CZ13993A3 - thermoplastic materials - Google Patents

Abstract

Thermoplastic plastic that can be unvulcanized and which comprises a blend of polymers consisting of elastomeric thermoplastic technical resins a a halogen-containing isomonoolefin cypolymer of Ca to C7 and para-alkylstyrene, and the process for preparing dynamically vulcanized plastics.

Description

Technical field - i -

The present invention relates to thermoplastic plastics having improved properties and to a process for the preparation of these plastics. Alternatively, these materials can also be dynamically vulcanized.

BACKGROUND OF THE INVENTION

In recent years, polymer blends having a combination of elastic and thermoplastic properties have enjoyed significant commercial interest.

These polymer blends were given the generic name thermoplastic! Greek olefins (TPO). They exhibit some of the properties of the vulcanized elastomer and can be reprocessed just like thermoplastic resins. Elastomeric characteristics may be enhanced if one component of the composition is a curable elastomer that is fully or partially crosslinked.

U.S. Patent 4,130,534 discloses elastoplastic plastics comprising a mixture of thermoplastic crystalline polyolefin resin and rubber, which may be either butyl rubber, chlorobutyl rubber or bromobutyl rubber.

U.S. Patent 4,172,859 discloses a thermoplastic plastic comprising a polyamide resin matrix and at least one polymer having a specified modulus of elasticity.

U.S. Patent 4,174,358 discloses a thermoplastic plastic comprising a polyamide resin matrix and at least one polymer with a specified modulus of elasticity.

The earliest work on the vulcanization of TPO materials was carried out by Gessler and Haslett, see II. U.S. Patent 3,037,954. This patent explains the concept of dynamic vulcanization in which a curable elastomer is dispersed in a resinous thermoplastic polymer and is vulcanized with continuous mixing and spreading of the polymer blend. The result is a microgel dispersion of vulcanized rubber in an unvulcanized resin matrix of a thermoplastic polymer.

Gessler U.S. Patent 3,037,954 discloses synthetic compositions comprising polypropylene and rubber, wherein the rubber may be butyl rubber, chlorinated butyl rubber, polybutadiene, polychloroprene, and polyisobutene. Described herein are plastics from 50 to 95 parts polypropylene and about 5 to 50 parts rubber.

U.S. Patent 4,639,487 discloses a heat-shrinkable thermoplastic blend of ethylene copolymer resin with dynamically vulcanized halogenated butyl rubber.

Dynamically vulcanized thermoplastic plastics containing polyamide and various types of elastomers are known, as described, for example, in U.S. Patent 4,173,556; AT,

4,197,379; U.S. Patent 4,207,404; AT.

4,297,453; U.S. Pat. No. 4,338,413; U.S. Pat. U.S. Patent 4,334,502 and U.S. Patent 4,419,499.

if. S. Patent 4,287,324 discloses a dynamically vulcanized plastic comprising a mixture of crystalline polyester and vulcanized epichlorohydrin.

U.S. Patent 4,226,953 discloses a dynamically vulcanized mass comprising a mixture of styrene acrylonitrile resin and nitrile rubber.

if. S. Patent 4, 350, 794 discloses a molded and extruded plastic prepared by mixing a molten polyamide resin and a polyamide reactive halogen functional elastomer.

S. Patent

S. Patent

There is still a need to improve the properties of unvulcanized and dynamically vulcanized compositions.

More recently, it has been found that plastics containing a thermoplastic technical resin and a halogenated copolymer of isooolefin and para-alkylstyrene have improved properties such as higher Vicat softening point, lower oil sorption, compression resistance and retention of properties after thermal aging. In addition, these compositions can be stabilized against ultraviolet radiation without adversely affecting their properties. These plastics may also contain unvulcanized or dynamically vulcanized elastomers.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the invention, the present invention provides a thermoplastic plastic comprising a polymer blend of a thermoplastic technical resin and a halogen-containing copolymer of isomonoolefin C4 to C7 and para-alkylstyrene.

According to another embodiment of the invention, there is provided a thermoplastic plastic comprising a vulcanized polymer blend of a thermoplastic technical resin and an elastomeric halogen-containing copolymer of isomonoolefin C4 to C7 and para-alkylstyrene.

DETAILED DESCRIPTION OF THE INVENTION

The thermoplastic plastic of the present invention comprises a mixture of a thermoplastic technical resin and an elastomeric halogen-containing copolymer of isomonoolefin C4-C7 and para-alkylstyrene, which may be unvulcanized or may be statically vulcanizable or subjected to dynamic vulcanization.

The term dynamic vulcanization is used herein to denote the vulcanization process in which the technical resins are present

And vulcanizing elastomer vulcanized under high friction conditions. As a result, the vulcanizable elastomer is simultaneously crosslinked and dispersed as fine microgel particles within the resin matrix.

Dynamic vulcanization is accomplished by mixing the components at a temperature that is exactly or above the vulcanization temperature of the elastomer in devices such as roller mills, Branbury® mixers, continuous mixers, kneaders or mixer extruders, eg with a twin screw.

A unique characteristic of dynamically vulcanized plastics is that although the elastomeric component can be fully vulcanized, the plastics can be processed several times in succession by conventional rubber processing techniques such as extrusion, injection molding, injection molding, compression molding, etc. The rest. can be maintained and reprocessed.

In an embodiment of the present invention in which it is desirable to obtain dynamically vulcanized compositions (DVA's), compositions are generally prepared by mixing at least one technical resin and at least one elastomer with stabilizers and fillers under dynamic vulcanization conditions.

In the preparation of the dynamically vulcanized plastic according to the invention, at least one part of one thermoplastic technical resin is mixed with a halogen-containing elastomeric copolymer.

Thermoplastic resins suitable for practicing the present invention may be used alone or in combination and are resins containing nitrogen, oxygen, halogen, sulfur or other groups capable of interacting with an aromatic haloalkyl group. Suitable technical resins are resins selected from the group consisting of polyamides, polycarbonates, polyesters, polysulfones, polyacetals, acrylonitrile-butadiene-styrene resins (ABS), polyphenylene oxides (PPO), polyphenylene sulfides (PPS), styrene acrylonitrile (SAN), ), aromatic polyketones (PEEK, PEK and PEKK) and mixtures thereof.

Suitable technical thermoplastic resins are polyamides. Particularly suitable polyamides are nylon 6 and nylon

11.

Suitable thermoplastic polyamides (nylons) consist of high molecular weight crystalline or resin solid polymers, including copolymers and terpolymers having repeating amide units in the polymer chain. The polyamides may be prepared by polymerizing one or more epsilon on-lactams such as caprolactam, pyrrolidone, lauryllactam and aminoundecanoic acid lactam, or amino acids, or by condensation of dibasic acids and diamines. Both fiber-forming nylons and moldable nylons are suitable. Examples of such polyamides are polycaprolactam (nylon-6), polylauryllactam (nylon-12), polyhexamethylenadipamide (nylon-6,6), polyhexamethylenenazelamide (nylon-6, 9), polyhexamethylenebakamide (nylon-6, 10), polyhexamethylenis (nylon-6, 10) ,

IP) and the condensation product of 11-aminoudecanoic acid (nylon-11). Other examples of suitable polyamides (especially those having a melting point below 275 ° C) are described in Kirk-Othmer's Encyclopedia of Chemical Technology, vol. 10, p. 919, and in Encyclopedia of Polymer Science and Technology, vol. 10, p. 392 - 414.

Commercially available thermoplastic polyamides may be advantageously used in the practice of this invention, linear crystalline polyamides having a melting point between 160-230 ° C are particularly suitable.

