Butyl rubber ionomer-thermoplastic graft copolymers and methods for production thereof

Abstract

The present invention is directed to the functionalization of butyl rubber ionomer and optionally the grafting of polyamide to halobutyl rubber ionomers. Specifically, disclosed are methods and products resulting therefrom for creating functionalized ionomers and grafting polyamide to halobutyl ionomers via reactive extrusion. The process comprises reacting a halobutyl polymer with at least one nitrogen and/or phosphorous based nucleophile to provide a halobutyl ionomer comprising conjugated diene units; grafting of an amine-reactive dienophile to said ionomer to form a functionalized ionomer; and optionally blending the resulting functionalized ionomer with polyamide.

Claims

1. A method for preparing a butyl graft copolymer, the method comprising: reacting a halobutyl polymer with at least one of a nitrogen based nucleophile and a phosphorous based nucleophile to provide a halobutyl ionomer; and grafting a non-halogenated amine-reactive dienophile to the ionomer through a reactive mixing process to provide a functionalized ionomer.

2. The method according to claim 1, wherein the halobutyl polymer comprises repeating units derived from at least one isoolefin and at least one multiolefin.

3. The method according to claim 2, wherein the isoolefin comprises isobutylene and the multiolefin comprises isoprene.

4. The method according to claim 1, wherein the at least one of the nitrogen based nucleophile and the phosphorus based nucleophile is a nucleophile according to the formula ##STR00003## wherein: A is a nitrogen or phosphorus, and R.sub.1, R.sub.2 and R.sub.3 are independently selected from the group consisting of linear or branched C.sub.1-C.sub.18 alkyl substituents, an aryl substituent which is monocyclic or composed of fused C.sub.4-C.sub.8 rings, and a hetero atom selected from a group consisting of B, N, O, Si, P, and S.

5. The method according to claim 1, wherein the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile is triphenylphosphine.

6. The method according to claim 1, wherein the non-halogenated amine-reactive dienophile is maleic anhydride.

7. The method according to claim 1, further comprising pelletizing the functionalized ionomer.

8. The method according to claim 1, wherein: the isoolefin comprises isobutylene; the multiolefin comprises isoprene; the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile is triphenylphosphine; the non-halogenated amine-reactive dienophile is maleic anhydride; and the method further comprises conducting the reacting and grafting in an extruder.

9. The method according to claim 8, further comprising conducting the reading and grafting in an extruder operated at a temperature of 25 to 250° C.

10. The method according to claim 9, further comprising: adding the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile to the halobutyl polymer in the extruder; and adding the amine-reactive dienophile to the ionomer in the extruder.

11. The method according to claim 1, wherein the method further comprises blending the functionalized ionomer with an amino-containing thermoplastic to form a butyl rubber ionomer-thermoplastic graft copolymer.

12. The method according to claim 11, wherein the amino containing thermoplastic is a polyamide, and the method further comprises conducting the blending in an extruder.

13. The method according to claim 11, further comprising conducting both the grafting and the blending in an extruder, wherein the extruder has a beginning portion and a point downstream of the beginning portion, and the method comprises introducing the dienophile and ionomer at the beginning portion, and adding thermoplastic at the point downstream of the beginning portion.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) For the purposes of the subject matter disclosed herein, the terms “halobutyl rubber”, “halobutyl polymer” and “halogenated isoolefin copolymer” may be used interchangeably. The halogenated copolymers used in the present invention are copolymers of at least one isoolefin monomer and one or more multiolefin monomers and optionally one or more alkyl substituted aromatic vinyl monomers.

(2) Isoolefins having from 4 to 7 carbon atoms are suitable for use in the present invention. Specific examples of such C.sub.4 to C.sub.7 isomonoolefins include isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and mixtures thereof. The preferred C.sub.4 to C.sub.7 isomonoolef in monomer is isobutylene. Suitable C.sub.4 to C.sub.8 conjugated diolefins include, for example, 1,3-butadiene, isoprene, 2-methyl-1,3-pentadiene, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene 1,3-hexadiene, 1,3-octadiene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene and the like, 1,3-butadiene and isoprene being preferred. The polymer based on an isoolefin and a conjugated diolefin monomer can be a copolymer comprising one or more conjugated diene monomers, or a terpolymer comprising a conjugated diene monomer and a vinyl aromatic monomer.

