DE2706693A1 - THERMOPLASTIC MIXTURES - Google Patents

Description

FROM KREISLER SCHONWALD MEYER EISHOLD FUES FROM KREISLER KELLER SELTING

K. PATENT AGENCIES

The B.F. Goodrich Company '

Dr.-Ing. by Kreisler ~ | ~ 1973

5oo South Main Street, Akron, Ohio, USA _Dr , ing. K. Schönwdd, Cologne

Dr.-Ing. Th. Meyer, Cologne Dr.-Ing. K. W. Eishold, Bad Soden Dr. J. F. Fues, Cologne Dipl.-Chem. Alek von Kreisler, Cologne Dipl.-Chem. Carola Keller, Cologne Dipl.-Ing. G. Setting, Cologne

5 COLOGNE! ¹⁶ February 1977

DEICMMANNHAUS AM HAUPTÜAMNHOF

Thermoplastic substance mixtures (additional registration to P 26 26 o98.o)

The main application relates to terminally amine-substituted liquids Polymers containing about 1.7 to 3 amine groups per molecule, which are primary, secondary or a mixture of these amine groups, included and the formula

0 0

H Il

5 Y-C C-Y

where Y is a monovalent radical obtained by removing hydrogen from an amine group of a aliphatic, alicyclic, heterocyclic or aromatic amine containing 2 to 20 carbon atoms and at least contains two amine groups which are primary, secondary or a mixture of such amine groups, and B one Polymer backbone is the C-C bonds and polymerized units at least one at least one terminal group of the formula CHp = C C containing Contains vinylidene monomers selected from the following group:

a) monoolefins with 2 to 14 carbon atoms,

b) Serves with 4 to 10 carbon atoms,

c) Vinyl and allyl esters of carboxylic acids with 2 to

8 carbon atoms, ₇₀₉ 834/0902

270G693

d) vinyl and allyl ethers of alkyl radicals with 1 to 8 carbon atoms and

e) Acrylic acids and acrylates of the formula

R 0

CH ₂ = CCOR ¹

wherein R is hydrogen or an alkyl radical having 1 to 3 carbon atoms and R is hydrogen, an alkyl radical having 1 to 18 carbon atoms or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with 2 to 12 carbon atoms.

The preparation of B-staged adhesives is described, for example, in US Pat. No. 3,340,224. New B-stage adhesives are desirable.

The invention relates to mixtures of substances that lead to a thermoplastic, elastomeric intermediate state are curable and then by heating over a molten State can be converted into a heat-cured, elastomeric, non-tacky final state. The mixtures of substances included according to the invention

A) 1 equivalent weight of at least one cycloaliphatic epoxy resin,

B) about 0.05 to 0.5 equivalent weight of at least one terminal amine-substituted liquid polymer which has a C-C main chain, and

25 C) about 0.4 to 1.5 equivalent weight of at least one anhydride.

70983A / 0902

As component (B) in the substance mixtures according to Terminal amine-substituted liquid polymers suitable for the invention have the formula

O O Y-C-4-B4-C-Y,

wherein Y is a monovalent radical obtained by removing a hydrogen atom from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two amine groups, at least of which two primary and / or secondary, and B is a polymer backbone, the C-C bonds contains. Generally, the C-C bonds make up at least about 90 weight percent, preferably at least about 95% by weight of the total weight of the polymer main chain. The terminally amine-substituted polymers contain on average about 1.7 to 3, preferably about 1.7 to 2.3 primary and / or secondary amine groups in the molecule. You can use Brookfield viscosities from about 500 to 2,500,000 cPs, preferably from about 500 to 500,000 cPs, measured with a Brookfield RVT viscometer at 27 ° C,

20 have.

The terminally amine-substituted liquid polymers can easily be converted into terminal carboxyl or liquid polymers containing ester groups and containing a C-C main chain with at least one aliphatic, alicyclic or heterocyclic amine containing at least two amine groups, at least of which two are primary and / or secondary. Terminal amine-substituted liquid polymers can also by reaction of terminal acid chloride-containing liquid polymers which have a C-C main chain contain, with at least one aliphatic, alicyclic, heterocyclic or aromatic amine, which contains at least two amine groups, of which at least two are primary and / or secondary, easily produced

35 places. 709834/0902

« Yo '

The liquid polymers used with terminal carboxyl groups can have Brookfield viscosities of about 500 to 500,000 cPs, preferably from about 500 to 250,000 cPs, and contain polymer backbones that C-C bonds included. The carboxyl functional groups are at least at the ends of one Polymer molecule, however, one or more additional groups can be pendant to a main polymer chain to be available. The average number of total carboxyl groups is generally about 1.7 to 3, preferably about 1.7 to 2.3 groups per molecule.

