DE2452567A1 - RUBBER VOLCANIZES - Google Patents

Description

The use of epoxy resins to vulcanize liquid polymers containing carboxyl groups, is'; known. This vulcanization can be done by using accelerated by catalysts, e.g. amines. A vulcanizable mixture based on molar Equivalents of carboxyl groups and epoxy is built up, but gives a very weak, rubbery one Vulcanizate. A slight molar excess of the epoxy can be used to achieve stronger vulcanization v / earth. For example, U.S. Patent 3,285,949 shows that a terminal carboxyl group-containing Polybutadiene rubber made using a small molar excess of the epoxy resin is vulcanized, vulcanizates with tensile strengths up to about

ο
35 kg / cm and. Elongations of 500 to 700 % can result. Unfortunately, these properties of the vulcanicates are not sufficient for many applications, e.g. for molded parts and accessories for automobiles. By increasing the molar ratio of epoxy resin to liquid polymer with terminal carboxyl groups, the tensile strength of the VuI-

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kanisats increased »The increase in tensile strength: is, however, at the expense of the elastomeric properties
reached, and the vulcanizate looks more like an art! fabric than a rubber. For example, a mixture that contains 100 parts by weight of a diepoxy resin and
Contains 100 parts by weight of a polymer with terminal carboxyl groups and is vulcanized with an amine catalyst J, a vulcanizate is obtained which has a!

ρ!

Tensile strength up to 141 kg / cm, but also an elongation that rarely exceeds 100% , has a higher hardness and a high Gehmann freezing point.

Simply adding reinforcing fillers to the liquid polymer mixture is not a completely satisfactory solution. The tensile strength can be increased by adding: carbon black (see Liquid Butadiene / Acrylonitrile Polymers With Reactive Terminals by Drake and; McCarthy, Rubber World, October 1968, where tensile strengths of 70 to 105 kg / cm with no significant deterioration
the rubber properties can be achieved).
Unfortunately, a powder mix that has enough carbon black
(or any other filler) has been added
is to improve the tensile strength significantly,
extremely viscous and resembles a thick putty or one
Filler. The polymer mixture is not thin and cannot be poured.

Rubber-like vulcanizates with a tensile strength of! more than 70 kg / cm and an elongation of at least about ^!

140 % and are characterized in that they have two different polymer phases, namely a closed elastomeric phase and a phase consisting of
hard, separate fine particles that form a
r.irchmesser from about 100 Ä to about 5 μ
c-us liquid polymer blends produced at
the application temperatures (room temperature to approx

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10O ⁰ C) 'are pourable. The liquid polymer mixtures contain 100 parts by weight of an epoxy resin with about 1.7 to 2.3 epoxy groups (-C - C-) in the molecule, about 100 to

250 parts by weight of a terminal carboxyl group-containing · liquid polymer containing about 1.6 to 2.4 carboxyl groups (-COOH) in the molecule and a from carbon-carbon- or carbon-oxygen- ' Has existing polymer main chain bonds, about 3 to 36 parts by weight of a divalent compound and

about 2 to 10 parts by weight of an amine which is suitable for a; Cairboxyl-Epoxy-Heaktion is selective. The vulcanizates are prepared by a method in which: there is, by mixing the ingredients of the liquid polymer mixture, the mixture is poured into a mold and heated to about 110 to 18O ⁰ C, until the mixture is vulcanized.

The liquid polymer mixtures contain 100 parts by weight an epoxy resin, about 100 to 250 parts by weight of one liquid polymer with terminal carboxyl groups, about 3 to 36 parts by weight of a divalent (dihydric) Compound and about 2 to 10 parts by weight of an amine which has selectivity for a carboxyl-epoxide reaction. The epoxy resin is preferably used in an amount of 100 parts by weight, the liquid polymer in an amount of about 140 to 225 parts by weight, the divalent (dihydric) compound in an amount of about 15 to 30 parts by weight and the amine is used in an amount of about 4 to 8 parts by weight. The epoxy must average about 1.7

contain up to 2.3 epoxy groups (-C C-) in the molecule.

■ V An epoxy resin with a significantly over or under

The number of epoxy groups in the molecule in this range is responsible for the manufacture of the unusual rubber vulcanizates useless according to the invention. It is believed that epoxy resins are much less

⁷ '"" ~ 6Ο88 "2θ7 ~ Οϊΐϊ

than an average of 1.7 epoxy groups in the molecule hold, no sufficiently strong chain extension and /

oder'Vrosslinking and epoxy resins with significantly more than 2 _% 3 epoxy groups in the molecule experience a crosslinking that is too strong for the new vulcanizates.

The epoxy resins can be solids or liquids, but are preferably liquids having a Mooney bulk viscosity of about 200 to 2,000,000 cPs (measured with a Brookfield LVT viscometer, # 7 spindle, at 0.5 to 100) Rpm and '< 25 ° C). The epoxy resins can have epoxy equivalent weights of about 150 to 6,000. The epoxy equivalent weights are preferably about 160 to 1000. The epoxy equivalent weight is the weight of the epoxy resin which contains 1 g equivalent of epoxy groups. The epoxy equivalent weight can be determined by the pyridium chloride-pyridine method to determine the epoxy content.

Numerous types of epoxy resins can be used. Examples of these types are the diglycidyl ethers of dihydric phenols, the diglycidyl ethers of di- i

valued aliphatic alcohols, the diglycidyl esters j of dicarboxylic acids, the diglycidyl ethers of diamino compounds and the oxidized fatty acids. Examples of each of these types of epoxy resins are in United States patents. Called $ 655,818 and 3,678,131 The epoxy resins can be halogenated.