(3) If vinyl aromatic monomers are used, they should be copolymerizable with the other monomers being employed. Generally, any vinyl aromatic monomer that is known to polymerize with organo alkali metal initiators can be used. Such vinyl aromatic monomers usually contain in the range of from 8 to 20 carbon atoms, preferably from 8 to 14 carbon atoms. Examples of suitable such vinyl aromatic monomers include styrene, alpha-methyl styrene, various alkyl styrenes including p-methylstyrene, p-methoxy styrene, 1-vinylnaphthalene, 2-vinyl naphthalene, 4-vinyl toluene and the like. P-methylstyrene is the preferred alkyl-substituted vinyl aromatic monomer.

(4) In one embodiment, the halogenated copolymer used in the formation of the ionomer of the present invention comprises at least one allylic halogen moiety.

(5) In one embodiment, the halogenated copolymer comprises repeating units derived from at least one isoolefin monomer and repeating units derived from one or more multiolefin monomers. In such an embodiment, one or more of the repeating units derived from the multiolefin monomers comprise an allylic halogen moiety.

(6) In one embodiment, the halogenated copolymer is obtained by first preparing a copolymer from a monomer mixture comprising one or more isoolefins and one or more multiolefins, followed by subjecting the resulting copolymer to a halogenation process to form the halogenated copolymer. Halogenation can be performed according to the process known by those skilled in the art, for example, the procedures described in Rubber Technology, 3rd Ed., Edited by Maurice Morton, Kluwer Academic Publishers, pp. 297-300 and further documents cited therein.

(7) During halogenation, some or all of the multiolefin content of the copolymer is converted to units comprising allylic halides. The total allylic halide content of the halogenated polymer cannot exceed the starting multiolefin content of the parent copolymer.

(8) In one embodiment, the monomer mixture used in preparing the butyl rubber comprises from about 80% to about 99.5% by weight of at least one isoolefin monomer and from about 0.5% to about 20% by weight of at least one multiolefin monomer. In one embodiment, the monomer mixture comprises from about 83% to about 98% by weight of at least one isoolefin monomer and from about 2.0% to about 17% by weight of a multiolefin monomer.

(9) In one embodiment, the butyl polymer comprises at least 0.5 mol % repeating units derived from the multiolefin monomers. In one embodiment, the repeating units derived from the multiolefin monomers are at least 0.75 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 1.0 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 1.5 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 2.0 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 2.5 mol %. In one embodiment, the multiolefin butyl polymer comprises at least 3.0 mol % repeating units derived from the multiolefin monomers. In one embodiment, the repeating units derived from the multiolefin monomers are at least 4.0 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 5.0 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are at least 6.0 mol %. In one embodiment, the repeating units derived from the multiolefin monomers at least 7.0 mol %.

(10) In one embodiment, the repeating units derived from the multiolefin monomers are from about 0.5 mol % to about 20 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are from about 0.5 mol % to about 8 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are from about 0.5 mol % to about 4 mol %. In one embodiment, the repeating units derived from the multiolefin monomers are from about 0.5 mol % to about 2.5 mol %.

(11) In one embodiment, the halogenated copolymer for use in the present invention includes a halogenated butyl rubber formed from isobutylene and less than 2.2 mol % isoprene, which is commercially available from LANXESS Deutschland GmbH and sold under the names Bromobutyl 2030™, Bromobutyl 2040™ and Bromobutyl X2™.

(12) In one embodiment, the halogenated copolymer for use in the present invention includes a high isoprene halogenated butyl rubber formed from isobutylene and at least 3 mol % isoprene or at least 4% isoprene, as described in Canadian Patent Application No. 2,578,583 and 2,418,884, respectively.

(13) In one embodiment, the halogenated copolymer of the present invention comprises copolymers of at least one isoolefin, one or more multiolefin monomers, and one or more alkyl substituted aromatic vinyl monomers. In such an embodiment, one or more units derived from the multiolefin monomers comprise an allylic halogen moiety.