Liquid polymer containing terminal carboxyl groups, e- ^! Risate which contain CC main chain bonds, polymerized units contain at least one vinylidene monomer that has at least one terminal group! of the formula CH ₂ = C <and is selected from the following group:

a) Monoolefins with 2 to 14 carbon atoms, preferably with 2 to 8 carbon atoms, e.g. ethylene, propylene, isobutylene,

1-butene, 1-pentene, 1-hexene and 1-dodecene;

b) Dienes with 4 to 10 carbon atoms, preferably with 4 to 8 carbon atoms, e.g. butadiene, isoprene, 2-isopropyl-1,3-butadiene and chloroprene;

25 c) Vinyl and allyl esters of carboxylic acids with 2 to 8

Carbon atoms, e.g., vinyl acetate, vinyl propionate and allyl acetate; ι

d) vinyl and allyl ethers of alkyl radicals with 1 to 8 carbon atoms, e.g. vinyl methyl ether and allyl methyl ether,

30 and

e) Acrylic acids and acrylates of the formula

709834/0902

R O

ι ti -I CH ₂ = CCOR

wherein R is hydrogen or an alkyl radical with 1 to 3 carbon atoms, R ^{1 is} hydrogen or an alkyl radical with 1 to 18 carbon atoms, preferably with 1 to 8 carbon atoms, or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with 2 to 12 carbon atoms Atoms, preferably with 2 'to 8 carbon atoms. Particularly preferred for R is hydrogen or an alkyl radical having 1 to 8 carbon atoms. Examples of suitable acrylates are ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, β-cyanoethyl acrylate, cyanoctyl acrylate, methyl methacrylate, and X.

Often two or more types of these are polymerizing Contain monomer units in the main polymer chain.

Particularly preferred are liquid polymers which contain polymerized units of at least one vinylidene monomer which contains at least one terminal group of the formula CH ₂ = C <and is selected from the following group:

a) monoolefins with 2 to 14 carbon atoms, preferably with 2 to 8 carbon atoms,

b) dienes with 4 to 10 carbon atoms, preferably with 4 to 8 carbon atoms, and

e) Acrylic acids and acrylates of the formula

R 0

I «I A

CH ₂ = CCOR

wherein R is a hydrogen atom or an alkyl radical with 1 up to 3 carbon atoms and R is hydrogen or an alkyl radical with 1 to 18 carbon atoms, preferably with 1 to 8 carbon atoms

70983 W0902

Atoms, or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with 2 to 12 carbon atoms, preferably with 2 to 8 carbon atoms, acrylic acids and

1
Acrylates in which R is hydrogen or an alkyl radical with 1 to 3 carbon atoms are particularly preferred.

Excellent results have been obtained with dienes containing 4 to C atoms, preferably 4 to 8 C atoms, especially with butadiene.

Leave the vinylidene monomers described above with 0 to 50 wt .-%, preferably with 0 to about wt .-% of at least one of the following comonomers polymerize easily:

f) vinyl aromatics of the formula

2
in which R is hydrogen, halogen or an alkyl radical having 1 to 4 carbon atoms, for example styrene, α-methylstyrene, chlorostyrene and vinyltoluene;

g) vinyl nitriles of the formula

R ³ CH ₂ -C CeN

where R is hydrogen or an alkyl radical having 1 to 3 carbon atoms, e.g. acrylonitrile and methacrylonitrile;

h) vinyl halides, e.g., vinyl bromide and vinyl chloride;

1) divinyls and diacrylates such as divinylbenzene, divinyl ether and diethylene glycol diacrylate;

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• / J.

j) amides of α, β-olefinically unsaturated carboxylic acids with 2 to 8 carbon atoms, e.g. acrylamide, and

k) allyl alcohol and the like.

Liquid polymer compositions, the polymerized units of a larger amount of at least one of the under (a) to (e) said vinylidene monomers with a smaller amount of at least one of those mentioned under (f) to (k) Containing comonomers fall within the scope of the invention.