Preferred epoxy resins diglycidyl ethers of dihydric \ phenols and diglycidyl ethers of di- 'aliphatic alcohols. Examples of suitable diglycidyl ethers of dihydric phenols are the bisphenol A / j epichlorohydrin resin types, for example the resins with the trade name "Epon" (manufacturer Shell Chemical) and "DEB" (manufacturer Dow'Chemical). As examples of the diglycidyl ethers of dialiphatic alcohols are the

1

Ethylene glycol / epichlorohydrin resins that are called . "D.E.E." of the 700 series are on the market (manufacturer Dow Chemical). The properties of these two preferred ones

Types of epoxy resins are described in the company's pamphlet "Dow

Although Epoxy Resins is called "170-1400-5M-267, the epoxy resins

can have an average epoxy content of about 1.7 to 2.3 epoxy groups in the molecule, epoxy resins with an average of about 2 epoxy groups in the molecule are particularly preferred. j

The liquid polymer has a main polymer chain that consists of carbon-carbon or carbon-oxygen bonds. The polymer must contain an average of 1.6 to 2.4 carboxyl groups (COOH) in the molecule. These groups must be at least at the ends of the polymer molecule, but they can also be side-by-side with respect to the main polymer chain. The polymers are called '■ as polymers having terminal carboxyl groups'. They contain about 0.5 "to 10% by weight, preferably about 1 to 6% by weight, of carboxyl groups, based on the weight of the polymer. The carboxyl group content can be determined by titration of a polymer solution up to the transition point of phenolphthalein using alcoholic KOH will be. |

j The liquid polymers have molecular weights of about 600 to 10,000, measured with a Mecrolab vapor pressure osmometer. The polymers are becoming more expedient _; called after their Mooney viscosity (bulk viscosity). They have Mooney viscosities of about 500 to j 2 000 000 cps (measured at 27 ° C with a _Brookfield: viscometer, model LVT, with spindle No. 7 at 0.5; b.is 100 rpm.). Polymers with a Mooney viscosity of about 5,000 to 1,000,000 cPs are preferred. : Polymers with a Mooney viscosity of about 10,000 to 600,000 cPs are particularly advantageous.

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The liquid polymers have polymer main chains that consist of carbon-carbon bonds or carbon-oxygen bonds. In the vulcanized state, the polymers are elastomers. Polymers with carbon-carbon bonds contain -'polymerized e units of one or more of the following vinylidene monomers: a) Monoolefins with 2 to about 14 carbon atoms, for example ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-dodecane; b) dienes with 4 to about 10 carbon atoms, ζ.B ₀ butadiene, isoprene, 2-isopropyl-1,3-butadiene and chloroprene; c) vinyl and allyl esters, for example vinyl acetate, vinyl propionate and allyl acetate; d) vinyl and allyl ethers, for example vinyl methyl ether and allyl methyl ether, and e) acrylates of the formula

H O i 1!

CH ₀ = CCOR "

in the E "is an alkyl radical having 1 to 18 carbon atoms or a Alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical

each with 2 to about 12 carbon atoms «, Alb examples;

such acrylates are to be mentioned: ethyl acrylate, butyl j

acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl- j

acrylate, octadecyl acrylate, methoxyatliyl acrylate, butoxy- '

ethyl acrylate, hexyl methyl acrylate, ß-cyano ethyl acrylate,

and cyanoctyl acrylate. Often there are two or more types _;

this polymerized. monomeric units in the poly; main chain included. {

The above-mentioned vinylidene monomers can be easily in larger amounts with smaller amounts of f) vinyl aromatics, e.g. styrene, oc-methylstyrene and Vinyl toluene, g) vinyl nitriles, e.g., acrylonitrile and methacrylonitrile, h) methacrylates and ethacrylates, e.g. Methyl methacrylate, ethyl methacrylate, octyl methacrylate and ethyl ethacrylate, and i) divinylene and diacrylates, e.g. divinylbenzene, divinyl ether and diethylene glycol

- early f t2 ~ Ö7 0 S ti

diacrylate, polymerize. Liquid polymer mixtures, the liquid carboxyl group-containing polymers containing polymerized units of combinations a larger amount of one or more vinylidene monomers mentioned above under (a) to (e) were, with a smaller amount of one or more of the vinylidene monomers mentioned under (f) to (i) exist also fall within the scope of the invention.

Examples of suitable liquid polymers with terminal carboxyl groups are: polyethylene with terminal carboxyl groups, polyisobutylene with terminal carboxyl groups, polybutadiene with terminal Carboxyl groups, polyisoprene with terminal carboxyl groups, butadiene-acrylonitrile copolymers with terminal carboxyl groups, butadier-styrene copolymers with terminal carboxyl groups, ethyl acrylate polymers with terminal carboxyl groups, Ethyl acrylate-n-butyl acrylate copolymers with terminal Carboxyl groups, n-butyl acrylate-acrylonitrile copolymers with terminal carboxyl groups and butyl acrylate-styrene copolymers with terminal Carboxyl groups. The polymers can be prepared by free-radical polymerization using carboxyl groups containing initiators and / or modifying agents, as in the United States patent 3 285 9 ^ 9 and in German patent specification 1 150 205 and by solution polymerization using lithium metal or organometallic compounds and aftertreatment of the polymers to form carboxyl groups, as in the US patents 3,135,716 and 3,431,235 will. The polymers can also be produced by reacting liquid polymers which do not have any terminal Carboxyl groups, but contain other end groups, with compounds in such a way that

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Carboxyl groups arise, are produced. For example, polymers with terminal groups can be prepared from polymers with terminal hydroxyl groups by reaction with dicarboxyl groups. Polymers with terminal mercaptan, amine or amide groups can be reacted with unsaturated carboxylic acids or their anhydrides to form polymers with terminal carboxyl groups. "Polymers with terminal halogen groups can be reacted with unsaturated anhydrides in the presence of Lewis acids, with carboxyl groups being formed» Es is thus apparent that the method of preparation of the liquid polymer having terminal carboxyl groups is not essential to the invention "the main features of the polymer besteh® ¹ in that it includes at least terminal carboxyl groups and having a polymer main chain composed of carbon-carbon or carbon-Säuerstoff bonds consists.

Be particularly advantageous butadiene-acrylic "nitrile copolymers proved carboxyl-terminated" These polymers contain about 5 to 40 wt .-% acrylonitrile, about 0.5 to 10 percent by "-% of carboxyl groups and about 50 to 95 wt _o -% butadiene based on the weight of the polymer.