(14) In one embodiment, the monomer mixture used in preparing the copolymer of isoolefin, the multiolefin and the alkyl substituted aromatic vinyl monomers comprise from about 80% to about 99% by weight of isoolefin monomers, from about 0.5% to about 5% by weight the multiolefin monomers, and from about 0.5% to about 15% by weight of the alkyl substituted aromatic vinyl monomers. In one embodiment, the monomer mixture comprises from about 85% to about 99% by weight of isoolefin monomer, from about 0.5% to about 5% by weight the multiolefin monomer and from about 0.5% to about 10% by weight alkyl substituted aromatic vinyl monomer.

(15) The mixture used to produce multiolefin butyl rubber polymer may further comprise a multiolefin cross-linking agent. The term cross-linking agent is a term known to a person skilled in the art and is understood to denote a compound that causes chemical cross-linking between the polymer chains as opposed to a monomer that will add to the chain. Examples of suitable cross-linking agents include norbornadiene, 2-isopropenylnorbornene, 2-vinyl-norbornene, 1,3,5-hexatriene, 2-phenyl-1,3-butadiene, divinylbenzene, diisopropenylbenzene, divinyltoluene, divinylxylene and C.sub.1 to C.sub.20 alkyl-substituted derivatives thereof. More preferably, the multiolefin crosslinking agent is divinyl-benzene, diisopropenylbenzene, divinyltoluene, divinyl-xylene and C.sub.1 to C.sub.20 alkyl-substituted derivatives thereof, and/or mixtures of the compounds given. Most preferably, the multiolefin cross-linking agent comprises divinyl-benzene and diiso-propenylbenzene.

(16) The halobutyl rubber or halobutyl polymer should have a total allylic halide content from 0.05 to 2.0 mol %, more preferably from 0.2 to 1.0 mol % and even more preferably from 0.5 to 0.8 mol %. In cases where there is residual multiolefin, the residual multiolefin level is the balance of the starting multiolefin content less the allylic halide content.

(17) The ionomers of the present invention are obtained by reacting a halobutyl rubber (i.e. halogenated isoolefin copolymer) with a nucleophile under reaction conditions well known in the prior art.

(18) According to the process of the present invention, the halobutyl polymer can be reacted with at least one nitrogen and/or phosphorus containing nucleophile according to the following formula:

(19) ##STR00001##
wherein A is a nitrogen or phosphorus, R.sub.1, R.sub.2 or R.sub.3 is selected from the group consisting of linear or branched C.sub.1-C.sub.18 alkyl substituents, an aryl substituent which is monocyclic or composed of fused C.sub.4-C.sub.8 rings, and/or a hetero atom selected from, for example, B, N, O, Si, P, and S.

(20) In general, the appropriate nucleophile will contain at least one neutral nitrogen or phosphorus center which possesses a lone pair of electrons which is both electronically and sterically accessible for participation in nucleophilic substitution reactions. Suitable nucleophiles include trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, and triphenylphosphine (TPP).

(21) According to one embodiment of the invention, the amount of nucleophile reacted with the halobutyl copolymer is in the range from 0.1 to 5 molar equivalents, more preferable 0.1 to 1 molar equivalents and more preferably 0.1 to 0.5 molar equivalents based on the total molar amount of allylic halide present in the high multiolefin halobutyl polymer.

(22) In one embodiment, the halobutyl based ionomer possesses from 0.05 to 2.0 mol % ionomeric groups. In another embodiment of the present invention, the halobutyl based ionomer possesses from 0.2 to 1.0 mol % ionomeric groups. In another embodiment of the present invention, the halobutyl based ionomer possesses from 0.2 to 0.5 mol % ionomeric groups. In another embodiment of the present invention, the halobutyl based ionomer possesses from 0.5 to 0.8 mol % ionomeric groups.

(23) According to one embodiment of the invention, the resulting ionomer is a mixture of the polymer-bound ionomeric moiety and allylic halide such that the total molar amount of ionomeric moiety and allylic halide functionality are present in the range not exceeding the original allylic halide content, such as from 0.05 to 2.0 mol %, more preferably from 0.2 to 1.0 mol % and even more preferably from 0.5 to 0.8 mol % with residual multiolefin being present in the range from 0.2 to 1.0 mol % and even more preferably from 0.5 to 0.8 mol %.