Suitable thermoplastic polyesters include high molecular weight linear crystalline rigid polymers having repeating

II

- c - o groups included

- o - c - o groups within the polymer chain. The term linear, as used herein with respect to polyester, means a polymer in which the repeating ester groups are within the polymer backbone and not suspended thereon. Linear crystalline polyesters having a softening or melting point above about 50 ° C are suitable, with polyesters having a softening or melting point above 100 ° C being preferred, and polyesters having a softening or melting point between 160-260 are more preferred Saturated linear polyesters (without olefinic unsaturation) take precedence, but unsaturated polyesters may be used provided that the rubber, when crosslinked, is crosslinked before blending with the polyester, or provided that the rubber is dynamically crosslinked using a crosslinking agents that will not significantly induce crosslinking in the polyester. Crosslinked polyesters are unsuitable for use in the practice of the present invention. If significant crosslinking of the polyester is permitted, the resulting mass is not thermoplastic. Many commercially available thermoplastic linear polyesters may be advantageously employed in the practice of this invention or may be prepared by polymerizing one or more dicarboxylic acids, anhydrides or esters and one or more diols. Examples of suitable polyesters include poly-trans-1,4-cyclohexylene-C2-6 ^- alkanedicarboxylates such as poly-trans-1,4-cyclohexylsuccinate and poly-cis- or

Co-2 'alkanedicarboxylates, - cyclohexane-dimethylene poly-trans-1,4-cyclohexane enadipate, trans-1,4-cyclohexanedimethylene such as poly-cis-1,4-oxalate and poly-cis-1,4-cyclohexane-di -methylensukcinát poly-C2-4-alkylene terephthalates, such as polytetramethylene after lyethy1entereftalát and poly-C 2 - 4 ^- a1ky1enizoftaláty like polyethy1enizofta 1AT and polytetramethylenizoftalát t

poly-para-phenylene-C 1-3 -alkanedicarboxylates such as poly-para-phenylene glutarate and poly-para-phenylene adipate, polypara-phenylene oxalate), poly-ortho-xylene oxalate, poly-para-phenylene di-C 1-5 -alkylene terephthalates such as poly-para-phenylene dimethylene phthalate and poly-paraphenylene di-1,4-butylene terephthalate, poly-C 2-10 -alkylene-1,2-ethylenedioxy-4,4-dibenzoates such as

-ethylenedioxy-4,4-dibenzoates, -ethylenedioxy-4,4-dibenzoates are polyethylene-1,2-polytetramethylene-1,2-polyhexamthylene-1,2-ethylenedioxy-4,4-dibenzoate, poly-C3-10-alkylene -4,4- dibenzoates such as polypentamethylene-4,4-dibenzoate, polyhexamethylene-4,4-dibenzoate and polydecamethylene-4,4-dibenzoate, poly-C 2-10 -alkylene-2,6-naphthalenedicarboxylates such as are polyethylene-2,6-2,6-naphthalenedicarboxylates, polytriraethylene-2,6-naphthalenedicarboxylates and polytetramethylene-2,6-naphthalenedicarboxylates; polydecamethylene sulfones 1-4,4-dibenzoate.

Other examples of suitable linear polyesters are described in Encyclopedia of Polymer Science and Technology, Vol. 11, pp. 68-73 and in the Polyester of Korshaka and Vinogradová, Pergamon Press, pp. 31-64. Reference is made to the data from here. Suitable polycarbonates are also commercially available. For suitable segmented polyether co-phthalates, see page 46, World Blue Book Rubber, supra. Polylactones such as polycaprolacto are suitable for practicing the present invention. Suitable polyesters of the invention are derived from aromatic dicarboxylic acids such as naphthoic acid or phthalic acid. More preferred polyesters are polyalkylene terephthalates, especially polytetramethylene terephthalate, or mixed polyphthalates derived from two or more glycols, two or more phthalic acids, or two or more glycols, and two or more phthalic acids, such as polyalkylenterecisophthalates. Alternatively, other thermoplastic polymers can be incorporated into the polymer blends, such as polyolefin resins - e.g. PP, HDPE, LDPE, EVA,

EMA, etc.

Elastomeric copolymer component containing halogen

Suitable halogen-containing copolymers of isomonoolefin

The C4-7 and para-alkylstyrene for use as components of the present invention comprise at least about 0.5% by weight of the para-alkylstyrene moiety. For elastomeric copolymers, the paraalkyl styrene moiety may range from 0.5 wt% to about 25 wt%, more preferably from about 1 to about 20 wt%, more preferably from about 2 to about 20 wt% of the copolymer. The halogen content of the copolymers may range from more than zero to about 10% by weight, preferably from about 0.1 to about 7% by weight. The halogen may be bromine, chlorine and mixtures thereof. Preferably, the halogen is bromine. A larger proportion of the halogen is chemically bonded to the para-alkyl group, i.e. the halogen-containing copolymer contains para-haloalkyl groups.

Copolymers of isomonoolefin and para-alkylstyrene useful for preparing halogen-containing copolymers useful as plastic components of the invention include copolymers of isomonoolefin having from 4 to 7 carbon atoms and para-alkylstyrene such as those described in European patent application 89305395 No. 9 filed May 26, 1989 (Publication No. 0344021 published November 29, 1989). A suitable isomonoolefin comprises isobutylene. A suitable para-alkylstyrene comprises para-methylstyrene. Suitable copolymers of isomonoolefin and para-alkylstyrene include copolymers having an average molecular weight (Mn) of at least about 25,000, preferably at least about 30,000, more preferably at least about 100,000. The copolymers also preferably have a weight average molecular weight ratio i (Mw) to number average molecular weight (Mn), i.e. MW / Mn less than about 6, more preferred copolymers having this ratio less than 4, even more preferably less than about 2.5, and most preferably less than about 2. Brominated copolymer of isooolefin and para-alkylstyrene formed in the polymerization of these individual monomers under certain specific polymerization conditions, they now make it possible to produce copolymers which contain a direct reaction product (ie in their polymerized form) and which have an unexpectedly homogeneous uniform distribution of the individual components. Thus, utilizing the polymerization and brination procedures described hereinbelow, copolymers suitable for practicing the present invention can be prepared. These copolymers, as determined by gel permeation chromatography (GPC), exhibit narrow molecular weight distributions and a truly homogeneous component distribution or component uniformity over the full range of the resulting plastics. At least about 95% by weight of the copolymer product has a para-alkyl styrene content of about 10% by weight and more preferably up to about 7% by weight of the average para-alkyl styrene content of the total mass, and preferably at least about 97% by weight of the copolymer product has a para-alkylstyrene content. up to about 10% by weight and more preferably up to 7% by weight of the average para-alkylstyrene content of the total plastic. This truly homogeneous composite uniformity is therefore particularly related to the inter-composite distribution. That is, for the specified copolymers, since between each selected fraction of a certain molecular weight the percentage in it or the ratio of para-alkylstyrene to isooolefin will be substantially the same in the method given below.

Moreover, since the relative reactivity of an isooolefin, such as isobutylene, with para-alkylstyrene is very close to one, the distribution of the components of these copolymers will thus be considerably homogeneous. That is, these copolymers are essentially random copolymers and in any single polymer chain the para-alkylstyrene and isooolefin units will in principle be randomly distributed throughout the chain.

Halogen-containing copolymers suitable for practicing the present invention have a truly homogeneous distribution of the components and comprise a para-alkylstyrene moiety represented by

Η

R ¹ wherein R and R ¹ are independently selected from the group consisting of hydrogen, alkyl having preferably from 1 to 5 carbon atoms, primary haloalkyl, secondary haloalkyl having preferably from 1 to 5 carbon atoms, and mixtures thereof and X is selected from the group consisting of chlorine, bromine and mixtures thereof, such as those disclosed in European Patent Application 8930595.9 filed May 26, 1989 (Publication No. 0344021 published Nov. 29, 1989).