Divalent aromatic compounds or bisphenol compounds are used as divalent (dihydric) compounds used". Examples of suitable divalent aromatic compounds are catechin, eesorcinol, Hydroxybenzyl alcohols, bisbenzyl alcohol and dihydroxynaphthalenes to name «, the bisphenols have the formula

in which R is an alkylene radical with 1 to 12 carbon atoms or a

is a divalent radical with 1 to 8 C, 0, S and / or N atoms. Examples of bisphenols are methylene bisphenol, Butylidenebisphenol, octylidenebisphenol, isopropylidenebisphenol, Bisphenol sulfide, bisphenol sulfone, bisphenol ether and bisphenolamine should be mentioned.

The amine used has selectivity for the carboxy1-epoxide reaction. This means that the amine first and foremost the reaction of the epoxy resin with the Caused terminal carboxyl-containing polymer with resulting chain extension and then linked the chains. This function of the amine is necessary for the unique two-phase system of the vulcanizate. The amine must also have good reactivity, i.e. a strong,

cause rapid vulcanization. ■ <

The amines are primary, secondary and tertiary aliphatic and alicyclic amines are used. Herein are saturated heterocyclic amines and the salts and Including adducts of the amines. Aromatic amines, i.e. amines whose nitrogen atom is directly attached to the aromatic Ring bound are not suitable. Amines falling under the above definition are in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967), Chapters 7 and 9, j called. . j

The following types and examples of amines may be mentioned:; Aliphatic diamines of the formula HpN - ^ - CH ^ - ^ NHo, in which η has a value from 1 to about 6, e.g. ethylenediamine, \ butylenediamine and 1-methylbutylenediamine, aliphatic polyamines, e.g. diethylenetriamine, bis (hexamethylene) triamine , Triethylenetetraamine, tetraathylenepentaamine, dimethylaminopropylamine, diethylaminopropylamine and aminoethanolamine, aliphatic amines containing aromatic groups, for example m-xylylenediamine, alicyclic

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Polyamines, Z ₀ B ₀ 1,3-diaminocyclohexane, N-aminoethyl 'piperazine and. Bis (aminoethyl) piperaz.in, alicyclic
secondary amines, for example, N-methylpiperazine, piperidine,; Morpholine and pyrrolidine, aliphatic tertiary amines,
for example tetramethylguanidine, triethylamine, tripropylamine
and diethylethanolamine, alicyclic tertiary amines, i eg Ν, Ν'-dimethylpiperazine and eexamethylftetraamine, j tertiary amines with an unsaturated ring, z <, B. Pyridine and '

Containing aroma> Nazi groups pyrazine, and aliphatic tertiary amines such as benzyldimethylamine and '■ 2,4,6-tris (dimethylaminomethyl) phenol. ι

Also suitable are adducts and salts of these amines, j ζ.B ₀ the adducts of ethylene and propylene oxide such as N- 'Hydroxyäthyldiäthylenetriamine, N- (2-hydroxylpropyl) - j

ethylenediamine, W ₅ N'-bis (hydroxyethyl) triethylenetetra-: amine and N- (hydroxypropyl) -1,2-diaminopropane, and salts [ of amines with acids, Z ₀ B ₀ tert-butylamine / benzoic acid, 'triethylenediamine / Dibenzoic acid, N-methylpiperidine / benzoic acid, 4, ^ -'-dipyridylpropane / dibenzoic acid, piperazine / | Octanoic acid and diethylamine / hydrochloric acid, and the tri-2-ethylhexoate salt of 2,4-, 6-tris (dimethylaminomethyl) phenol.

Preferred amines are the aliphatic polyamines, the alicyclic polyamines, the alicyclic secondary ones Amines and the aliphatic tertiary amines containing aromatic groups and their salts. as Examples of the preferred amines are diethylenetriamine, iDriäthylenetetraamine, N-Aminoäthylpiperazin, F-Methylpiperazin, Piperidine, 2,4,6-tris (dimethylaminomethyl) phenol and to name its ethylhexanoic acid salt.

The epoxy resin, the liquid polymer, the divalent ^(dihydric) compound and the amine are mixed and the mixture is heated for vulcanization to a temperature of about 110 to 180 ⁰ C. It is believed that

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the vulcanization in the range mentioned the formation of the desired particle size range in the two-phase Vulcanizate causes.

The vulcanizate of the liquid polymer is a ^; rubbery solid with a tensile strength above

70 kg / cm and an elongation of at least about 140 %, these properties are achieved without the need for reinforcing fillers such as carbon blacks, silicates, carbonates and the like. The vulcanizates also have low Gehman freezing point values, ie values that are typical of the liquid polymer. Using / rubbery butadiene-acrylonitrile Oopolymerisaten G-ehman-freezing points below -20 ⁰ C and -40 ⁰ C frequently achieved and below are. The Durometer A hardness is between about 50 and 100 or more.

The vulcanizate can be an opaque solid with two phases, a closed rubber phase and a finely divided hard phase. The size of the particles that make up the finely divided phase form, is in the range of about 100 S to 5 1 * diameter. The diameter of the particles can vary according to a normal distribution curve, or the size ranges of the particles can be a bipodal one Follow a distribution curve or a distribution curve with even more peaks. Generally gives a low Particle size a vulcanizate with high modulus and great hardness, while with large particles a vulcanizate with lower modulus and hardness is obtained.

The finely divided phase consists essentially of one a larger amount of an epoxy resin, a smaller amount of a dihydric compound, a small amount of a liquid polymer and a small amount of an amine. The phase is tough and has a high Gehman freezing point value. The closed one

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The phase is a rubber-like solid with a Gehman freezing point value, which is typical for the liquid polymer used Amount of amine ₀ The finely divided phase and the closed phase are chemically bound to one another |

In addition to the four main components, i.e. _o h _o the epoxy resin, the liquid polymer, the dibasic; Compound and the phenol, the liquid polymer mixtures and their vulcanizates wide variety contain compounding ingredients "These components are typical components that are used in the compounding of rubber and / or epoxy resin ₀ These ingredients are used in customary amounts known to those skilled used "the only limitation which the concentrations of the mixing ■ ingredients are used, is that the .flüssige polymer mixture containing these components, · at temperatures of about 20 to 100 ⁰ C flowable, d _o h _o be pourable Must »This will reduce the amount of reinforcing fillers and other ingredients which thicken the liquid mixture to low concentrations; about 20 Ge?, r _o parts, based on the weight of the liquid polymer mixture, limited «,