Comonomers from group (f) are particularly preferred, i.e. vinyl aromatics of the formula

CH ²

wherein R is hydrogen, halogen or an alkyl radical with 1 to 4 carbon atoms, and from group (g), i.e. vinyl nitriles of the formula

R ³
15 CH ₂ = CC = N,

wherein R ^{3 is} hydrogen or an alkyl radical having 1 to 3 carbon atoms. Excellent results have been obtained using styrene and acrylonitrile.

As examples of suitable liquid polymer main chains, which contain C-C bonds are: polyethylene, polyisobutylene, polyisoprene, polybutadiene, vinyl methyl ether polymers, Ethyl acrylate polymers and butyl acrylate polymers as well as copolymers of putcdiene and acrylonitrile, butadiene / styrene copolymers, vinyl acetate / isoprene copolymers, Vinyl acetate / chloroprene

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Copolymers, vinyl ethyl ether / diallyl ether copolymers, Vinyl ethyl ether / a-methylstyrene copolymers, Vinyl ethyl ether / vinyl bromide copolymers, methyl acrylate / butadiene copolymers, Methyl acrylate / ethyl acrylate copolymers, Methyl acrylate / butyl acrylate copolymers , Methyl acrylate / 2-ethylhexyl acrylate copolymers, Ethyl acrylate / ethylene copolymers, ethyl acrylate / isobutylene copolymers, Ethyl acrylate / isoprene copolymers, Ethyl acrylate / butadiene copolymers, ethyl acrylate / vinyl acetate copolymers, ethyl acrylate / styrene copolymers, Ethyl acrylate / chlorostyrene copolymers, X thy lacrylate / styrene / butadiene copolymers, Xthyl acrylate / n-butyl acrylate copolymers, Xethyl acrylate / n-butyl acrylate / 2-ethylhexylate copolymers, Ethyl acrylate / vinyl bromide copolymers, ethyl acrylate / acrylic acid copolymers, Ethyl acrylate / aerylamide copolymers, Ethyl acrylate / allyl alcohol copolymers, butyl acrylate / Styrene / isoprene copolymers, butyl acrylate / styrene copolymers, Butyl acrylate / acrylonitrile copolymers and butyl acrylate / vinyl chloride copolymers.

Liquid polymers with terminal carboxyl groups can by free radical polymerization using initiators containing carboxyl groups and / or modifying agents in the manner and by means of US Pat. No. 3,285,949 and German Pat. No. 1,150,205 Solution polymerization using lithium metal or organometallic compounds and post-treatment the polymers to form carboxyl groups in the manner described in U.S. Patents 3,135,716 and 3,431,235 getting produced. The polymers can also be obtained by reacting liquid polymers, their terminal Groups that are not carboxyl groups can be made with compounds that give rise to carboxyl groups. For example can liquid polymers with terminal carboxyl groups from liquid polymers, the terminal Contain hydroxyl groups, by reaction with dicarbon

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acids or their anhydrides. Liquid Polymers that are terminally halogen-substituted can with unsaturated anhydrides in the presence of Lewis acids are reacted, with carboxyl groups being formed. It is clear from this that the procedure not for the production of the liquid polymers with terminal carboxyl groups in the context of the invention is crucially important. The essential characteristics of the polymer are that it is at least terminal Contains carboxyl groups and a polymer main chain made up of C-C bonds.

Examples of preferred liquid polymers with terminal carboxyl groups are terminal carboxyl groups polyethylene containing, terminal carboxylic groups-containing polyisobutylene, terminal carboxyl groups containing polybutadiene, terminal carboxyl group-containing polyisoprene, terminal carboxyl groups ethyl acrylate polymer containing as well as terminal carboxyl group containing copolymers of butadiene with acrylonitrile and of butadiene with styrene. Copolymers containing terminal carboxyl groups of butadiene with acrylonitrile or styrene proved to be particularly advantageous. These polymers about 50 to 99.6% by weight of butadiene, about 0 to 40% by weight of acrylonitrile or styrene and about 0.4 to 10% by weight % By weight of carboxyl groups, based on the total weight of the polymer.