(24) According to another embodiment of the invention, the resulting ionomer comprises only the polymer-bound ionomeric moiety with essentially no remaining allylic halide functionality.

(25) The non-halogenated amine-reactive grafting material contains a C.sub.4 to C.sub.16 unsaturated carboxylic acid derivative. Any compound that combines a C═C double bond and a carboxylic acid or carboxylic acid derived group in the same molecule can be used according to the present invention. The carboxylic acid derived group may be selected from the list of carboxylic acid, carboxylic amides, carboxylic esters, carboxylic acid halides and carboxylic anhydrides. The unsaturated carboxylic acid derivatives may be selected from the group consisting of maleate, itaconate, acrylate, methacrylate, hemic acid salts or the corresponding carboxylic acids, amides, esters and anhydrides, and their C1 to C16 alkyl-substituted derivatives. Preferably, the carboxylic acid derivative is an anhydride. More preferably the unsaturated carboxylic acid derivative is a cyclic anhydride. The unsaturated carboxylic acid derivative may be selected from the group consisting of maleic anhydride, chloromaleic anhydride, itaconic anhydride, hemic anhydride or the corresponding dicarboxylic acids, such as maleic acid or fumaric acid, or their esters. Preferably, the unsaturated carboxylic acid derivative is maleic anhydride.

(26) By conventional definition, a thermoplastic is a synthetic resin that softens when heat is applied and regains its original properties upon cooling. For purposes of the present invention, a thermoplastic (alternatively referred to as thermoplastic resin) is a thermoplastic polymer, copolymer, or mixture thereof optionally having a Young's modulus of more than 200 MPa at 23° C. The resin has a melting temperature of about 160° C. to about 260° C. Thermoplastic resins may be used singly or in combination. At least one of the thermoplastic resins used comprises an amino group, such as is present in, for example, polyamides.

(27) Suitable polyamides (nylons) comprise crystalline or resinous, high molecular weight solid polymers including copolymers and terpolymers having recurring amide units within the polymer chain. Polyamides may be prepared by polymerization of one or more epsilon lactams such as caprolactam, pyrrolidione, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines. Both fiber-forming and molding grade nylons are suitable. Examples of such polyamides are polycaprolactam (nylon-6), polylauryllactam (nylon-12), polyhexamethyleneadipamide (nylon-6,6) polyhexamethyleneazelamide (nylon-6,9), polyhexamethylenesebacamide (nylon-6,10), polyhexamethyleneisophthalamide (nylon-6, IP) and the condensation product of 11-amino-undecanoic acid (nylon-11). Commercially available polyamides may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160° C. and 260° C. being preferred.

(28) An illustrative example of a reaction scheme whereby halobutyl rubber (XIIR) is converted to a butyl-based ionomer (Iono-XIIR) by reaction with a nitrogen or phosphorous based nucleophile is shown in Scheme 1, below. Iono-XIIR is further reacted with an amine reactive grafting material, such as the dienophile maleic anhydride, resulting in the functional group grafted butyl-based ionomer (FG-Iono-XIIR) or functionalized butyl ionomer. The latter is amenable to the grafting of polyamide (PA) in a melt-mixing process, such as a reactive extrusion process, leading to a blend where some or all of PA is covalently grafted to some or all of the functionalized butyl ionomer (PA-FG-Iono-XIIR).

(29) ##STR00002##

(30) According to one embodiment of the invention, both (i) the thermal grafting of dienophile, to conjugated diene or allylic halo butyl ionomer through Diels-Alder cycloaddition and (ii) the blending of the resulting dienophile-grafted ionomer with polyamide, can be implemented in the same extrusion step by providing dienophile and ionomer at the beginning of the extruder and adding a thermoplastic (polyamide) at a later point along a barrel of the extruder.

(31) A functionalized butyl ionomer according to the invention desirably exhibits a preferred blend of properties. For example, the functionalized butyl ionomer desirably exhibits a Mooney viscosity of at least 20 and an ultimate tensile strength of at least 15 MPa. The functionalized butyl ionomer can be processed at temperatures of up to 260 C prior to measuring this desirable balance of physical properties. This makes it amenable to processing in an extruder.