Examples of possible mixing additives are? Reinforcing fillers, z _o B “Sweet _? Metal-

carbonates and - silicates, glass, asbestos = -and- textile fibers, colorants, Z _{0 0} B metal oxides, and metal sulfides, i mad organic dyes, lubricants and ^{plasticizers;} ^ ₀ Bo oils obtained from crude oil, Biiinusöl, Glycerin, 'Bilieon © ", aromatic and paraffinic oils, and alkyl = phthalate9 - = s @ feacate rad Srimellitate and aromatisehe

Phthalates, sebacates and trimellitates, antioxidants and stabilizers, e.g. phenyl-ß-naphthylamine, 2,6-di-tert-butyl-p-cresol, 2,2'-methylene-bis (4-ethyl-6-tert-butylphen oil) , 2,2'-thiobis- (4-methyl ~ 6-tert-butylphenol), 4,4 ^l -butylidenebis- (6-tert-butyl-m-cresol), tris- (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, hexahydro-1,3,5-tri s-ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyltriazine, tetrakismethylene-3 (3 '>5' - <iitert-butyl-4'-hydroxyphenyl) propionate methane, distearyl thiodipropionate and tri (nonylated phenyl) phophitol.

The liquid polymer, the epoxy resin, the divalent compound and the amine and any additives used are mixed by conventional methods using mixing kettles, Henschel mixers, paint mills, Banbury mixers and the like. 'Heating at temperatures up to about 10O ⁰ C can contribute to achieve dissolution and uniform dispersion of the materials. The mixture, etc. in fixed forms, rotating molds. Poured or injected and heated to about 110 to 180 ⁰ C. The ■ mixtures can be used without further ado for the production of molded parts according to the rotary molding process or centrifugal casting process. The ability of the liquid. Polymer blends that are easy to pour and, after vulcanization, to form rubber-like reinforced VuI canizates, is unusual and unique. Prior to the invention, reinforced liquid polymer blends were not pourable. If they were castable, only soft vulcanizates with low tensile strength or: vulcanizates with high tensile strength and low elongation could be obtained.

The new liquid polymer mixtures according to the invention are suitable for. the production of castable sealing collars and washers, castable closure

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pieces and sealing rings, molded parts for automobiles and
Hoses, flowable coatings for drive belts and
Metals, flowable adhesives, investment and casting compounds for electrical parts, cast gears and
Machine parts and general moldings for the
Use in technology and household.

The invention is further illustrated by the following examples
explains «The quantities given are as parts by weight
understand, unless otherwise stated »

Examples General mixing process

The new vulcanizates are produced according to a general 'mixing process' * The constituents, with the exception of the amine, are placed in a mixing vessel. j If apart from the epoxy resin, the divalent hydroxy. Compound and the liquid polymer with terminal carboxyl groups still used other constituents; these will normally be with the others! Components mixed as a batch. To remove
trapped air, a vacuum mixer is used. ■ This greatly reduces the formation of bubbles and; an improved, bubble-free product (test specimen in plate form for the tensile test) was formed. The mixing \ temperature is ° C about 60 to 95 wt. The materials ^; are mixed until the mixture is uniform. This takes about 20 to 30 minutes, 'The amine will then! added to the uniform mixture at the mixing temperature or below (usually about 60 ° C) another suitable shape).
The vulcanizable mixture has at this point
a viscosity of less than 10,000 cPs and can.

- j

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easily pour into molds. The filled shape will then
during the allotted time at a set
Temperature placed in an oven with air circulation.
The mold is taken out of the oven and cooled and that
Vulcanized material taken for use or for testing purposes. ■ ^:

Materials j

The epoxy resins, divalent compounds, and amines described herein are all known materials. ; Most are cheap and readily available. All '< epoxy resins, divalent compounds and amines that are used in
used in the experiments described in the examples
are commercially available products. i

The liquid polymers described here with terminal carboxyl groups are known. They are either commercially available or can be easily traced according to the
in U.S. Patents 3,285 94-9, 3,135,716 and
3 431 235 described method. The at
these experiments are liquid polymers used
commercially available products or processes were made by the \, the j in the United States Patent

3 285 9 ^ -9 is described. j

i ι All other materials described here

and in the experiments described in the examples> are commercially available products. ;

Example 1 j

A liquid polymer with terminal carboxyl groups was treated with an epoxy resin and a divalent one . Compound in various weight ratios of ^; Polymer mixed with epoxy resin. The mixture was

vulcanized using an amine. The following j

i materials were used: a rubbery one

Butadiene-acrylonitrile copolymer with terminal $ 09820/0911

245256?

Carboxyl groups, hereinafter referred to as CTBN, 17} 1% by weight of acrylonitrile (measured by the Kjehldahl method for determining nitrogen) and 2.44% by weight of carboxyl groups, based in each case on the total weight of the polymer, and a Mooney Had a viscosity of 106,000 cPs at 27 ° C and a molecular weight of about 3400 (measured with a Mechrolab vapor pressure osmometer), an epoxy resin, which is hereinafter referred to as "Epon 828" and a bisphenol A / epichlorohydrin resin with two terminal epoxy groups, an epoxy equivalent weight of about 185 and a Mooney viscosity of 12,000 cPs at 25 ° C, ρ, ρ'- _: Isopropylidenebisphenol as a divalent compound, hereinafter referred to as BPA, and as an amine the tris (hexanoic acid salt) of tri ( dimethylaminomethyl) phenol, hereinafter referred to as Vulcanizing Agent D (Cure Agent D) or CA.D. designated. ;

The materials were mixed according to the general mixing procedure. The composition of the approaches and the Properties of the vulcanizates are given in the table below. !

CTBN
Epon 828
BPA
CAD

Vulcanization time, hours

Temperature, C

Tensile strength, kg / cm

psi

Elongation, ¹ %
Hardness, durometer A

107 124 143 165 100 100 100 100 24 24 24 24 7.5 I ^ I ^ 7.5 16 16 16 16 120 120 120 120 161 110 150 133 2290 1560 2130 1890 150 270 220 240 86 79 75 69

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Compression set, % Gehman freezing point, 0 swell in No. 3 oil.