Various methods can be used to produce the copolymers of isomonoolefin and para-alkylstyrene, as described in said European Published Application. It is desirable to perform the polymerization continuously by a typical continuous polymerization process using a tank-type bulkhead reactor equipped with powerful mixing means such as a turbomixer or propeller stirrer and a draft tube, external cooling jacket and internal cooling coils or other means to remove polymerization heat, monomers, catalysts and solvents, temperature sensors and solid waste overflow at the clamping cylinder or cooling tank. The reactor is devoid of air and moisture and filled with a dry purified solvent or solvent mixture prior to introduction of monomers and catalysts.

Reactors that are commonly used to polymerize butyl rubber are generally suitable for use in a polymerization reaction in which it is desirable to prepare para-alkylstyrene copolymers suitable for use in the process of the invention. The polymerization temperature can range from about -35 ° C to about -100 ° C, more preferably from about -40 ° C to about -97 ° C.

The processes for preparing the copolymers can be carried out in the form of a polymer suspension formed in the solvents used or as a homogeneous reaction in solution. However, the slurry process is preferable, since in this case mixtures of lower viscosity are formed in the reactor and a polymer concentration in the slurry of up to 40% by weight of polymer can be achieved.

Copolymers of isomonoolefins and para-alkylstyrene can be prepared by admixing isomonoolefin and para-alkylstyrene to the copolymerization reactor under copolymerization conditions in the presence of a solvent and a Lewis acid catalyst.

Typical examples of solvents that may be used alone or in a mixture are propane, butane, pentane, cyclopentane, hexane, toluene, Reptane, isooctane, etc., and various halogenated hydrocarbon solvents that are particularly preferred herein, such as methylene chloride, chloroform, carbon tetrachloride methyl chloride, methyl chloride being particularly preferred.

An important element in the preparation of copolymers is the elimination of impurities from the polymerization reactor, since impurities, if present, cause catalyst degradation or excess molecular weight reduction by complexation with catalyst or copolymerization with isomonoolefins or para-alkylstyrene, which in turn prevents it from effectively forming. a para-alkylstyrene copolymer product useful in the practice of this invention. In particular, these impurities include catalyst poisons such as moisture and the like and other copolymerizable monomers such as meta-alkylstyrenes and the like. These impurities should not have access to the reaction system.

For the preparation of suitable copolymers, it is preferred that the para-alkylstyrene is at least 95% pure, more preferably 97.5% pure and most preferably 99.5% pure, and that the isomonoolefin is at least 99.5% pure, more preferably at least 99.8% by weight pure and that the solvents used are at least 99% by weight pure and more preferably at least 99.8% by weight pure.

Preferred catalytic Lewis acids are ethyl aluminum dichloride and suitable mixtures of ethyl aluminum dichloride with diethyl aluminum chloride. The amount of such catalysts used will depend upon the desired molecular weight and the desired weight distribution of the copolymer produced, but will generally be in the range of about 20 ppm to 1% by weight, and more preferably from about 0.01 to about 0.2% by weight, based on the total. the amount of monomer to be polymerized.

Halogenation of the polymer may be carried out in the volume of the reaction mixture (eg, in the melt) or in either a solution or a finely dispersed suspension. Bulk halogenation may be carried out in an extruder or other internal mixer suitably adapted to provide proper mixing and to handle the halogen and corrosive by-products. Details of such volumetric halation processes are also disclosed in U.S. Pat. No. 4,554,995, which is incorporated herein by reference.

-14Vhodná solvents for the halogenation in the solution are within the group of hydrocarbons of low boiling point _(C4 to C7) and halogenated hydrocarbons. Since the high boiling point of para-methylstyrene makes its removal by conventional distillation impractical and because it is difficult to prevent completely halogenation of the solvent, it is very important where halogenation is to take place in solution or suspension to choose a non-halogenated diluent. and to reduce the residual para-methylstyrene concentration to an acceptable level.

It should be noted that radical bromination to achieve. The desired bromobenzyl functional group of the copolymer-chained para-methylstyrene unit which is useful in the practice of this invention can be performed very specifically, with almost exclusively substitution on the para-methyl group. Thus, the high specificity of the bromination reaction can be maintained over a wide range of reaction conditions, provided that we avoid factors that would support the ionic reaction mechanism (i.e., polar diluents, Friedel-Crafts catalysts, etc.).

Thus, solutions of suitable para-methyl styrene isobutylene copolymers in hydrocarbon solvents such as pentane, hexane, heptane or cyclohexane can be selectively accumulated using light, heat, or selected radical initiators (depending on the conditions, i.e., such individual radical initiator must be selected a reaction having a suitable half-life for those particular temperature conditions used, with longer halves in general being preferred at higher halogenation temperatures) as radical halogenation promoters to achieve the almost exclusively desirable bromo15 benzyl functionality by substitution on the para-methyl group and without appreciable cleavage; chaining.

This reaction may be initiated by the formation of a bromine atom, either photochemically or thermally (with or without the use of sensitizers), or a radical initiator that preferentially reacts with a bromine molecule rather than one that reacts without discrimination with bromine atoms or solvent, or with a polymer (i.e., removal of hydrogen). Said sensitizers are those photochemical sensitizers that will themselves absorb low energy photons and dissociate, thereby causing bromine dissociation, including also substances such as iodine. It is convenient to use an initiator having a half-life of between 0.5 and 2500 minutes under the desired reaction conditions, more preferably about 10 to 300 minutes. The amount of initiator used is generally between 0.02 and 1% by weight of the copolymer, preferably between about 0.02 and 0.3%. Suitable initiators are bis-azo compounds, such as azo-bis-isobutyronitrile (AIBN), azo-bis- (2, N-dimethylvinyl) nitrile, and the like. Other free radical initiators may also be used, but it is preferable to use a free radical initiator which is relatively ineffective in hydrogen removal so that it reacts preferentially with bromine molecules to form bromine atoms, rather than with a copolymer or solvent to form alkyl radicals.

Indeed, in these cases, the molecular weight of the resulting copolymer would be lost and undesirable reactions such as crosslinking would be promoted. The free-radical bromination reaction of the copolymers of para-methylstyrene and isobutylene can be highly selective under appropriate conditions and almost exclusively gives the desired bromobenzyl functional groups. Indeed, the only major side reaction that occurs is the disubstitution on the para-ethyl group, thereby producing dibromo derivatives, but even this does not occur to more than about 60% of the monosubstituted parameters of the aryl units in the chain. Thus, any desired amount of bromobenzyl functional groups in monobrominated form can be introduced into the above-described copolymers up to about 60 molar X of the para-methyl styrene content.

It is desirable that the termination reactions during bromination be minimized so that rapid radical chain reactions take place for a long time and so that many bromobenzyls are involved in each initiation with a minimum of side reactions arising from termination. Thus, the purity of the system is important and the equilibrium radical concentrations must be kept low enough to prevent extensive recombination and possible cross-linking. The reaction must also be stopped as soon as bromine is consumed so as to prevent the continued formation of radicals with subsequent secondary reactions (in the absence of bromine). The reaction may be terminated by cooling, turning off the light source, adding dilute caustic, adding a radical scavenger, or combinations thereof.

Since 1 mol of HBr is produced per mole of bromine reacted or substituted on the para-methylstyryl unit incorporated in the chain, it is also desirable to neutralize or otherwise remove this HBr during the reaction, or at least during polymer removal to prevent its reaction with HBr or catalyzing adverse reactions. Such neutralization and removal of HBr may be accomplished by lye purging after completion of the reaction, usually using a molar excess of caustic to HBr. Alternatively, the neutralization can be carried out with a lump base (which is relatively not 17 reactive with bromine), such as a calcium carbonate powder present in dispersed form during the bromination reaction to adsorb HBr as soon as it is formed. Removal of HBr can also be achieved by distillation with an inert gas (e.g. N 2) preferably at elevated temperatures.

Brominated, terminated and neutralized para-methylstyrene / isobutylene copolymers can be obtained and finalized using conventional means with the addition of suitable stabilizers to obtain highly desirable and universally functional saturated copolymers.