(32) When the functionalized butyl ionomer is used to form a butyl ionomer grafted thermoplastic copolymer, said copolymer desirably exhibits an ultimate tensile strength of at least 6 MPa and/or an elongation at break of at least 150% or at least 175%. Butyl ionomer grafted thermoplastic copolymers formed using a non-functionalized butyl ionomer desirably exhibit an ultimate tensile strength of from 5 to 5.9 MPa and/or an elongation at break of from 95% to 149%.

EXPERIMENTAL

(33) General

(34) Extrusion of selected commercial butyl rubber grades experimental butyl ionomer grades was conducted in the presence of, and without MAH, respectively. The purification of an aliquot of the extrudates led to sample for characterization by .sup.1H NMR and IR. Respective polyamide rubber blends were also prepared. These extrudates emerged as strands or pellets and were further processed into dumbbells via injection molding or into thin sheets via compression molding to be subjected to tensile testing and gravimetric extraction, respectively.

(35) Materials

(36) Commercial materials used in the examples are outlined in Table 1.

(37) TABLE-US-00001 TABLE 1 Chemical name Supplier Trade name Butyl rubber LANXESS LANXESS Butyl 402 Bromobutyl rubber LANXESS LANXESS Bromobutyl 2030 LANXESS Bromobutyl X2 Maleic anhydride (MAH) Sigma- Maleic anhydride Aldrich Polyamide 612 EMS- Grilon CR8 Grivory Polyamide 6I LANXESS Durethan CI 31 F n-Butylbenzene LANXESS Uniplex 214 Sulfonamide Talc Imerys Talc Mistron CB Pentaerythritol Tetrakis(3- Ciba Irganox 1010 (3,5-di-t-butyl-4- hydroxyphenyl)propionate)

Extrusion for Examples 1a-4b

(38) Extrusion was performed in a Leistritz ZSE27MX-48D co-rotating twin screw extruder at a temperature between 100° C. to 250° C., between 50-300 rpm. The extruder had a screw diameter of 27 mm, L/D ratio of 28:1 and 12 barrels/zones (including the die) with individual heating or cooling.

(39) Soxhlet Extraction

(40) 3.0 g of PA containing samples were pressed into thin sheets. A portion of the sheet was subjected to a sequence of Soxleth extractions using glass microfibre thimbles.

(41) The masses of the compounds and thimbles were recorded before beginning extraction. The thimbles were added to the Soxhlet apparatus and extracted with refluxing toluene for 4 h, formic acid for 4 h, toluene for 4 h, and finally formic acid for 4 h again. After the final extraction, the thimbles were dried under vacuum and % mass remaining was calculated. In cases where there was residual mass, the residue was characterized by ATR IR spectroscopy.

(42) Purification of Extrudates

(43) Extrudates that did not contain thermoplastic were purified for use in IR and NMR analysis to remove any un-grafted MAH or other volatiles which may interfere in analysis. A small amount of sample (<1 g) was dissolved in toluene at room temperature. The compound was then coagulated out with acetone and any excess solvent was allowed to air dry. This process was repeated. Samples were finally dried in a vacuum oven overnight before analysis.

(44) DSM Injection Molding

(45) The compounds which contained PA were injection molded in the DSM Xplore Micro-compounder (DSM) to form dumbbells for tensile testing. The DSM was heated to 220° C. and approximately 12 grams of each compound (as pellets or strands) was added to the barrel (100 rpm) and allowed to melt for 2 min. The compound was then injection molded into the S2 micro-dumbbell mold.

(46) Tensile Test

(47) Injection molded S2 micro-dumbbells were measured in triplicate for stress-strain properties on the T2000 Tensometer according to ASTM D412.

(48) Mooney Viscosity

(49) If applicable, extrudates were analyzed by Mooney Viscosity measurements ML 1+8 @ 125° C. (ASTM D1646).