55 62 44 43 -45 -45 -46 -42 58 41 44 46

These values show that the vulcanizates have good tensile strength and elongation. The properties are comparable to those of a solid, high molecular weight butadiene-acrylonitrile copolymer is at. For example, 100 parts of an NBR rubber with a Mooney viscosity (ML-4 at 100 ^° C.) of 50 and an acrylonitrile content of about 20% by weight, 40 parts of carbon black N-550, 5 parts of zinc oxide, 1.0 part Stearic acid and 3> 5 parts tetramethylthiuram disulfide mixed. The mixture was vulcanized for 30 minutes at 154 ^° C. and then tested. The vulcanizate had the following properties: Tensile strength 166 kg / cm ² (2500 psi), elongation 410%, durometer A hardness of 63, Gehman freezing point -41 ⁰ C. Dieces example shows that the properties of the produced polymer from the liquid Vulcanizates according to the invention are comparable to those of vulcanizates produced from solid polymers. In contrast to the solid polymer mixtures, however, the liquid polymer mixtures are pourable. The above four mixes were easily poured into molds for tensile test specimens. The mixtures had a viscosity of 2,000 cps at about · about 80 ⁰ C. I

Example 2

Liquid polymer mixtures were produced in which the butadiene-acrylonitrile rubber used was terminated with Carboxyl groups had different contents of carboxyl groups and acrylonitrile. The polymers had the following metrics:

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Carboxyl
groups, % Acrylonitrile
salary, % "Bulk" -Viscosi-
ity, cPs at
27 ⁰ C CTBN-1 2.44 17.1 106,000 CTBN-2 2.44 17.4 136,000 CTBN-3 2.61 17.8 1.17.000 CTBN-4 2.61 26.2 544.OOO

The composition of the mixtures and the properties

of the vulcanizates are mentioned below. \

i 1 2 3 4 ^:

CTBN-1 Elongation, % 124 _ 165 165 CTBN-4 Compression set, % - 124 - 100 Epon 828 Gehman freezing point, ⁰ C 100 100 100 24 BPA 24 24 24 7.5 C.Ä..D. 7.5 7.5 vulcanization 1 Time, hours 16 16 1 130 Temperature, ⁰ C 120 120 130 139 Tensile strength, kg / cm 150 139 125 1980 psi 2140 ' 1970 1780 300 200 170 300 95 41 41 101 -23 -48

Swelling in oil Kr. 3,% 4 - 1 18 -

These values show that the tensile strength and elongation of the Vulcanizates by changing the content of carboxyl groups and / or acrylonitrile in the liquid polymer with terminal carboxyl groups are not greatly influenced. Of course, the Gehman freezing point value will be as well as the swelling in oil no. 3, since both change with the content of acrylonitrile. These results agree with the assumed structure of the vulcanizate, i.e. one made of a closed elastomeric polymer

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phase 'and a hard epoxy resin phase dispersed therein existing structure. The example illustrates the ease and advantage of manufacturing of vulcanizates with a given resistance to swelling in oil and flexibility at depths Temperatures without significant loss of tensile strength and elongation.

Example 3 ■

The above example illustrates the relatively small influence that the acrylonitrile content of the liquid butadiene-acrylonitrile copolymer has on the stress-strain properties. The present Example further illustrates the essence of Example 1, namely the influence of the weight ratio of liquid polymer and epoxy resin on the properties. The compositions of the mixtures and the properties are given in the following table.

CTBN-2 $ 84 224 -

CTBU-4 - - 345 224 165

Epon 828 100 100 100 100 100

BPA. 24 24 24 24 24

CA.D. 7.5 7.5 7.5 7.5 7.5

vulcanization

Time, hours 2 2 2 2 2

Temperature, ⁰ C I30 I30 I30 I30 I30

Tensile strength, kg / cm ² 56 110 56 95 136

psi 790 1560 800 1350 1930 elongation, % 640 400 670 420 410

These values show that when using the liquid polymer with terminal carboxyl groups in amounts of more than about 300 parts per 100 parts by weight of epoxy

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Resin the vulcanizates do not have the good strength properties obtained with the liquid polymer loops according to the invention (samples 2, 4 and 5)

Example 4

Liquid polymer blends were made using polymers with terminal carboxyl groups and Epoxy resins produced in various weight ratios and vulcanized with various amines. the The composition of the mixtures and the results obtained are given in the following table «

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CD
CO
CD

CTBN-I
CTBN-2
CTBN-4
Epon 828
BPA
DMP-30 ^a
Piperidine
^b

1 2 3 4th 5 6th 7th 8th 9 10 11 124 143 165 143 165 _- - - - - - 143 165 - - - - - - - 143 165 - - 143 165 100 100 100 100 100 100 ■ 100 100 100 100 100 24 24 ■ 24 24 24 24 24 24 24 24 24 7.5 7.5 7.5 - - - - - - - - - - - 7.5 7.5 7.5 7.5 - - - - - - - - - - - 7.5 7.5 7.5 7.5 16 16 " 16 16 16 16 16 3 3 3 3 120 120 120 120 120 120 120 120 120 120 120

vulcanization
• Duration, hours
Temperature, ⁰ C

Tensile strength, kg / cm ² 294 161 14-9 141 129 119 80 155 153 181 148

psi 276O 229O 2120 2000 ΐ84θ Ι690 1ΐ4θ 2210 2ΐ8θ 2580 2110

Elongation, % 145 170 170 4θΟ 470 330 390 I60 200 200 210

Hardness, durometer A 86 85 80 - - - 95 94 93 94

Compression set,% 50 Gehman freezing point., C -45 swelling in oil No. 3, % 38

60

-45

41

52 90 95 -47 43 47 50

90

19th

82

-54

88
-42

84
-46

ro

^a tri (dimethylaminomethyl) phenol b

Amin ο äthy Ip ip er az in

This example illustrates the suitability of various amines for the production of the new vulcanizates. In each case, the vulcanizates achieved good properties. In general, the higher the weight ratio of polymer to epoxy resin, the lower the tensile strength and the higher the elongation. The same behavior can be found in the experiment described in Example 1, in which the tris (hexanoic acid salt) of tri (dimethylaminomethyl) phenol (CA ₀ D ₀ ) was used as the amine »

Combinations of two or more amines can also be used. For example, CTBN-3 and CTBN-4 were separated in an amount of 165 parts by weight with 100 parts of the bisphenol A / epichlorohydrin resin "Epon 828", 24 parts of BPA and 3.75 parts each CAD and DMP-30 mixed. The product "Agerite D" was added in an amount of 1.0 part. After vulcanization for one hour at 130 ° C., the tensile strength and elongation were 125 kg / cm ² and 190% and 135 kg / cm ² and 220 %, respectively.