In summary, halogenation to form copolymers useful as plastic components of the present invention is preferably accomplished by halogenating isobutylene-para-methyl styrene copolymers with bromine in a solution of a normal alkane (e.g. hexane or heptane) using a bis-azo initiator, e.g. AIBN or VAZO ^R 52: 2,2'-azo-bis (2,4-dimethylpentanonitrile), at about 55 to 80 ° C for about 4.5 minutes to about 30 minutes, followed by stopping with lye. The obtained polymer is washed with basic water and water / isopropanol, separated, stabilized and dried.

Since a small (if any) amount of tertiary bromobenzyl is formed in the molecule (if the halogenating agent is a brominating agent), a potential dehydrohalogenation reaction will be almost completely excluded. This results in a halogen polymer with the improved stability required for high temperature processing required for melt blending and processing with technical resins.

An aromatic haloalkyl group, such as a halomethyl group, allows for easy crosslinking in a variety of ways, e.g., either directly through the halomethyl group or by conversion to other functional groups that allow the desired crosslinking reactions to be utilized. Direct crosslinking may be accomplished by various polyfunctional nucleophilic reagents such as ammonia, amine, polyamines, metal dicarboxylates, metal dithiolates, excited metal oxides (i.e., ZnO and dithiocarbamates), etc. Crosslinking may also be due to polyalkylation reactions. The aromatic halomethyl groups thus provide for a wide variety of crosslinking reactions that are compatible with the requirements of dynamic vulcanization in a melt blend with the technical resin component of the present invention.

In the plastics of this invention, thermoplastic technical resins may suitably be present in an amount ranging from about 10 to 98 wt%, more preferably from about 20 to 95 wt%, the elastomeric halogen-containing copolymer of isomonoolefin and para-alkylstyrene may be present in an amount of from about 2 to 90 wt.%, preferably from about 5 to 80 wt.%, based on the polymer blend.

The term polymer blend is used herein to denote a blend of one or more thermoplastic technical resins, an elastomeric halogen-containing copolymer, and any other polymers (elastomers or non-elastomers) that may be a component of the plastic. Optionally, other elastomers and / or non-elastomeric polymers may be incorporated into the plastic of the present invention.

The flexural cutting modulus of thermoplastics may range from about 100 kg / cm ² to about 400 000 kg / cm ² , preferably from about 200 kg / cm ² to about 100 000 kg / cm ² , measured according to ASTMD 790 at stress 1.

A suitable thermoplastic composition according to the invention comprises a polyamide such as nylon.

The polymer blend may comprise about 25 to 98% by weight of the total plastic. The composition of the invention may contain, in addition to its polymeric components, fillers and additives such as antioxidants, stabilizers, oil lubricants for rubber processing (e.g. oleamides), anti-sticking agents, flame retardants, pigments, filler binders and other processing aids known in the art. rubber compounds. Metal oxides such as MgO can be used to act as acid acceptors. The pigments and fillers may represent up to 30% by weight of the plastic, based on the polymer components with the additives. Preferably, the pigments and fillers represent about 1 to 30% by weight of the plastic, more preferably about 2 to 20% by weight of the total plastic.

Suitable fillers are talc, calcium carbonate, glass fibers, clays, silica, carbon black, and mixtures thereof. Any type of carbon black, such as channel black, retort black, thermal black, acetylene black, lamp black, and the like can be used. Titanium dioxide, also considered a pigment, can give the final product a white color.

Rubber processing oils have a special ASTM designation depending on whether they are in paraffin, naphthenic or aromatic process oils. The type of process oil used will be that customary to use in conjunction with a rubber component. An experienced rubber chemist will know which type of oil to use for each type of rubber. The amount of process oil used is based on the total rubber content and can be defined as the weight ratio of process oil to rubber in the plastic. This ratio can range from about 0.3 / 1 to about 1.3 / 1, more preferably 0.5 / 1 to about 1.2 / 1, even more preferably from about 0.8 / 1 to about 1.1 / 1 . Non-petroleum oils may also be used, such as oils derived from coal tar and spruce tar. In addition, organic esters and other synthetic plasticizers can be used with process oils for processing petroleum-derived rubber. The term process oil as used herein means both oil derived from oil and synthetic plasticizer.

Technological oil may be contained in the plastic to ensure good flow properties of the material. The amount of oil used will depend in part on the amount of blend of polymers and filler used and also to the same extent on the type of vulcanization system used. The process oil, if present, can usually comprise about 30% by weight of the plastic. Larger amounts of process oil may be used, but the reduced physical strength is a drawback.

Antioxidants may be used in the plastic of the present invention to further improve the aging properties of the component consisting of the astomeric copolymers of the present invention and to protect technical resins. The use of individual antioxidants will depend on the rubbers and plastics used, and more than one tvp may be required. Their correct selection depends on the experience of a rubber chemist. Antioxidants will generally fall into the class of chemical protectors or physical preservatives. Physical preservatives are used where there should be little movement in a component to be made of plastic. They are usually waxy materials which refine the surface of the rubber component and form a protective sheath or protect the component from oxygen, ozone, etc.

Chemical protective agents usually fall into three groups: secondary amines, phenolic substances and phosphites. By way of illustration, selected non-exhaustive examples of types of antioxidants useful in the practice of this invention are blocked phenols, arainophenols, hydroquinones, alkyldiamines, amine condensation products, etc. Non-exhaustive examples of these and other types of antioxidants are styrene phenol,

2,2-methylene-bis- (4-methyl-6,1-butylphenol),

2,6-di-t-butyl-o-dimethylamino-p-cresol, hydroquinone monobenzyl ether, octylated diphenylamine, phenyl-beta-naphthyl amine, N, N'-diphenylethylenediamine, aldol-alpha-naphthylamine, N, N > diphenyl 1-p-phenylenediamine, etc. Physical antioxidants include blended petroleum waxes and microcrystalline waxes.

It is within the scope of the invention to incorporate unvulcanised rubber in combination with dynamically vulcanized rubber in the plastic. This may be accomplished either by selecting the unvulcanized rubber, the vulcanizing rubber which is not vulcanizable with the agent used to vulcanize the elastomeric halogenated copolymer component of the present invention, which should be dynamically vulcanized, or by adding the rubber vulcanizable with the vulcanizing vulcanizing agent copolymer components of the invention. For example, when the elastomeric halogenated component of the invention is vulcanized by a vulcanizing system containing zinc oxide, any other rubber that requires other vulcanizing agent to vulcanize or which is not vulcanizable may be present. Such rubbers are ethylene-propylene polymers (EPM), ethylene-propylene-diene polymers (EPDM), polyisobutylene, natural rubber, etc. Another possibility is that the DVA can first be prepared from a resin and a curable elastomer by dynamic vulcanization and then blended into Two unvulcanised rubber at a temperature above the melting point of the thermoplastic resin. In an embodiment in which the unvulcanized rubber is introduced into the dynamically vulcanized mass, the unvulcanized rubber may be present in an amount ranging from zero to about 25% by weight, preferably from about 5 to about 20% by weight, of the total rubber (i.e. elastomer) content of the plastic.

If it is desired to prepare a vulcanized plastic, any conventional vulcanizing system capable of vulcanizing saturated halogenated polymers may be used to vulcanize at least the elastomeric halogenated copolymers of C4-C7 and para-alkylstyrene isomonoolefin, except for peroxide vulcanizing agents which are specifically excluded from implementation of the invention, if the thermoplastic technical resins selected as components are such that the peroxide would cause these thermoplastic resins to cross-link with each other. Furthermore, any vulcanizing agents that would cause the individual technical resin used to crosslink under the technological conditions that would be used to prepare the dynamically vulcanized mixture should be excluded from the vulcanizing system used.