(50) Extension Cycling Fatigue

(51) Samples were tested according to ASTM D 4482 with the exception of the strain cycle. This standard method requires the use of a tester controlled by cams to induce a strain cycle consisting of increasing strain for one quarter the time, decreasing strain for one quarter the time, then zero strain for half the time (pulsed-type test). Here, samples were tested using the DeMattia flex tester, which induced an increasing strain for half the time and a decreasing strain for half the time. Injection molded Die C dumbbells were cyclically strained at 1.7 Hz (100 cpm) to a specified initial extension ratio. The extension ratio is defined as L L.sub.0.sup.−1 where L is the extended length of the specimen and L.sub.0 is the unextended length. As a result of the flexing, cracks usually initiated by a naturally occurring flaw, grow and ultimately cause failure. The fatigue life of the specimen was determined by the number of cycles to failure, where failure was defined by complete rupture of the sample. A bench mark of 25 mm was placed on the sample to determine the initial extension ratio. After 1000 cycles, the grips were adjusted for permanent set of the specimen, which reduces the extension ratio. The average number of cycles to failure for two specimens was reported. The initial extension ratio was 0.24.

(52) Nuclear Magnetic Resonance (NMR)

(53) NMR analysis was performed on a Bruker 500 MHz spectrometer in CDCl.sub.3. NMR spectra of MAH-containing extrudates showed signals at 3.2 and 3.4 ppm, which have been previously attributed to the Diels-Alder adduct of the exo-CD unit with maleic anhydride. Mol % of grafted MAH was calculated from the integration of the above signals.

Examples 1a-4a

(54) The butyl ionomer used in these examples were derived from LANXESS Bromobutyl 2030 and triphenylphosphine and had an ionic content of 0.5 mol % as well as a Mooney viscosity of 58. This set of examples was carried out in absence of thermoplastic in order to allow for processing and characterization of the resulting extrudates in solution. The butyl polymers were dusted with talc (7 phr). The extrudate composition is stated in Table 2 for each example. The composition was extruded as described above. The extrudates were purified and subjected to IR and .sup.1H NMR analysis. Table 2 furthermore states the absence or presence for spectroscopic evidence for MAH grafting (i.e. IR absorbance at 1780 cm.sup.1 and resonances in the .sup.1H NMR spectrum at 3.2 and 3.4 ppm).

(55) TABLE-US-00002 TABLE 2 Example 1a 2a 3a 4a Example type comparative comparative comparative inventive LANXESS Butyl 100 100 0 0 402 Butyl ionomer 0 0 100 100 MAH (phr).sup.c) 0 2 0 2 Irganox 1010 2 2 2 2 (phr).sup.c) Talc.sup.c) 4 2 4 2 IR: MAH- absent absent absent present absorbance at 1780 cm.sup.−1 NMR: n.d. n.d. absent present Resonances at 3.2 and 3.4 ppm

(56) Table 2 shows that grafting of MAH is only successful if the combination of MAH and butyl ionomer is used. The extrusion of bromobutyl rubber in lieu of regular butyl and butyl ionomer resulted in an extrudate of unsuitably low viscosity.

Examples 1b-4b

(57) The butyl ionomer used in these examples were derived from LANXESS Bromobutyl 2030 and triphenylphosphine and had an ionic content of 0.5 mol % as well as a Mooney viscosity of 58. This set of examples was carried out in presence of thermoplastic (Durethan CI 31 F). The butyl polymers were dusted with talc (7 phr). The extrudate composition is stated in Table 3 for each example. Extrusion took place at 219° C. average barrel temperature, 150 rpm. With exception of Durethan CI 31 F, all ingredients were fed into the extruder in Zone 0 with a rate of 5 kg h.sup.−1; Durethan CI 31 F was added to the extruder via a side stuffer located at Zone 8 at a rate of 4.75 kg h.sup.−1. The extrudates were pelletized, dried and injection molded into test specimen for further characterization by stress-strain measurements and extraction.