Example 5>

Using DMP-30 as the amine catalyst liquid polymer mixtures using polymers containing terminal carboxyl groups different acrylonitrile content. the Composition of the mixtures and the properties of the vulcanizates are listed in the following table.

CTBN-1 - 165 165 224 224 CTBN-2 124 - 100 - 100 CTBN-4 100 - 24 100 24 Epon 828 24 100 7.5 24 7.5 BPA 7.5 24 7.5 DMP-30 7.5

609820/091 1

vulcanization
Time, hours, temperature, ° C

Tensile strength, kg / cm

psi

Elongation, %

Gehman freezing point, ⁰ O swelling in oil # 3,% compression set,%

16 0.5 0.5 2 2

120 140 140 130 130

186 146 170 106 122

2650 2080 2420 I510 1730

140 170 210 25O 300

- '-47 -26

18 -

53 73 75 80 105

As the values show, the acrylonitrile content of the liquid polymer with terminal carboxyl groups changes the tensile strength, elongation and compression set of the vulcanizate are not significant. A tendency to higher tensile strengths can be determined when a polymer with a higher acrylonitrile content is used. Of course, when using polymers Vulcanizates with a higher acrylonitrile content with lower swelling in oil no. 3 and higher Gehman freezing points obtain. Here, too, the results show that higher tensile strengths and lower elongations and compression set at lower weight ratios of

Polymer to epoxy resin can be obtained. ι

For comparison, 100 parts by weight of the liquid polymer CTBN-1 were mixed with 30 parts by weight of carbon black N-550, 10 parts by weight of epoxy resin "Epoh 828" and 0.6 parts by weight of DMP-30 mix equal ^{einer.Zusammen-:} settlement, which is described in a paper by Drake and colleagues in "Rubber World", October 1968. The system was not flowable and was similar in consistency to a putty. It could not be poured.-The mixture was poured into a mold for a test specimen for the tensile test and was held for 16 hours

609820/0911

2 8 Γ "^ Γ * Ο ^ 7
4525ο /

C vulcanized =, the vulcanizate had a tensile

O
strength of 109 kg / cm and an elongation of 400% "

Sample 4, in which the weight ratio of poly »
merisat to iSpoxy resin was lower, produced comparable results, but could be poured easily "

Example 6 ,

A repetition of that described in Example 5;

Try using piperidine and AEP as a
Amines produced similar results “When used
of piperidine the tensile strength was one of ^j

124: 100 to 165: 100 increasing weight ratio of
Polymer to epoxy resin when using the polymer

GTBN-1 between 152 and 129 kg / cm and when in use

ρ
of the polymer CTBN-4 between 133 and 80 kg / cm. at

Using AEP, the tensile strength was one of
124: 100 to 224: 100 increasing weight ratio of ^: polymer to epoxy resin when using the polymer CTBN-2 between 174 and 114 kg / cm '"and when using
of the polymer CTBN-4 between 172 and 108 kg / cm ^. _: '

Example 7 !

The duration and temperature of the vulcanization play a role in the development of optimal properties of the
Vulcanizates. Generally high temperatures
(above 18.0 ⁰ C) unfavorable for achieving optimal tensile strengths and ■ elongations. The series of vulcanizations compiled in the following table shows the influences of vulcanization time and:

-temperature. , j

609820/0911

CO OO Ν> O

Cl ¹ BN-5 ^a CTBN-I CTBN-3

Epon BPA C.A.D.

DMP-30

Vulcanization .time, hours_ Temp.,

⁰ C

l43 143 143 1 _ - - - - 150 143 143 143 143 143 100 100 100 100 100 100 100 100 24 24 24 24 24 24 24 24 7.5 7.5 7.5 - - - 7.5 7.5 - 7.5 7.5 7.5 « 1 1 1 2 4th 0.5 1.0 130 l40 130 130 130 i4o i4o

Tensile strength ^ kg / cm ^ psi 1720

Elongation, %

Compression set,%

118 105 157

l68O 14902230 2030

270 320 150

99 98 70

124 94

1770 134ο ιβ70

Ι4θ 280

66 106

9 10 11 12 13

143 143

143 143 143 ^{left +} 3

100 100 100 100

24 24 24 24

7.5 7.5 7.5 7.5

100 24

7.5

100 24

7.5

1.5 0.5 ΐ ο 1.5 1.0 1.0 l4o 150 150 150 ι8θ 18ο

134 89 88 72 75 191012601250 1020 1ObO 270 320 290 230 310

88 103 104 97 -

1340 ΐ6θ

76

^a The polymer contains 17 »9% acrylonitrile and 2.29% carboxyl groups
and has a viscosity of about 11C,000 cPs at 27 ° C.

cn ro cn

Example 8

Numerous additives for rubber mixtures can be added to the liquid polymer mixtures »This example illustrates the use of fillers, plasticizers and antioxidants «

609820/0911

CO

O (O

CTBN-I Elongation, % 143 _ 1 _ _ _ - CTBH-4 Compression set, % '165 130 165 I65 165 165 Ροη 828 Gehman freezing point, ⁰ C 100 100 159 100 100 100 100 BPA 24 24 1980 24 24 24 24 DMP-30 7.5 - 300 - _ - - C.A..D. 7.5 95 7.5 7.5 7.5 7.5 Carbon black ΙΓ-907 - - -23 - 10 10 10 TiO ₂
Agerite D ^a - : 10
I.O6 1.0 1.0 1.0 Dioctyl phthalate 10 - vulcanization Duration, hours 16 1 1 1 1.5 Temp., ⁰ C 120 130 130 150 i4o ρ
Tensile strength, kg / cm 162 108 91 89 106 psi 23IO 1540 1300 1260 I5IO i4o 290 280 300 29Ο 62 100 98 90 91 - -24 -27 -25