The liquid polymers with terminal carboxyl groups can be mixed with an aliphatic monohydric alcohol be esterified by known processes, liquid polymers having terminal ester groups being obtained will. For example, a polymer with terminal carboxyl groups with an aliphatic monohydric alcohol in a distillation column or under reflux in the presence of a small amount of one Acid catalyst are implemented. As an acid catalyst

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organic acids are suitable, e.g. monoesters and diesters of orthophosphoric acid, alkarylsulfonic acids, e.g. p-toluenesulfonic acid, inorganic acids, e.g. boric acid, phosphoric acid and sulfuric acid, and Lewis acids such as tetraisopropyl titanate. One is enough Amount of acid catalyst from about 0.01 to 5% by weight based on the total weight of the reactants. Suitable aliphatic monohydric alcohols for the esterification reaction contain 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and have boiling points below about 150 ° C, preferably below about 100 ° C. Primary ones are preferred aliphatic monohydric alcohols. Examples of suitable aliphatic monohydric alcohols are alkenols with 1 to 6 carbon atoms, e.g. methanol, ethanol, 1-propanol and 1-butanol to call. Other suitable aliphatic monohydric alcohols are, for example, 2-methoxyethanol and 2-ethoxyethanol. Excellent results can be obtained with ethanol, 1-propanol, or 1-butanol.

The liquid polymers with terminal carboxyl groups can be converted into liquid polymers by known processes with terminal acid chloride groups. For example, a terminal containing carboxyl groups Polymer can be reacted with thionyl chloride to form a polymer with acid chloride end groups. HCl and SO- are mainly developed as gases and can easily be removed from the polymer with acid chloride end groups split off. Any excess thionyl chloride can be removed by vacuum distillation or by washing with a solvent, Easily remove e.g. methanol. Phosphorus tri-chloride and phosphorus pentachloride are also suitable, however, they are less preferred as acylating agents.

Among the amines which are terminated with the above-described polymers with terminal carboxyl groups Ester groups and terminal acid chloride groups react well, include aliphatic amines with 1 to 20 carbon atoms, preferably with 1 to 12 carbon atoms and at least two, pre-

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optionally two primary and / or secondary amine groups. Alicyclic amines with 4 to 20 are also suitable C atoms, preferably with 4 to 12 C atoms and at least two, preferably two primary and / or secondary Amine groups. Heterocyclic amines containing 2 to 20 carbon atoms preferably 2 to 12 carbon atoms and at least two, preferably two, primary and / or secondary amine groups can also be used. Examples of the above-mentioned suitable amines may be named: aliphatic amines, e.g. ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 2-methyl-1,2-propanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine; aliphatic polyamines, e.g. diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine and 3,3'-iminobispropylamine; alicyclic diamines and polyamines such as 1,2-diaminocyclohexane and 1,8-p-menthane diamine, and heterocyclic ones Diamines and polyamines, e.g. 4- (aminomethyl) piperidine, Piperazine, N- (aminoalkyl) piperazines with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms in each alkyl radical, e.g. N- (2-aminoethyl) piperazine, N- (3-aminopropyl) piperazine and N, N · ice (3-aminopropyl) piperazine.

Particularly preferred of the above-mentioned amines are those which have at least two primary and / or contain secondary amine groups with different reactivity. The presence of amine groups with different responsiveness makes the response the addition of terminal amine groups is more likely than the coupling of the liquid polymers, and a smaller excess of amine is required to avoid coupling. Among the most preferred Amines include, for example, some alicyclic amines, e.g. 1,8-p-menthediamine, and some heterocyclic ones Amines, e.g., 4- (aminomethyl) piperidine and N- (aminoalkyl) piperazines with 1 to 12 carbon atoms, preferably with 1 to ο carbon atoms in the alkyl radical, e.g. N- (2-aminoethyl) piperazine

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and N- (3-aminopropyl) piperazine. Excellent results were obtained when using N- (2-aminoethyl) piperazine.

Aromatic diamines and polyamines can be used to manufacture used by terminal amine-substituted polymers will. The high temperature required to react the aromatic amine with polymers with carboxyl end groups If required, it can make you overly strong Breakdown of reactants and products vprnrsarhpn.

10 and is therefore far less preferred. on the other hand

aromatic amines react well with the above-mentioned polymers with acid chloride end groups. Suitable are aromatic amines that have at least two primary or secondary amine groups directly attached to at least are bound to an aromatic ring. Examples of suitable aromatic amines are 4,5-acenaphthenediamine, 3,5-diaminoacridine, 1,4-diaminoanthraquinone, 3,5-diaminobenzoic acid, 2,7-fluorenediamine, 1,5-naphthalenediamine, 1,8-naphthalenediamine, 2,4-toluenediamine, 2,6-toluenediamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.