Vulcanizing compositions suitable for the elastomeric halogenated copolymer component of the present invention comprise zinc oxide in combination with zinc stearate or stearic acid and optionally one or more of the following accelerators or vulcanizing agents: Permalux (di-ortho-tolylguanidine dicatecholborate salt), HVA -2 (di-ortho-tolylguanidine salt of dicatechol borate), HVA-2 (m-phenylene-bis-maleimide), Zisnet (2,4,6-trimercapto-5-triazine), ZDEDC (zinc diethyldithiocarbamate) and other dithiocarbamates, Tetron A (dipenta-methylenediuramhexasulfide), Vultac-5 (alkylated phenyldisulfide), SP 1045 (phenol formaldehyde resin), SP 1056 (brominated alkylphenol form 1dehyde resin), DPPD (diphenylenediamine), salicylic acid (o-hydroxybenzoic acid) rosin (abietic acid) and TMTDS (tetramethylthiuram disulfide) in combination with sulfur.

The vulcanization is conducted under conditions such that the halogenated elastomeric copolymer is vulcanized at least partially, preferably completely.

In practicing the present invention, the technical resins, elastomeric copolymer and optionally other polymers are mixed at a temperature sufficient to soften the resin, or more commonly at a temperature above its melting point, when the resin is crystalline at room temperature. If the mixture is to be dynamically vulcanized, the curing agent or agents are added after the resins and other polymers have been intimately mixed. Heating and mastication at vulcanization temperatures typically correspond to complete vulcanization in about 0.5 to about 10 minutes. The vulcanization time can be shortened by increasing the vulcanization temperature. A suitable range of vulcanization temperatures is from about the melting point of the resin matrix to about 300 ° C, more usually the temperature can range from about the melting point of the matrix resin to about 275 ° C. a temperature about 20 ° C higher than the softening or melting point of the resin matrix.

It is advisable to continue stirring until the vulcanization is complete to the desired extent. If vulcanization is allowed to continue after mixing is complete, the plastic as thermoplastic may become unprocessable again. However, the dynamic vulcanization can be carried out in stages. E.g. vulcanization may be initiated in a twin-screw extruder and beads (pellets) formed from DVA material using an underwater pelletizer will stop vulcanization before it is complete.

Under dynamic vulcanization conditions, the vulcanization may be completed later. Those skilled in the art will appreciate the appropriate amounts, types of vulcanizing agents, and the degree of mixing time required to perform vulcanization of the rubber. Where necessary, the rubber may be vulcanized by itself with varying amounts of vulcanizing agent to determine the optimal vulcanizing system and suitable vulcanizing conditions to achieve full vulcanization.

It is preferred that all components be present in the mixture prior to performing the dynamic vulcanization of the present invention, but this is not a necessary condition. E.g. in one embodiment, the elastomer to be cured may be dynamically vulcanized in the presence of some or all of the technical resin. This mixture is then added to another technical resin. Similarly, it is not necessary to add all fillers and oil prior to dynamic vulcanization. Some or all of the additives, fillers and oil may be supplied during or after the vulcanization. Certain ingredients, such as stabilizers and process additives, are more effective when delivered after vulcanization.

The term rubber is used interchangeably with the term elastomer.

The term fully vulcanized as used herein with respect to the dynamically vulcanized rubber components of the present invention means that the rubber components to be vulcanized have been vulcanized to a state in which the physical properties of the rubber are developed to impart to the rubber the elastomeric properties usually associated with the rubber. rubbers in their conventional vulcanized state. The degree of vulcanization of the vulcanized rubber can be described by the gel content or, conversely, by the extractable components. Alternatively, the degree of vulcanization can be expressed by the crosslinking density.

Where the appropriate measurement of the vulcanization state is the determination of extractables, improved thermoplastic elastomeric materials are produced by vulcanizing the vulcanizable rubber components of the compositions to such an extent that they contain no more than about 4% by weight of the vulcanizable rubber components extractable at room temperature with a solvent that dissolves rubbers. they are intended for vulcanization, and more preferably to the extent. wherein the composition comprises less than 2% by weight of the extractable fraction. Generally, the less extractables are from the vulcanized rubber components, the better the properties, and even more suitable are materials containing substantially no extractable rubber from the vulcanized rubber phase (less than 0.5% by weight). The gel content, expressed as% gel, is determined by a procedure consisting of determining the amount of insoluble polymer by soaking the sample for 48 hours in an organic solvent at room temperature, weighing the dry residue and making appropriate corrections based on

- 26 knowledge of plastic. Thus, the adjusted initial and final weights are obtained by subtracting the weights of the soluble components from the initial weight - meaning soluble components other than the rubber to be vulcanized, such as extender oils, plasticizers and mass components that are soluble in organic solvents and also any rubber component, if present, from a DVA not intended to be vulcanized. Any insoluble pigments, fillers, etc. are subtracted from both initial and final weight.

To utilize the crosslinking density as a measure of the vulcanization state that characterizes the improved thermoplastic elastomeric masses, the compositions are vulcanized to the extent that the same rubber is vulcanized both in a statically vulcanized under pressure molding composition with such amounts of the same surfactant vulcanization and in the composition; under such time and temperature conditions to give an effective crosslinking density of greater than about 3 x 10 ^-5 moles per milliliter of rubber and more preferably greater than about 5 x 10 -5 s or even more preferably 1 x 10 ^-4 moles per milliliter of rubber. The mixture is then dynamically vulcanized under similar conditions with the same amount of vulcanizing agent based on the rubber content of the mixture as required for the rubber itself. Thus, the determined crosslinking density can be considered to measure the amount of vulcanization that provides improved thermoplastics. However, the fact that the amount of vulcanizing agent is related to the rubber content of the mixture and is the amount that gives the rubber itself the previously mentioned crosslinking density should not be assumed that the vulcanizing agent does not react with the resin or that there is no reaction between the resin and the rubber.

Sukem. Very significant reactions may occur, but to a limited extent. However, the assumption that the crosslinking density determined as described provides a useful approximation of the crosslinking density of thermoplastic elastomeric materials is consistent with the thermoplastic properties and that a large proportion of the resin can be removed from the mass by solvent extraction at high temperature using a solvent. suitable for the resin used.

The crosslinking density of the rubber is determined by equilibrium swelling in the solvent using the Flory-Rehner equation as shown in J. Rubber Chem. and Tech. 30, p. 929. Suitable Huggins solubility parameters for the rubber-solvent pairs used in the calculation were obtained from a review by Sheehan and Bisia, J. Rubber Chem. and

Tech. 39, 149. If the gel content extracted from the vulcanized rubber is low, it is necessary to use a Bueche correction in which the term v is multiplied by the gel portion (X gel / 100). The crosslinking density is the half effective density of the chain network in the determined in the absence of resin. Thus, the crosslinking density of the vulcanized compositions will be understood herein as referring to the value determined for the same rubber as in the composition described herein. However, with more suitable plastics, both of the aforementioned types of measurement of the vulcanization state, namely the determination of the crosslinking density and the% extractable rubber, are encountered.

A suitable plastic according to the invention comprises nylon as a thermoplastic technical resin and a bulk copolymer of isobutylene and para-methylstyrene.

Examples

The following examples are given to illustrate the invention. All proportions and percentages herein are by weight unless specifically stated otherwise.

Example 1

The plastics prepared according to the invention and the comparative plastics as described in Tables I to V were mixed in a three-pound mixer in a 10-15 minute cycle. The materials were dynamically vulcanized during such a cycle by extending the mixing for about 5 minutes after adding the curing agent and draining or removing at an elevated temperature of about 375-450 ° F (about 190-232 ° C).

Elastomer (s), polyamide resin (nylon), stabilizer, mineral filler and processing aids were incorporated and mixed at high speed until liquefaction. The temperature was brought to about 30 ° F above the melting point of the polyamide resin and then oil was added portionwise. Then vulcanizing agents were added and common current and rotational shocks were observed, stirring was continued for 5 minutes to terminate the vulcanization and distribution of the vulcanized elastomer. The rotor speed was suitably adjusted to maintain the desired temperature range for this batch. Then all the remaining oil was added and the mass was discharged from the mixer.