(58) TABLE-US-00003 TABLE 3 Example 1b 2b 3b 4b Example type comparative comparative comparative inventive LANXESS Butyl 100 100 0 0 402 (phr) Butyl ionomer 0 0 100 100 (phr) Durethan CI 31 F 103 103 103 103 (phr) MAH (phr) 0 2 0 2 Irganox 1010 2 2 2 2 (phr) Mistron CB (phr) 4 2 4 2 Mass Remaining 1.2 0.3 0.4 10.5 after extraction (%) IR of extraction n.d. n.d. n.d. present residue: PA absorbance at 1650 cm.sup.−1 Elongation at 32 31 40 90 break (%) Tensile strength 17.4 15.9 11.6 15.6 (MPa)

(59) Example 4b, which was compounded based on MAH as well as an allylic bromide containing butyl ionomer, shows a significantly improved elongation at break over the remaining comparative examples (Examples 1 b, 2b and 3b). Furthermore, this blend does not dissolve completely upon extraction. IR analysis on the extraction residue furthermore shows the presence of absorption bands that are attributable to polyamide and butyl rubber. The residual masses observed upon extraction of MAH-containing Durethan CI 31 F/butyl ionomer blends supports that MAH mediates the covalent grafting between ionomeric butyl rubber and polyamide.

Examples 5-9

(60) The butyl ionomer used in Examples 5-9 was derived from LANXESS Bromobutyl X2 and triphenylphosphine and had an ionic content of 0.3 mol % and a Mooney viscosity of 56. For Examples 5-9, a composition of 100 phr Ionomer with 3 phr talcum, 2 phr maleic anhydride and 1 phr Irganox 1010 were extruded using a co-rotating twin-screw extruder from Leistritz with a screw diameter of 27 mm and an L/D ratio of 57 at a throughput of 15 kg/h and 350 rpm using different temperature profiles. The temperature set values for the barrels (Zones 0-13 and Die) are given in Table 4. The Mooney viscosity and amount of grafted MAH, as determined from signals in the .sup.1H NMR spectra of the Diels-Alder adduct formed for the individual examples is reported in Table 5. Results from Table 5 show that the higher the temperature, the higher is the amount of grafting achieved and the lower is the Mooney viscosity of the extrudate.

(61) TABLE-US-00004 TABLE 4 Temperature profile Barrel #185 #200 #215 #230 #245 0  25° C.  25° C.  25° C.  25° C.  25° C. 1  25° C.  25° C.  25° C.  25° C.  25° C. 2  80° C.  80° C.  80° C.  80° C.  30° C. 3  80° C.  80° C.  80° C.  80° C.  80° C. 4  80° C.  80° C.  80° C.  80° C.  80° C. 5 106° C. 110° C. 114° C. 118° C. 125° C. 6 133° C. 140° C. 148° C. 155° C. 170° C. 7 159° C. 170° C. 181° C. 193° C. 210° C. 8 185° C. 200° C. 215° C. 230° C. 245° C. 9 185° C. 200° C. 215° C. 230° C. 245° C. 10 185° C. 200° C. 215° C. 230° C. 245° C. 11 198° C. 205° C. 213° C. 220° C. 225° C. 12 210° C. 210° C. 210° C. 210° C. 210° C. 13 210° C. 210° C. 210° C. 210° C. 210° C. Die 205° C. 205° C. 205° C. 205° C. 205° C.

(62) TABLE-US-00005 TABLE 5 Mooney Grafted Temp. Viscosity MAH Example Profile [MU] [mol %] Example 5 #185 34 0.00 Example 6 #200 34 0.00 Example 7 #215 34 0.00 Example 8 #230 27 0.05 Example 9 #245 23 0.07

(63) Table 5 shows that using temperatures according to temperature profile #230 or higher leads to grafting of maleic anhydride to butyl ionomer. In particular, temperature profile #230 leads to a desirable balance of Mooney viscosity and maleic anhydride grafting.

