formed by the reaction of malefic anhydride and a primary amine.

7. The method of claim 6 wherein the primary amine is selected from the group consisting of: alkyl amines; alkyl benzyl amines; alkyl phenyl amines; alkoxybenzyl amines; alkyl aminobenzoates; and alkoxy aniline; containing from 1 to 50 carbon atoms in the alkyl and alkoxy substituents in the primary amine.

8. The method of claim 1 wherein said diamine is selected from the group consisting of aliphatic or cycloaliphatic diamines corresponding to the following general formula: R1(NH)2 wherein R1 represents an aliphatic hydrocarbon group having from 2 to 20 carbon atoms, a cycloaliphatic hydrocarbon group having from 4 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 20 carbon atoms or R1 represents an N-heterocyclic ring having from 4 to 20 carbon atoms.

9. The method of claim 1 wherein said diamine is selected from the group consisting of: ethylene diamine; 1,2- and 1,3- propylene diamine; 1,4-diaminobutane; 2,2-dimethyl-1,3-diaminopropane;
1,6-diaminohexane; 2,5-dimethyl-2,5-diaminohexane; 1,6-diamino-2,2,4-trimethyldiaminohexane;
1,8-diaminooctane; 1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane;

1-methyl-4-(aminoisopropyl)-cyclohexylamine; 3-aminomethyl- 3,5,5-trimethyl-cyclohexylamine;
1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-dimethylbenzene; 1,2- and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin; 1-methyl-4-aminoisopropyl-cyclohexylamine; 4,4'-diamino-dicyclohexyl; 4,4'-diamino- dicyclohexyl methane;
2,2'-(bis-4-amino-cyclohexyl)-propane; 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane;
1,2-bis-(4-aminocyclohexyl)-ethane; 3,3',5,5'-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane; 1,4 - bis-(2-aminoethyl)-benzene; benzidine; 4,4'-thiodianiline, 3,3'-dimethoxybenzidine;
2,4-diaminotoluene, diaminoditolylsulfone; 2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine; diaminodiphenyl ether; 4,4'-bis(o-toluidine); o-phenylenediamine;
o-phenylenediamine, methylenebis(o-chloroaniline); bis(3,4-diaminophenyl)sulfone;
diaminodiphenylsulfone; 4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;
4,4'-C1-C6-dianiline such as 4,4'-methylenedianiline; aniline-formaldehyde resin; trimethylene glycol di-p-aminobenzoate; bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine, bis-(4-aminobutyl)-amine;
bis-(6-aminohexyl)-amine, isomeric mixtures of dipropylene triamine and dibutylene triamine; and mixtures thereof.

10. A high damping centipede polymer gel composition, comprising:
a polyalkylene grafted poly(.alpha.-olefin-co-maleimide) comprising from about 50 wt% to about 99 wt% of a poly(.alpha.-olefin-co-maleimide) and about 1 wt% to about 50 wt% of a maleated polyalkylene and from about 0.01 to about 10 wt% of a diamine, and an extender in an amount sufficient to form a gel.

11. The centipede polymer gel composition of claim 10 wherein the weight percent ratio of said polyalkylene grafted poly(.alpha.-olefin-co-maleimide) to said extender is from about 100:1 to about 1:100.

12. The centipede polymer gel composition of claim 10, wherein the monomer for forming the alkenyl benzene moiety of said poly(.alpha.-olefin-co-maleimide) is selected from the group consisting of .alpha.-olefins containing from 3 to about 20 carbon atoms.

13. The centipede polymer gel composition of claim 10, wherein the monomer for forming the alkylene moiety of said maleated polyalkylene is selected from the group consisting of ethylene, propylene and combinations thereof.

14. The centipede polymer gel composition of claim 10, wherein said diamine is selected from the group consisting of: ethylene diamine; 1,2- and 1,3- propylene diamine; 1,4-diaminobutane;
2,2-dimethyl-1,3-diaminopropane; 1,6-diaminohexane; 2,5-dimethyl-2,5-diaminohexane;
1,6-diamino-2,2,4-trimethyldiaminohexane; 1,8-diaminooctane; 1,10-diaminodecane;
1,11-diaminoundecane; 1,12-diaminododecane; 1-methyl-4-(aminoisopropyl)-cyclohexylamine;
3-aminomethyl- 3,5,5-trimethyl-cyclohexylamine; 1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-dimethylbenzene; 1,2- and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;
1-methyl-4-aminoisopropyl- cyclohexylamine; 4,4'-diamino-dicyclohexyl; 4,4'-diamino-dicyclohexyl methane; 2,2'-(bis-4-amino-cyclohexyl)-propane;
3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane; 1,2-bis-(4-aminocyclohexyl)-ethane;

3,3',5,5'-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;
1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4'-thiodianiline, 3,3'-dimethoxybenzidine;
2,4-diaminotoluene, diaminoditolylsulfone; 2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine; diaminodiphenyl ether; 4,4'-bis(o-toluidine); o-phenylenediamine;
o-phenylenediamine, methylenebis(o-chloroaniline); bis(3,4-diaminophenyl)sulfone;
diaminodiphenylsulfone; 4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;
4,4'-C1-C6-dianiline such as 4,4'-methylenedianiline; aniline-formaldehyde resin; trimethylene glycol di-p-aminobenzoate; bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine, bis-(4-aminobutyl)-amine;
bis-(6-aminohexyl)-amine, isomeric mixtures of dipropylene triamine and dibutylene triamine; and mixtures thereof.