Table II shows a comparison between DVA nylon resins prepared using ethylene propylene elastomer, maleic anhydride, grafted ethylene propylene elastomer and bulk copolymers of isobutylene and para-methylstyrene, herein designated Copolymer T. DVA prepared using Copolymer T, i.e., mass C, which was mass prepared according to the present invention had higher Vicat softening temperatures and higher compression resistance at higher temperatures. Table IV shows the properties of other nylon and DVA compositions. All materials have high Vicat softening temperatures.

Table V shows dynamically vulcanized masses prepared using higher melting point nylon resins. The bromobutyl elastomer DVA was used as a control. The DVA containing the bulk copolymers of the present invention, i.e. Copolymer T or Copolymer Y, had increased tensile strength, higher ductility, higher Vicat softening temperatures, and improved compression properties at elevated temperatures. They were also much more gummy and cracked than the control samples and did not create voids that cause the surface to whiten when stretched.

Table III shows the characteristics of the cross-linked IB-PMS copolymers, i.e., the cross-linked copolymers of isobutylene and para-methyl styrene.

Example 2

Table II shows a comparative mass and a DVA mass according to the present invention, comprising Copolymer Z, prepared using styrene and acrylonitrile as the matrix resin in DVA. The compositions were prepared in a similar manner to that described in Example 1. Copolymer Z containing DVA showed improved tensile strength, elongation, tear strength, and Vicat softening temperature compared to the corresponding control bromobutyl DVA (mass K).

The compositions of the present invention and the comparative compositions as described in Tables VIII to XII were mixed in a 0.8 inch Welding Engineers twin screw extruder and a fiber counter equipped with a fiber mold at the extruder outlet. The extruded fibers were then cooled in a water bath before being treated with a pelletizer into pellets of approximately 1/8 times 1/8-times. All technical resins were dried under the drying conditions recommended by the methods of the invention. All pelletized masses were dried at 150 ° F under vacuum for at least 4 hours to remove surface moisture before the mass was formed into various test samples on a 15 ton Boy injection molding machine. In the vulcanized blend trials, an unvulcanized blend was first prepared and only after drying to remove surface moisture, the blend of unvulcanized beads and additives was reextruded using a Welding Engineers extruder to prepare finished pellets.

Example 3

Table VIII lists vulcanized and unvulcanized mixtures of Copolymer A with a polyetheramide block copolymer (Pebax 5533 SA). Both materials give extremely soft and tough materials, as shown by their low flexural modulus and considerable elongation capabilities. Vulcanized versions showed an improvement over the unvulcanized material in the Izod Notch Tensile Test.

Example 4

Table IX lists 50/50 mixtures of Copolymer A with copolyetherster copolymer (Riteflex 555 HS), both unvulcanized and vulcanized. The physical properties of both materials were substantially the same except that a decrease in flexural modulus was observed with the vulcanized composition.

Example 5

Table X shows a comparison of vulcanized and unvulcanized mixtures of 70/30 polybutylene terephthalate with copolymer A. Improvements in elongation and stiffness were observed in the vulcanized composition, although both compositions had excellent notch toughness at low temperature.

Example 6

Table XI lists the melt of two technical resins with bulk copolymers of isobutylene and para-methyl styrene. The two selected technical resins were polybutylene terephthalate and copolyetherester copolymer using copolymer A as a mixing agent. The vulcanized version was a softer and firmer mass compared to the unvulcanized mass, as shown by a decrease in flexural modulus and improved elongation properties.

Example 7

Table XII lists the three compositions containing polyamide 6 and Copolymer B at 20, 30 and 40 percent respectively. All three mixtures exhibited excellent mechanical properties.

In these examples, the masses C, D, E, E, Η, I, J, L, Μ, N, O, P, Q, R, S, T, U, V and W are the masses prepared in accordance with the present invention. Abbreviations and / or trademarks used to measure properties are listed in Table XIV.

Table I

Plastic A_B_C

Ethylenpropylene elastomer - VISTALON 3708 39.3 - - Ethylenpropylene elastomer - VISTALON 3708 - 0,2% painted - 39.3 - Copolymer T - - 39.3 Rilsan BMNO 17.3 17.3 17.3 Sunpar 150 Oil 29.0 29.0 29.0 Nucap 190 Clay 10.0 10.0 10.0 Titanox 2071 1.0 1.0 1.0 Sunolite 127 Wax 1.4 1.4 Stearic acid (polymer) 0.4 0.4 0.5 Irganox 1010 - 0 0.2 Irganox 1076 0.3 0.3 - Ultranox 626 - - 0.2 Chimassorb 944 - - 0.2 TLnuvin 770 - - 0.2 SP 1056 Resin 0.5 0.5 Protox 166, zinc oxide 0.8 0.8 1.0 Stearic acid (with vulcanization) - - 0.2 Zinc diethyldithiocarbamate - - 0.5 Zinc stearate zace) - - 0.5

AND

Table II

Plastic A_B_C

Workability

Stripes on a rubber mill Spiral flow test Yes Yes Yes - cm at 800 psi Physical properties, injection molded 11 12 10 Hardness, strut A, instantaneous 65 65 58 Tensile strength, dogs 620 620 420 Extension, X 90 60 84 Direction at break,% 9 3 3 Perforated cube B, lb / inch 130 120 62 Insert B pressed 22 hours, @ 70C,% 74 71 37 22 hrs., @ 100C, X 92 92 40 22 hrs., @ 150C, X - 49 Vicat softening temperature, C (200 g weight) 80 80 176 Description soft, rubbery, 1 amber, stripes

on a rubber mill

Table III

Plastic_p E

Copolymer T 39.30 37.30 35.37 Rilsan BMNO 19.30 21.40 22.37 Sunpar 150 Oil 32.0 27.46 28.71 Sunpar 2280 Oil - - 5.00 Nucap 190 Clay 5.00 9.50 4.50 Titanox 2071 1.00 1.00 0.90 Irganox 1010 0.20 0.20 0.18 Ultranox 626 0.20 0.20 0.18 Chimassorb 944 0.20 0.20 0.18 Tinuvin 770 0.20 0.20 0.18 Stearic acid (polymer) 0.50 0.48 0.45 Protox 166, zinc oxide 1.00 0.95 0.90 Zinc diethyldithiocarbamate 0.50 0.48 0.45 Stearic acid (vulcanized) 0.20 0.20 0.18 Zinc stearate zace) 0.50 0.48 0.45

Table IV

Plastic D E F Workability Stripes on a rubber mill Yes Yes Yes Spiral flow test - cm at 800 psi 12 6 9 Physical properties, molded spray Hardness - strut A, 5 sec. 65 62 70 Tensile strength, dogs 535 626 773 Extension, X 84 58 97 Perforated cube B, lh / inch 70 - Perforated cube C, lb / inch 130 108 Inserted compression 22 hrs., @ 70C, X 42 66 65 22 hrs., $ 100C, X 39 - 22 hrs., @ 150C, X 56 Vicat softening temperature, C 174 181 180

(200 g weight)

Description soft, rubbery, brittle, stripes on rubber mill

Table V

Plastic G H AND J Bromobutyl 2244 45 - - - Copolymer T - 45 - 45 Copolymer Y - - 45 - Capron 8209F 30 30 30 30 Sunpar 150 Oil 15 Dec 15 Dec 15 Dec - Paraplex G 52 < ¹ > - .15 Omyacarb UFT - 7 7 7 Maglite D 0.5 - - - Irganox 1010 0.2 0.2 0.2 0.2 Chimassorb 944 0.2 0.2 0.2 0.2 Tinuvin 770 0.2 0.2 0.2 0.2 Vulcanizing agents Protox 169 zinc oxide 5.0 1.1 1.1 1.1 Stearic acid 0.5 0.2 0.2 0.2 ZDEDC 1 0.6 0.6 0.6 End of vulcanization Zinc stearate - 0.5 0.5 0.5 Surface whitish --- rubbery, brittle - —— bars on rubber mill Physical properties Hardness, Strut A (2) 80/77 89/88 88/88 93/91 Hardness, Strut D (2) 13/8 25/21 21/19 - 100% module, psi - 1389 1223 1300 Tensile strength, dogs 975 1505 1328 1811 Elongation,% 12 122 124 216 Perforated cube C, lb / in 222 236 226 303 Inline stroke, i @ 1001 extension 21 24 29 (1) epoxidized soybean oil (C. P. Halí)

(2) (instant / 5 sec.)