Examples 10-14

(64) The butyl ionomer used in Examples 10-12 was derived from LANXESS Bromobutyl X2 and triphenylphosphine and had an ionic content of 0.3 mol % and a Mooney viscosity of 56. For Examples 10-14, the compositions stated in Table 6 were extruded (103 phr ionomer=100 phr ionic polymer with 3 phr talcum) using a co-rotating twin-screw extruder from Leistritz with a screw diameter of 27 mm and an L/D ratio of 57 at the throughput stated in said table and 200 rpm using temperature profile #230 described in Table 4. The Mooney viscosity and amount of grafted MAH, as determined from signals in the .sup.1H NMR spectra of the Diels-Alder adduct formed for the individual examples is reported in Table 6. Also, pelletization of the extrudates by means of an underwater pelletizer was possible in Examples 10 through 12. The extrudates from comparative Examples 13 and 14 were too low in viscosity to be processed into pellets or to be subjected to a Mooney viscosity measurement. Comparative Examples 13 and 14 thus show that bromobutyl cannot be thermally grafted with maleic anhydride while maintaining a Mooney viscosity above 10, while Examples 10-12 show that a Mooney viscosity well above 10 is obtained when butyl ionomers are used. Examples 10 and 11 show that it is possible to graft maleic anhydride to butyl ionomer in a reactive mixing process, achieving grafting levels of greater than or equal to 0.05 mol %, for example grafting levels of 0.16-0.17 mol %

(65) TABLE-US-00006 TABLE 6 Results Composition [phr] Extruder Mooney Grafted Pellet- Bromobutyl Irganox throughput Viscosity MAH ization Example Type Ionomer X2 MAH 1010 Talcum [kg/h] [MU] [mol %] possible Ex. 10 Inventive 103 2 1 15.00 30 0.16 Yes Ex. 11 Inventive 103 4 2 15.45 25 0.17 Yes Ex. 12 Comparative 103 1 2 14.00 19 0.00 Yes Ex. 13 Comparative 103 15.00 n.d. 0.00 No Ex. 14 Comparative 103 4 2 15.45 n.d. 0.11 No

Examples 15-19

(66) Examples 10-12 were further subjected to blending with polyamide. Examples 15-19 relied on Grilon CR8 as polyamide, and n-butylbenzensulfonamide (BBSA) as plasticizer. Polyamide blends were prepared using elastomer at a level of 102 phr (=100 phr elastomer+2 phr dusting agent) and 63 phr Grilon CR8 and 14 or 27 phr BBSA. Since comparative Examples 13 and 14 were not processible, no polyamide blends could be prepared from these materials. LANXESS Bromobutyl X2 was used instead for Example 15. Compositions of Examples 15-19 are summarized in Table 7. The barrel temperatures in these examples were 200-230° C. and screw speeds 500-700 rpm. The extrudate strand was cooled in water troughs and pelletized. The resulting pellets were dried to a humidity content under 0.08 wt. %. For the preparation of the test specimen (dumbbells) an Arburg 320-500 injection molding machine was utilized. The obtained samples were characterized as molded, no conditioning to a specific humidity was performed. Properties of the resulting materials are summarized in Table 8.

(67) TABLE-US-00007 TABLE 7 MAH- grafted Example Example Example Grilon Throughput Example polymer BBX2 12 10 11 CR8 BBSA [kg/h] Example 15 No 102 63 27 19.05 Example 16 No 102 63 27 19.05 Example 17 Yes 102 63 14 17.71 Example 18 Yes 102 63 27 19.07 Example 19 Yes 102 63 27 19.05

(68) TABLE-US-00008 TABLE 8 Extension MAH- Tensile Elongation cycling grafted strength at break Tensile fatigue Example polymer [Mpa] [%] set [%] [kilocycles] Example 15 No Example 16 No 5.1 ± 0.5 108 ± 13 Broke 1.2 Example 17 Yes 7.8 ± 0.3 244 ± 12 21.0 ± 2.3 not tested Example 18 Yes 6.8 ± 0.7 212 ± 25 15.0 ± 0.0 not tested Example 19 Yes 6.8 ± 0.3 251 ± 26 11.0 ± 2.3 7.3

(69) Comparative Example 15 could not be processed into pellets, hence no test specimens were prepared. This shows that bromobutyl is not suitable for the preparation of polyamide elastomer blends. Comparative Example 16 (comprising a butyl ionomer without any grafted maleic anhydride) could be processed into a test specimen, but exhibited inferior properties (lower tensile strength, lower elongation at break, breaks during tensile set measurement, breaks after only 1200 cycles in flex fatigue test) vs. inventive Examples 17-19 that are based on a maleated butyl ionomer. Thus, maleated butyl ionomer gives a polyamide blend with improved properties.