A solvent is used for the reaction to attachment of amine end groups not required, but can be used will. Mixtures of solvents are also available suitable. Examples of suitable solvents are aliphatic and cycloaliphatic ethers with 3 to 10 carbon atoms, preferably with 3 to 6 carbon atoms, e.g. Tetrahydrofuran and diethyl ether, halogenated aliphatic hydrocarbons with 1 to 10 carbon atoms, preferably with 1 to 6 carbon atoms, e.g. chloroform, carbon tetrachloride, 1,2-dichloroethylene, trichlorethylene and Tetrachlorethylene, and esters with 3 to 10 carbon atoms, preferably with 3 to 6 carbon atoms, e.g. ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate and ethyl propionate. Aromatic compounds of the formula

709834/0902

wherein R is hydrogen, halogen or an alkyl radical with

4 is 1 to 3 carbon atoms and at least two of the radicals R are hydrogen, are also suitable as solvents

4 and are particularly preferred. R preferably represents hydrogen, chlorine or an alkyl radical with 1 to 2

4 carbon atoms, at least three of the radicals R being hydrogen. Examples of suitable aromatic solvents are Benzene, chlorobenzene, toluene, o-, m- and p-xylene, o-, m- and p-diethylbenzene, cumene and mesitylene.

A sufficient amount of at least one of the above described amines can with one of the above-described liquid polymers with carboxyl end groups, Ester end groups or acid chloride end groups are converted to a terminally amine-substituted one to produce liquid polymer that is about 1.7 to Contains 3 primary and / or secondary amine groups in the molecule. In general, the average number is total carboxyl, ester or acid chloride groups in a liquid polymer before the reaction is about 1.7 up to 3 groups per molecule, preferably about 1.7 to 2.3 groups per molecule. In this typical case you can about 1.2 to 6 mole equivalents and more, preferably about 1.2 to 3 mole equivalents of at least one of the above mentioned amines per mole equivalent of the carboxylated, esterified or acylated described above liquid polymer can be used. However, if the carboxylated, esterified or acylated liquid Polymer also significant amounts of acrylic acid, acrylates or the like. contains polymerized, the amount must of the reacted amine are limited so that the terminal amine-substituted liquid polymer is no longer

709834/0902

than contains an average of 1.7 to 3 primary and / or secondary amine groups in the molecule.

A catalyst is not required and numerous Types of mixing devices can be used for Reaction 5 for the addition of terminal amine groups

will. For example, simple mixers including turbine blades as well as propeller mixers can be used. The reaction components can be combined in any order. The reaction mixture can be heated to a temperature of about 00 to 150 ° C. (or, if a solvent is used, heated on the reflux condenser), the duration generally being about 1 to 6 hours. By-products can be removed to the extent that they are formed by evaporation or the like (for example water from the carboxyl-amine reaction, HCl from the acid chloride-amine reaction and alcohol from the ester-amine reaction). The terminally amine-substituted liquid polymer can be purified by vacuum distillation or by washing with a solvent, for example a benzene-methanol mixture, to remove unreacted amine and then dried. The amine content of the terminally amine-substituted liquid polymers can be determined quantitatively by infrared spectroscopy. It can also be determined quantitatively using the method described by Siggia in "Quantitative Organic Analysis via Functional Groups" (Wiley and Sons, Inc., New York 1963, pages 452-456).

Cycloaliphatic liquid polymers with terminal epoxy groups

30 As cycloaliphatic epoxy resins, which are used as component (A)

be used in the substance mixtures according to the invention, For example, liquid polymers of the formula containing terminal cycloaliphatic epoxy groups are suitable

709834/0302

? ^{Η Μ} 9. ρ,

MM MM

Herein L is a monovalent radical obtained by removing a non-cycloaliphatic epoxy group from an epoxy resin, the at least one non-cycloaliphatic epoxy group and at least one cycloaliphatic group, preferably one non-cycloaliphatic epoxy group and one containing cycloaliphatic epoxy group has been obtained. In the above formula, M represents hydrogen or an alkyl radical with 1 to 4 carbon atoms, preferably for hydrogen, while B has the meaning already mentioned. A cycloaliphatic epoxy group is to be understood as meaning an oxirane group which itself is part of a cycloaliphatic group Is a ring structure, e.g. the group

Under a non-cycloaliphatic epoxy group is an oxirane group that is not part of a cycloaliphatic ring structure is, i.e. the group

where M has the meaning given above, to be understood.