Table V (continued)

Plastic_G_H_I_J

Thermal properties

Embedded Voltage B,%

22 hrs @ 100C 124 62 68 69 22 hrs @ 150C 131 88 79 112 Vicat (220g), C 163 218 217 > 230 (1000 g), C - " 174 Flow Spiral flow, cm 20 May 7 11 neměř

Plastic

Table VI

Exxon Bromobutyl 2244

Copolymer Z

Lustran SAN 31 ·

Sunpar 150 Oil

Omyacarb UFT

Maglite D

Irganox 1010

Chimassorb 944

Tinuvin 770

Vulcanizing agents

Protox 169, zinc oxide

Stearic acid

Zinc diethyldithiocarbamate

End of vulcanization

Zinc stearate

Physical properties

Hardness, Strut A (5 sec)

100¾ module, psi

Tensile strength, dogs

Prolongation, 1

Perforated cube C, ft-lb / in

Thermal properties

Insertion pressed B,% hr @ 150C

Vicat (200g), C

Flow

Spiral flow, cm

0.5

0.2

0.2

0.2

0.5

450

500

106

103

0.2 0.2 0.2 0.2

1.1

0.2

0.6

0.5

881

883

170

130

Table VII

Used bulk isobutylene-para-methylstyrene copolymers % ^<And> Molar. 5 < ^b >

Polymer # Bromine Brominated PMS MW <c Copolymer T 1.75 1.10 1 200 000 Copolymer Y 1,25 θ ^'80 1 200 000 Copolymer Z 1.75 1.10 1 200 000 Copolymer A 1.65 1.0 280 000 Copolymer B 1.0 0.6 450 000

Notes (a) Total bromine in polymer determined by x-ray fluorescence (b) Molar. % of accumulated para-methylstyrene (PMS) units determined by nuclear magnetic resonance (NMR) (c) Viscosity average mol.wt. determined by dilute solution (DSV) of diisobutylene at 68F.

Table VIII

Plastic M

Pebax 5533 SA 50

Copolymer A 50

Irganox B-215 0.2

0.2

Vulcanizing agents

Zinc oxide (Protox 169) Zinc diethylditbiocarbamate Stearic acid

Physical properties

0.35 0.35 0.6

Fracture pull, dogs 1500

Elongation at break 450

Bending modulus < ¹ >, kpsi 7.1

Notched Izod - 1 / 4--, ft-lb / in

-30 ° C

- 40 ° C 0.3

1200

440

4.1 (1) The measured flexural modulus for 100% Pebax 5533 SA is 29 kps

- 41 Table IX

Plastic_Q P

Riteflex 555 HS Irganox B-215 Copolymer A

Vulcanizing agents

Zinc oxide (Protox 169)

Zinc diethyldithiocarbamate Stearic acid

Physical properties

Pull at break, dogs

Fracture elongation,%

Flexural modulus, kpsi ⁽¹ >

Notched Izod-1 / 4. · -, ft-lb / in

23 ° C - 30 ° C

50 50 50 50 0.2 0.2

0.35 - 0.35 - 0.6

1000 1020 460 380 5.9 4.2 2.8 3.2 1.6 1.1

(1) The measured flexural modulus for 100¾ Riteflex 555 HS is 25 kpsi; the notched Izod at room temperature (23 ° C) is 7.0 ft-lb / in.

Table X

Plastic_Q_R

Celanex 2002

Copolymer A

Irganox B-215

Vulcanizing agents

Zinc oxide (Protox 169)

Zinc diethyldithiocarbamate Stearic acid

Physical properties < ¹ >

Pull at break, dogs

Fracture elongation,%

Flexural modulus, kpsi

Notched Izod-1 / 4->, ft-1b / in

-30 ° C -40 ° C

70 70 30 30 0.2 0.2

- 0.2 - 0.2 0.4

3600 3000 38 136 161 125 13 9.4 9.5 3.1

(1) The measured properties of 100% Celanex 2002 are: Elongation max. - 150%

Flexural modulus - 370 kpsi

Notched Izod-1/4 ,, at room temperature- 0.9 ft-lb / in.

- 43 Table XI

Plastic_S_T

Celanex 2002 Riteflex 555 HS Irganox B-215 Copolymer A

60 60 20 May 20 May 20 May 20 May 0.2 0

Vulcanizing agents

Zinc oxide (Protox 169) - 0,1 Zinc diethyldithiocarbamate - 0,1 Stearic acid - 0,2

Physical properties < ¹ >

Pull at break, dogs

Fracture elongation,%

Flexural modulus, kpsi

Notched Izod -1 / 4 **, ft-lb / in

3200 3200

110

114 88

30 ° C 6 6 (1) See footnotes to Tables IX and X for an explanation of the physical properties of Celanex 2002 and Riteflex 555 HS.

Table XII

Plastic AT IN W Capron 8209F 80 70 60 Copolymer 20 May 30 40 Irganox B-215 0.1 0.1 0, Physical Properties) ¹ ) Pull at break, dogs 8400 6800 5200 Fracture elongation,% 116 224 134 Flexural modulus, kpsi 268 208 175 Notched Izod-1/4, ft-lb / in <z> 23o c 21 22nd 21 O® C 17 21 21 - 10 «c 3.4 20 May 21 - 20o c 2.6 4.8 17 - 30o c 1.7 2.6 3 - 40 ° C 1.6 1.6 1, (1) Dry as shape properties (2) Measured notched Izod impact force at room i : eploti

(230 c) for 100X Capron 8209F is 1.0 ft-lb / in.

Table XIII Component Description Ethyl Zimate R.T. Vanderbilt zinc diethyldithiocarbamate (ZDEDC) Maglite D C. P. Halí Co. magnesium oxide Vistalon 3708 Exxon Chemical Co. ethylene propylene diene terpoler, Mooney viscosity according to ASTM D1646, ML 1 + 4 at 125 ° C = 54+ - 5 Sunpar 150 Oil R. E. Carroll paraffin oil, ASTM D2226 type 104B Sunpar 2280 Oi2 R. E. Carroll paraffin oil, ASTM D 2226 Type 104B Sunolite 127 Wax Witco Chemical mixture of petroleum waxes Irganox 1010 Ciba Geigy tetrakis (methylene-3,5-di- tert-butyl-4-hydroxyhydro- Cinnamate) methane Irganox 1075 Ciba Geigy thiodiethylene bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamate Irganox B-215 Ciba Geigy 33/67 Irganox 1010 a Irgafosu 168 Irgafos 168 Ciba Geigy tris (2,4-di-tert-butylphenyl) phosphite Ultranox 626 Borg-Warner bis with (2,4-di-t-butylphenyl) pentaerythritol diphosphite Chimassorb 944 Ciba Geigy N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexanediamine polymer with 2,4,6-trimethyl-1,2-pentanamine inuvinvin 770 Ciba Geigy bis-2,2,7,6-tetramethyl-4-piperidyl sebacate SP 1056 Resin Schenectady Chemical bromomethylated alkylphenol formaldehyde resin Protox 166 New Jersey Zinc Co. zinc oxide Protox 169 New Jersey Zinc Co. zinc oxide