It polymerizes 1 ^ -dihydro ^^^ - trimethylquinoline

ro -ο

452567

Example 9

Numerous different liquid polymers with terminal Carboxyl groups can be used to produce the new vulcanizates, some of those in experiments The polymers used are listed below,

Polymer Carboxyl
groups
content, weight ₀ % polymer
main chain "BuIk" -
Viscosity,
cPs at
27 ⁰ C CTB-1 2.12 But adi en 33 = 000 CTB-2 1.98 But adi en 38,000 HC-434 2.48 Butadiene - CTBS-1 2.43 90 butadiene /
10 styrene 36o700 CTBS-2 1.99 70 butadiene /
30 styrene PBAN ^a - Butadiene / acrylo-
nitrile / acrylic acid CTBNX 3.20 Acrylonitrile
16 ₅ 6 % 12O ₀ OOO CTBNXX 3.28 Acrylonitrile 17.0 % -

^a Only pendant carboxyl groups, no terminal carboxyl groups.

Using CoAoD ₀ as the amine catalyst, the following liquid polymer blends were prepared and cured for 1.5 hours at 140 ⁰ C "

CTB-2
HC-434 CTBS-1 CTBS-2 Bpon 828

143 165

165

143 165

- - - - 143 165

100 100 100 100 100 100 100

24 24 24 24 24 24 24

7.5 7.5 7.5 7.5 7.5 7.5 7 _S 5

-3 4 -5 6 7

Tensile strenght,

kg / cm ² 140 129 124 143 145 130 113

dto., psi 1990 1830 1770 2030 2060 1850 1610

Elongation, % 170 190 180 180 200 210 210

Hardness,

Durometer A 79 76 74 83 83 -

Compression set, % 67 68 82 73? 1 - 89

This example illustrates the use of a number of carboxyl terminated liquid polymers and various polymer backbones and / or carboxyl groups. These fourth complement the already mentioned values that the suitability of butadiene-acrylonitrile Copor.ymerisaten with different acrylonitrile content. illustrated.

Example 10 :

In the manner described in Example 9, various liquid polymers used to produce mixtures that have been vulcanized. As an amine piperidine was used. The composition of the mixtures and the properties of the vulcanizates are hereinafter referred to as. ;

CTB-I I65 - 1β5 124 124 124 CTBS-I _ 124 - 100 PBAN _ _ 100 24 CTBNX - _{- m} 100 24 7.5 CTBNXX _ 100 24 7.5 Epon 828 100 100 24 7.5 BPA 24 24 7.5 Piperidine 7.5 7.5

609820/0911

1 16 1 16 16 16 130 120 130 120 120 120 131 196 116 21 , 143 127 1870 2790 1650 300 2040 1800 270 190 280 110 190 150 _ - 78 _. _ 76 105 63 103 41 76 78 -75 -68 -53 -40 -35

_1_ 2 _ 3 4-56

Vulcanization time, hours

Temp., ⁰ G

Tensile strength, kg / cm

. psi

Elongation, % hardness, durometer A compression set, % Gehman freezing point, ⁰ G

The values show * that liquid polymers with many different polymer main chains are suitable for the production of the new vulcanizates «It should be noted that that with sample 4 a very weak vulcanizate was obtained. The polymer used for sample 4 does not contain terminal carboxyl groups, i.e. the Carboxyl groups were randomly distributed and pendent to the main polymer chain. For samples 5 and 6 were also used liquid polymers with pendant carboxyl groups * but contained these polymers additional terminal carboxyl groups.

Example 11

The experiment described in Example Io essentially worked repeated with the difference that AEP was used as the AmIn. The composition of the mixtures and the properties of the vulcanizates are given below:

609820/0911

CTB-2 165 192 224

CTBS-I - 22 * -

Epon 828 100 100 100 100

BPA 24 24 24 24

AEP 7.5 7-5 7-5 7-5

Vulcanization, 2 hours, 130 ° C

Tensile strength, kg / cm ² I36 12ο 121 97

p _S i IQiI ₀ 1700 1720 1380

Elongation, % ' Ϊ60 I70 200! TO

Compression set, % 80 87 68 78

Example 12 ;

143 parts by weight of the polymer CTBN-3 were mixed with 100 parts of the epoxy resin "Epon 828" and 24 parts of BPA, and the mixture was vulcanized using 3 × 75 parts of DMP-30. The vulcanizate had a tensile strength of 14 l kg / cm, an elongation of 14 %, a durometer A hardness of 85 and a compression set of

Example I3

Numerous amines are suitable for the production of the new vulcanizates, but the use of different ones leads to Types of the specified amines for vulcanizates with different modules. So the manufacturer can be Choose amine to make high or low modulus vulcanizates. The following blends were made and vulcanized and the vulcanizates tested:

609820/0911

124 124 100 100 24 24

= 32-

CTBN-I

Epon 828

C.A.Do - 7 = 5

Piperidine 7.5

Vulcanization;

Duration. Hrs. 16 l6 Tempο C 12o 12o

Modulus at loo % elongation,

kg / cm 55 57 psig 470 8I0

Tensile strength, _p

kg / cm 152 150 psig 2160 2l4o

Elongation, $ 27o 2oo

These values show that when using .C.A.D. as Amine a vulcanizate with a much higher modulus than when using piperidine is obtained. Using of DMP-30 and AEP as amines become vulcanates with even higher modulus values than when using C.A.D. obtain.

Example 14 1

Vulcanizates were made from known blends. The blends were made in exactly the same way as handled and vulcanized the mixtures according to the invention. DEN 4j58 is an epoxy novolak resin with an epoxy equivalent weight of 176 to 181. It is considered a triepoxy resin. The composition of the mixtures and the properties of the vulcanizates are named below:

609820/0911

1 - - 2 7th - 3 6th 4th Epon 828 91 54 - 100 mm 100 100 THE 438 9 20th - - - - CTBN-I 5 - 4th 100 Io 100 CTBN-5 4th 35 150 - 120 - BPA 150 18th - - Monuron ^a - -, \ 186 - Piperidine 91 - 264o - .- C.A.D. 1500 loo DMP-30 50 6th vulcanization Duration, hours Io Temp. C 12o tensile strenght kg / cm ^ 222 psi 3160 Elongation, % 80

a) Jp-chlorophenyl-ljl-dimethylurea _;

b) stiff, cheese-like material, unsuitable for producing flawless test specimens for the tensile test.