The liquid polymers with terminal epoxy groups contain on average about 1.7 to 3, preferably an average of about 1.7 to 2.3 cycloaliphatic epoxy groups in the molecule. You can use Brookfield viscosities (measured with a Brookfield RVT viscometer at 27 ° C) from about 500 to 2,500,000 cPS, preferably from about 500 up to 500,000 cPS.

709834/0902

• Uv-

The liquid polymers with terminal epoxy groups can be prepared by reacting one of the above described liquid polymers with terminal carboxyl groups with an epoxy resin, the at least one non-cycloaliphatic epoxy group and at least one cycloaliphatic epoxy group, preferably containing a non-cycloaliphatic epoxy group and a cycloaliphatic epoxy group are easily produced will. It has been found that the terminal carboxyl groups are preferably non-cycloaliphatic Epoxy groups react, causing a coupling during the formation of a liquid polymer with terminal cycloaliphatic epoxy groups is avoided.

As examples of suitable epoxy resins which contain at least one non-cycloaliphatic epoxy group and at least contain a cycloaliphatic epoxy group, may be mentioned: 1,2-8,9-diepoxy-p-menthane, 1,2-epoxy-6- (2,3-epoxypropoxy) hexahydro-4,7-methanindane, p- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, l- (2,3-epoxypropoxy) phenyl-5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-Epoxy / cyclopentylphenyl-2,3-epoxypropyl ether and 4- (1,2-epoxyethyl) -l, 2-epoxycyclohexane (also known as 4-vinylcyclohexane dioxide). Excellent Results were obtained using 4-vinylcyclohexene dioxide in making a terminal obtained liquid polymer containing cycloaliphatic epoxy groups, referred to as ETBN will and the formula

OH 0 0 OH

, 11 I "I

JH-CH ₂ -OC (B JCO-CH ₂ -CI

wherein B is a polymer backbone containing C-C bonds and is described in detail above became.

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Catalysts are used for the production of the liquid polymers with terminal cycloaliphatic Epoxy groups not required but can be used. Examples of suitable catalysts are Chromium (III) bis-3,5-diisopropyl salicylate, triphenylphosphine and tinil) octoate. A solvent is not required for the reaction but can be used. Suitable are the solvents that above in connection with the preparation of the terminally amine-substituted liquid polymers were called.

Many types of mixers, such as turbine stirrers and propeller mixers, can be used for the reaction will. The reaction components can be combined in any order. The mixture can heated to a temperature of about 80 to 150 ° C, generally for about 1 to 6 hours (or, if a Solvent is used, heated on the reflux condenser) will.

Thermoplastic, thermosetting elastomeric compositions

The thermoplastic compositions according to the invention contain (A) 1 equivalent weight of at least one of cycloaliphatic epoxy resins mentioned below, (B) at least about 0.05 to 0.5 equivalent weight one of the terminally amine-substituted liquid polymers described above and (C) about 0.4 up to 1.5 equivalent weight of at least one of the anhydrides mentioned below. The properties of the Masses can be increased by changing the amounts of the terminally amine-substituted liquid polymer Boundaries are changed. The anhydride serves both as a chain extender and as a crosslinking agent.

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The thermoplastic compositions according to the invention can be subjected to a partial reaction and thereby in a thermoplastic, elastomer intermediate state (B-state) can be converted. It is believed that this is a state of the masses in which the amine-anhydride reaction is essentially complete (mainly chain extension), but the masses are melted or softened by heat, i.e. still thermoplastic Are elastomers. Certain cycloaliphatic epoxides, e.g. 3,4-epoxycyclohexylmethyl- (3,4-epoxy) -cyclohexanecarboxylate, can go into the non-sticky B-stage while those described above liquid polymers with terminal cycloaliphatisehen Epoxy groups can form sticky masses present in the B-state. Those in the B state Masses can be heated, whereby they form a flowable adhesive, which by further heating can be converted into a heat-hardened C-state. Below the C-stage is a non-sticky one To understand the final state in which the crosslinking is essentially completed and the mass is a thermoset Elastomeric (i.e., essentially fused and insoluble but still elastomeric).