15. The centipede polymer gel composition of claim 10, wherein the gel has damping properties having a tan 8 in the range of about 1 to about 0.10 over the temperature range of -10 °C. to 100 °C.

16. The centipede polymer gel composition of claim 10, wherein the gel has a Shore A hardness ranging from about 0 to about 50 at about 20 °C to 25 °C.

17. The centipede polymer gel composition of claim 10, wherein the gel has a Shore A hardness ranging from about 0 to 35 at about 20 °C to 25 °C.

18. The centipede polymer gel composition of claim 10, further comprising from 1 to 350 parts of a inorganic filler, additive or compounding ingredient based on 100 parts by weight of the grafted copolymer composition component.

19. The centipede polymer gel composition of claim 10, wherein the extender is at least one compound selected from the group consisting of softening agents, plasticizers, tackifiers, oligomers, lubricants, petroleum hydrocarbons, silicone oil, aromatic oil, naphthenic oil and paraffinic oil.

20. A centipede polymer composition, comprising:
a polyalkylene grafted poly (.alpha.-olefin-co-maleimide) comprising from about 50 wt% to about 99 wt% of a poly(.alpha.-olefin-co-maleimide) and about 1 wt% to about 50 wt% of a maleated polyalkylene and from about 0.01 to about 10 wt% of a diamine.

21. The centipede polymer composition of claim 20, wherein the monomer for forming the .alpha.-olefin moiety of said poly(.alpha.-olefin- co-maleimide) is selected from the group consisting of .alpha.-olefins containing from 3 to about 20 carbon atoms.

22. The centipede polymer composition of claim 20, wherein the monomer for forming the alkylene moiety of said maleated polyalkylene is selected from the group consisting of ethylene, propylene and combinations thereof.

23. The centipede polymer composition of claim 20, wherein said diamine is selected from the group consisting of: ethylene diamine; 1,2- and 1,3- propylene diamine; 1,4-diaminobutane;
2,2-dimethyl-1,3-diaminopropane; 1,6-diaminohexane; 2,5-dimethyl-2,5-diaminohexane;
1,6-diamino-2,2,4-trimethyldiaminohexane; 1,8-diaminooctane; 1,10-diaminodecane;
1,11-diaminoundecane; 1,12-diaminododecane; 1-methyl-4-(aminoisopropyl)-cyclohexylamine;
3-aminomethyl- 3,5,5-trimethyl-cyclohexylamine; 1,2-bis-(aminomethyl)-cyclobutane; 1,2-diamino-3,6-dimethylbenzene; 1,2- and 1,4-diaminocyclohexane; 1,2-; 1,4-; 1,5- and 1,8-diaminodecalin;
1-methyl-4-aminoisopropyl- cyclohexylamine; 4,4'-diamino-dicyclohexyl; 4,4'-diamino-dicyclohexyl methane; 2,2'-(bis-4-amino-cyclohexyl)-propane;
3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane; 1,2-bis-(4-aminocyclohexyl)-ethane;
3,3',5,5'-tetramethyl-bis-(4-aminocyclohexyl)-methane and -propane;
1,4-bis-(2-aminoethyl)-benzene; benzidine; 4,4'-thiodianiline, 3,3'-dimethoxybenzidine;
2,4-diaminotoluene, diaminoditolylsulfone; 2,6-diaminopyridine; 4-methoxy-6-methyl-m-phenylenediamine; diaminodiphenyl ether; 4,4'-bis(o-toluidine); o-phenylenediamine;
o-phenylenediamine, methylenebis(o-chloroaniline); bis(3,4-diaminophenyl)sulfone;
diaminodiphenylsulfone; 4-chloro-o-phenylenediamine; m-aminobenzylamine; m-phenylenediamine;
4,4'-C,-C6-dianiline such as 4,4'-methylenedianiline; aniline-formaldehyde resin; trimethylene glycol di-p-aminobenzoate; bis-(2-aminoethyl)-amine, bis-(3-aminopropyl)-amine, bis-(4-aminobutyl)-amine;
bis-(6-aminohexyl)-amine, isomeric mixtures of dipropylene triamine and dibutylene triamine; and mixtures thereof.