Table XIII (cont.) Component Description Titanox 2071 DuPont Titanium dioxide Lustran SAM Monsanto Co. styrene acrylonitrile resin Omyacarb UFT Omya calcium carbonate, surface- tower covered ‘ Capron 8209F Allied Signal Polyamide 6 Rilsan BMNO Atochem lne. Polyamide 11 Pebax 5533 SA Atochem lne. Polyetheramide block copolymer Riteflex 555 HS Hoechst-Celanese copolyetherester copolymer Celanex 2002 Hoechst-Celanese polybutylene terephthalate

Table XIV

Test Test met Strut A, hardness, 5 sec ASTM D2240 Tensile strength, dogs ASTM D412 Fracture direction, X ASTM D412 Perforated cube, lb / inch ASTM D624 Perforated cube, lb / inch ASTM D624 Inline compression, method B ASTM D395 Vicat softening temperature, ⁰ ° C ASTM D1525 Spiral flux cm @ -1 at 800 psi see note. Bending module, dogs ASTM D790 Notched Izod character ASTM D256 Ft-lb / inch Tensile strength < ² >, psi ASTM D638 Elongation < ² >, X ASTM D638

(1) The spiral flow method is performed by injecting a test mass at an injection temperature of 220 ° C and a pressure of 800 psi into a spiral form comprising a semicircular cross-sectional path of 0.3 cm radius and measuring the length of the pathway filled with mass.

Claims (28)

CLAIMS 1. Thermoplastic plastic comprising a polymer blend of thermoplastic technical resin and a halogen-containing copolymer of isomonoylpholine C 1 to C 7 and para-alkylstyrene. matter team 2. Thermoplastic synthetic characterized by vulcanized mass. Thermoplastic according to claim 1, characterized in that the plastic is an intangible material according to claim 1, characterized in that the vulcanized claim is a technical plastic. 1, characterized in that the plastic is a vulcanized material. 4. Thermoplastic plastic 3, characterized in that the plastic is a dynamically vulcanized material. 5. Thermoplastic plastic according to 1, characterized in that the resin is present in an amount ranging from about 10 to 98 weight percent, and the elastomeric halo-containing copolymer is present in an amount ranging from about 2 to 90 weight percent, based on the polymer blend. 6. The thermoplastic polymer composition of claim 1, wherein the technical resin is present in an amount ranging from about 20 to 95 weight percent and the elastomeric halogen-containing copolymer is present in an amount ranging from about 5 to 80 weight percent, based on polymer blend. Thermoplastic plastic according to claim 7 1, The 49 halogen-containing copolymer is present in the plastic in the form of particles dispersed in the technical resin. 8. Thermoplastic artificial The composition of claim 3, wherein the elastomeric halogen-containing copolymer is at least partially vulcanized. Thermoplastic plastic according to claim 9 3, characterized in that the elastomeric halogen-containing copolymer is fully vulcanized. Thermoplastic plastic according to claim 10 1, characterized in that the technical resin is selected from the group consisting of polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile butadiene styrene resins, polyphenylene oxide, polyphenylene sulfide, styrenacrylonitrile resins, polystyrene maleate, styrene maliraetes. artificial according to claim that technical Thermoplastic plastic 10, wherein the resin comprises polyamide. 12. Thermoplastic plastic 11, _wherein: is selected from the group consisting of nylon 6, nylon 6,6; nylon 11 and mixtures thereof. Thermoplastic plastic 11. 1, characterized in that the polyamide is according to claim 1, wherein the technical resin is selected from the group consisting of polyetheramide block copolymers, copolyetherester copolymer, polybutylene terephthalate and mixtures thereof. The thermoplastic plastic of claim 1, wherein the elastomeric halogen-containing copolymer comprises from about 0.5 to about 25 weight percent para-alkylstyrene. 15. The thermoplastic plastic of claim 1, wherein the elastomeric halogen-containing copolymer comprises from about zero to about 10 weight percent of said halogen. 16. The thermoplastic plastic of claim 1 wherein the halogen is selected from the group consisting of chlorine, bromine and mixtures thereof. 17. The thermoplastic plastic of claim 1 wherein the halogen consists of bromine and wherein said bromine is chemically bonded to para-alkyl styrene. 18. Thermoplastic artificial 1 á mass according to claim 1, v y indicating s e team that isomonoo1efin Yippee isobutylene and para-alkylstyrene je para- methy1 styrene. 19 Dec Thermoplastic mass according to claim 3, v y indicating s e by that additionally sáhuj e unvulcanised rubber. 20 May Thermoplastic mass according to claim 1, v y marking s e by that additionally sáhuj e folder selected from the group consisting of a filler, rubber compounding additives and mixtures thereof. 21. The thermoplastic plastic of claim 1, further comprising a component selected from the group consisting of rubber process oils, plasticizers, and mixtures thereof. 22. The thermoplastic plastics material of claim 1, wherein the mass has a mowing flexural modulus of movement of from about 100 to about 400,000 kg / cm &^lt; ^{2 &gt}; measured according to ASTMD 790 at 1% stress. 23. A process for preparing a vulcanized thermoplastic composition comprising the steps of: (a) mixing the thermoplastic technical resin, the unvulcanised elastomeric halogen-containing copolymer of isomonoolefin Ca to C7 and para-alkylstyrene and a vulcanizing agent capable of vulcanizing the elastomeric halogen-containing copolymer; sufficient time to form a vulcanized thermoplastic resin. The method of claim 23. characterized in that the vulcanized thermoplastic composition comprises cross-linked discrete particles of an elastomeric halogen-containing copolymer dispersed in a thermoplastic technical resin. 25. The process of claim 23, wherein the vulcanization conditions comprise a temperature ranging from about the melting point of the technical resin to about 300 ³ C. 26. The process of claim 23, wherein the technical resin is selected from the group consisting of polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile butadiene styrene resins, polyphenylene oxide, polyphenylene sulfide, styrenacrylonitrile polymers, styrene polymers, styrene polymers, styrene polymers, styrene polymers, styrene polymers, styrene polymers, styrene polymers. mixtures thereof. 27. The process of claim 26 wherein the technical resin comprises polyamide. The method of claim 27, wherein the polyamide is selected from the group consisting of nylon 6, nylon 6,6; nylon 11 and mixtures thereof. The process of claim 23, wherein the technical resin is selected from the group consisting of a polyether polyamide block copolymer, a copolyether ester copolymer, polybutylene terephthalate, and mixtures thereof. 30. The process of claim 23, wherein the elastomeric halogen-containing copolymer contains from about 0.5 to about 25 weight percent para-alkylstyrene. 31. The process of claim 23 wherein the elastomeric halogen-containing copolymer comprises from about zero to about 10 weight percent halogen. 32. Method according to claim 23, in y of n a č u j I C Í t í m that halogen is selected from groups consisting of chloro- ru, bromine and mixtures thereof. 33. Method according to claim 23, in y of n a č u j I C Í t í m that halogen contains bromine and in whose bromine is chemically bound to para -alkylstyrene. 34. Method according to claim 23, in y of n a č u j I C Í wherein the isomonoolefin is isobutylene and the para-alkylstyrene is para-methylstyrene. 35. The process of claim 23, wherein the thermoplastic plastic comprises from about 10 to about 98 weight percent of the technical resin, and from about 2 to 90 weight percent of the elastomeric copolymer based on the technical resin plus the elastomeric copolymer. 1-halogen-containing copolymer. 36. The process of claim 23 wherein the additional rubber, which is not curable by the curable agent, is added before step (b) or after step (b). 37. The method of claim 23, wherein the additional rubber which is curable by the curable agent is added to the volcanic mass after the curable agent has been fully consumed.