The cycloaliphatic compounds suitable as component (A) in the thermoplastic compositions according to the invention Epoxy resins contain at least an average of about 1.7, preferably about 1.7 to 3 epoxy groups in the molecule, with about 1.7 to 2.3 epoxy groups in the molecule being particularly preferred. Under a cycloaliphatic Epoxy resin is to be understood as a resin in which at least one oxirane group is itself part of a cycloaliphatic Is ring structure. The cycloaliphatic epoxy resins can be liquids or low-melting Be solids, but are preferably liquids with a Brookfield bulk viscosity of

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about 100 to 2,000,000 cps (measured using a Brookfield RVT viscometer at 25 ° C). she can have an epoxy equivalent weight (g molecular weight per epoxy group) from about 70 to 6000, preferably from about 70 to 2000. More suitable as examples Cycloaliphatic epoxy resins are: 4- (1,2-epoxyethyl) -l, 2-epoxycyclohexane, 1,2-8,9-diepoxy-p-menthane, 2,2-Bls (3,4-epoxycyclohexyl) propane, 1,2-5,6-diepoxy-4,7-hexahydromethanoindane, 1,2-epoxy

10 6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane,

p- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, 1- (2,3-epoxypropoxy) pheny1-5,6-epoxyhexahydro-4,7-methanoindane, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) -cyclohexanecarboxylate, 3 ^ -Epoxy-e-methylcyclohexylmethyl ^ -epoxy-e-methylcyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) -cyclohexane-mdioxane and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. The liquid polymers described above with terminal cycloaliphatic epoxy groups are

20 also suitable.

Preferably at least two epoxy groups, in particular two epoxy groups themselves, are part of a cycloaliphatic Ring structure. Examples of particularly preferred cycloaliphatic epoxy resins are: 2,2-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl- (3rd ^ -epoxyjcyclohexanecarboxylate, S ^ -epoxy-e-methylcyclohexylmethyl ^ -epoxy-e-methylcyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) -cyclohexane-m-dioxane and bis (3,4-epoxyo-methylcyclohexyl methydadipate. Excellent results have been obtained using 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate and the above-described liquid polymers with terminal cycloaliphatic epoxy groups.

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.26 ·

Non-cycloaliphatic epoxy resins were found to be unsuitable as component (A) for the purposes of the invention because no intermediate state or B-state can be produced when they are used. Non-cycloaliphatic epoxy resins are to be understood as meaning resins in which no oxirane group is part of a cycloaliphatic ring structure. Instead, all of the oxirane groups are separate three-membered rings (CH ₀ -CH). As examples of unsuitable non-

Cycloaliphatic epoxy resins are the diglycidyl ether of bisphenol A (trade name "Epon 828", manufacturer Shell Chemical Company) and the 1,4-butanediol diglycidyl ether of the trade name "Araldite" RD-2 "(manufactured by Ciba-Geigy Chemical Company)

Call 15.

The anhydrides suitable as component (C) in the thermoplastic compositions according to the invention can be 4 to Contains 24 carbon atoms. The anhydrides are preferably liquids or low melting solids. as Examples of suitable anhydrides are: maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dodecenylsuccinic anhydride and bicyclo / 2 ". 2. ^ 7h & pt-S-en-methyl- 2,3-dicarboxylic anhydride. Excellent results were obtained when using hexahydrophthalic anhydride, dodecenyl succinic anhydride and bicyclo / ^. 2. ^ / hept-5-en-methy1-2,3-dicarboxylic anhydride.

The above-described constituents of the thermoplastic compositions can or the like using mixing kettles, Henschel mixers, paint mills, Banbury mixers. be mixed according to standard methods. Heating the mixture to about 150 ° C may help to achieve dissolution and uniform dispersion of the materials, but this has overheat E _r

709834/0902

as a result, the masses harden faster. The reaction mixture is generally prior to curing pourable and can be produced by centrifugal casting, rotary pressing or pouring into fixed trays or molds are processed. The reaction mixture can also be used for liquid injection molding LIM), also known as reactive injection molding (RIM), is used will. The latter process is much more economical than conventional injection molding processes and is about to become popular.