Sample 1 has a composition suggested in U.S. Patent 3,655,818. A good tensile strength is achieved, but the elongation is very low and the vulcanizate is not rubbery. Sample 2, having a composition suggested in U.S. Patent 5,678,130, has an even less rubbery texture. Samples 3 and 4 show that at a weight ratio of 50:50 only low elongations are achieved if no divalent compound is used. '·

609820/0911

Claims (12)

existing group, where R in the formula is an Al-, kylene radical with 1 to 12 carbon atoms or a divalent radical with 1 to 8 carbon, 0, S = and / or N atoms is, C) a small amount of a terminal carboxyl \ groups-containing liquid polymer which: a carbon-carbon bonds or: carbon-oxygen bonds consisting of poly. has mere main chain and, based on the weight of the polymer, contains about 0.5 to 10% carboxyl groups and has a "bulk" viscosity of about 500 to 2,000,000 cPs and D) a small amount of one of the following amines: a) aliphatic diamines of the formula H ₂ N - {- 609820/0 in which η has a value from 1 to about 6, to) aliphatic polyamines, c) aliphatic amines containing aromatic groups, d) al! cyclic polyamines e) alicyclic secondary amines; f) aliphatic tertiary amines g) alicyclic tertiary amines; h) tertiary amines with an unsaturated ring and i) aliphatic tertiary amines, the aromatic! Groups contain, wherein the particles have a diameter of about 100 a to 5 y, and
II. A closed rubber phase containing ^: A) a larger amount of the abovementioned liquid polymer, i B) a smaller amount of the above epoxy resin, C) a small amount of the above-mentioned dihydric compound, and '. D) a small amount of the above-mentioned amine, the vulcanizate being composed of 100 parts by weight of epoxy resin, about 100 to 25o parts by weight of the liquid polymer with terminal carboxyl groups, about J to J> 6 parts by weight of the dihydric compound and about 2 to Io parts by weight of the amine. ; 2. vulcanizates according to claim 1, characterized _marked: characterized in that they contain epoxy resins as diglycidyl ethers of dihydric phenols and / or diglycidyl ether of dialjphatischen alcohols, 'the epoxy resin a "bulk" viscosity of about 2oo to 2 ooo ooo cps and an epoxy - Has an equivalent weight of about 160 to 1,000 and contains an average of about 2 epoxy groups in the molecule. 3 vulcanizates according to claims 1 and 2, characterized in that that the liquid polymer with terminal carboxyl groups on average about 1.6 to 2.4 609820/0911 Contains carboxyl groups in the molecule and has a "bulk" viscosity from about 5,000 to 1,000,000 dPs and has a polymer backbone consisting of C-C bonds derived from polymerize units derived from one or more of the following monomers: a) monoolefins with 2 to about 14 carbon atoms, b) Serves with 4 to about Io C atoms, c) vinyl and allyl esters, d) vinyl and allyl ethers and e) acrylates of the formula H O ι » CH ₀ = CCOR " in which R "is an alkyl radical having 1 to about 18 carbon atoms, an alkoxyalkyl radical, an alkylthioalkyl radical or is a cyanoalkyl radical, each with 2 to about 12 C- i atoms, and optionally from a larger amount of a monomer (a) to (e) with a smaller amount of a monomer from the (f) vinyl aromatic compounds, (g) vinyl nitriles, (h) methacrylates and ethacrylate th and (i) divinylene and diacrylates Group exists. 4. Vulcanizates according to claim 1 to 3 »thereby characterized in that they contain catechin, resorcinol, hydroxybenzyl alcohol, bisbenzyl alcohol, Dihydroxynaphthalene, methylenebisphenol, butylidenebisphenol, Octylidenebisphenol, Isopropylid ^ nbisphenol, Bisphenol sulfide, bisphenol sulfone, bisphenol ether and / or contain bisphenolamine. j 5. Vulcanizates according to claim 1 to 4, characterized characterized in that they are diethylenetriamine, triethylenetetraamine, N-aminoethylpiperazine, N-methyl- 609820/091 1 .37- piperazine, piperidine, 2,4,6-tris (dimethylaminomethyl) phenol and / or the 2-ethylhexanoic acid salt of 2,4,6-tris- (diraethylaminomethyl) phenol contain. 6. Vulcanizates according to claim 1 to 5 *, characterized in that the liquid polymer with terminal carboxyl groups contains an average of about 1.6 to 2.4 carboxyl groups in the molecule, has a "bulk" viscosity of about 10 ooo to 6oo ooo cPs and, in each case based on the total weight of the polymer, about 5 to 4o wt -.% acrylonitrile, from about o, 5 to Io wt -.% of carboxyl groups and about 5o to 95 wt .- contains ^ butadiene and in an amount of about l4o to 225 wt .-parts per loo parts by weight of epoxy resin is present. i 7. Vulcanizates according to claim 6, characterized in that that they are the dihydric compound methylenebisphenol, butylidenebisphenol, octylidenebisphenol, isopropylidenebisphenol, Bisphenol sulfide, bisphenol sulfone, bisphenol ether and / or bisphenolamine and contain the dihydric compound in an amount of about 15 to 5 ° parts by weight is present per loo parts by weight of the epoxy resin. 8. Vulcanizates according to claim 6 and 7> characterized in that it contains the amine in an amount from about 4 to 8 parts by weight per 100 parts by weight of epoxy resin and as dihydroxy Compound isopropylidenebisphenol contain. 9. Vulcanizates according to claim 6 to 8, characterized in that they contain piperidine as the amine. ₅ 10. Vulcanizates according to claim 6 to 8, characterized in that that they contain N-aminoethylpiperazine as the amine. 11. Vulcanizates according to claim 6 to 8, characterized in that they are 2,4,6-tris (dimethylaminomethyl) phenol as the amine contain. 609820/0911 12. Vulcanizates according to claim 6 to 8, characterized characterized in that it is the salt of 2-ethylhexanoic acid as the amine with 2,4,6-tris (dimethylaminomethyl) phenol. 609820/091 t