The conversion of the thermoplastic, thermosetting compositions according to the invention to the B stage can be carried out by heating the reactive components to a temperature which is generally in the range from about 25 ° to 180 ° C., preferably in the range from about 50 to 150 ° C .The junction of the components in the B-stage begins generally in about 20 minutes to about 1 hour at 12O ⁰ C, and a non-klerriger state may already be achieved in about 20 minutes at this temperature. The shelf life of the B-staged material is excellent, often 6 months or more. The curing of the C-state may be accomplished by the present B-stage material is heated for about 20 minutes to about 1 hour at a temperature of about 120 to 160 ⁰ C, for example from about 150 ° C.

The compositions in the B-stage can be calendered at around 45 ° C. to form films of the desired width and thickness suitable for the production of tapes and laminate tubes. The non-sticky ones Films can 1) between layers of rubber compounds and / or fabric layers for the production of Conveyor belts, hoses or the like. pressed and 2) heated to a flowable, sticky state.

709S34 / 0902

3) When heated in the manner described above, the foils go into the C-state through curing over and have excellent adhesion and cohesion. The thickness of the foils and plates can vary widely Limits are from 2.5 mm or less to 25.4 mm or more.

The masses present in the B-stage can also be prepared by known methods, e.g. by granulating and chopping, be crushed. The crushed masses can be kneaded, extruded, through on roller mixers Injection molding processed, calendered, mixed in the Banbury mixer or the like. Before kneading, that Mix in a Banbury mixer or the like. or during this treatment, the crushed, B-staged ones may be present Mass mixing additives are added. These additives are used in the usual quantities used that are well known.

Examples of possible mixing additives include: reinforcing fillers, e.g. carbon blacks, metal carbonates and silicates, glass, asbestos and textile fibers, non-reinforcing fillers, e.g. titanium dioxide and silica, dyes such as metal oxides and metal sulfides, and organic dyes, lubricants and plasticizers such as petroleum oils, castor oil, glycerin, silicones, aromatic and paraffinic oils, and Alkyl and aromatic phthalates, sebacates and trimellitates, and antioxidants and stabilizers, e.g. Phenyl-ß-naphthylamine, 2,6-di-t-butyl-p-cresol, 2.2 - Methylenebis- (4-methyl-6-t-butylphenol), 2,2'-ThIObIs- (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-m-cresol), Tris- (3,5-di-t-butyl-4-hydroxybenzyl-isocyanurate, hexahydro-1,3,5-tris-ß- (3,5-di-t-butyl-4-hydroxyphenyl) propionyltriazine, Tetrakis-methylen-3- (3 ·, 5'-di-t-buty1-4 · -hydroxyphenyl) propionate methane, Distearyl thiodipropionate and tri (nonylated phenyl) -

709834/0902

phosphite. Peroxides as hardeners, e.g. dicumyl peroxide, can also be used.

Sulfur-containing accelerators are suitable as further suitable mixture additives. More suitable as examples Accelerators may be mentioned: metal salts of dialkyl, diaryl and alkaryl dithiocarbamates, e.g. Bismuth, copper, lead and zinc dimethyldithiocarbamate, Cadmium, selenium, tellurium and zinc diethyldithiocarbamate, sodium and zinc dibutyldithiocarbamate, zinc ethylphenyldithlocarbamate and zinc dibenzyl dithiocarbamate, other dithiocarbamates, e.g. piperidinium pentamethylene dithiocarbamate, N-Cyclohexylethylammoniumcyclohexyläthyldithiocarbamat and N-pentamethylene ammonium-N-pentamethylene dithiocarbamate, Benzothiazoles, e.g. 2-mercaptobenzothiazole and its zinc salt, 2.2 - Benzothiazyl disulfide, morpholinothiobenzothiazole and 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, benzothiazole sulfenamides, e.g. N-diethyl-2-benzothiazylsulfenamide, N-t-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylen-2-benzothiazolesulfenamide, and thiuram sulfides, e.g. tetramethylthiuram disulfide, tetraethylthiuram disulfide, Dimethyldiphenylthiuram disulfide and dipentamethylene thiuram hexasulfide. Excellent results have been obtained using N-t-butyl-2-benzothiazole sulfenamide and N-cyclohexyl-2-benzothiazole sulfenamide.

The compositions according to the invention in the B-stage can be used on the roller mixer, in the Banbury mixer or the like. be compounded with a wide variety of other organic polymeric materials. These materials are generally used in amounts of from 0 to about 1000 parts by weight, preferably from 0 to 200 parts by weight or more is used per 100 parts by weight of the B-staged composition. As examples of such Materials are natural rubber, cis-polyisoprene,

709834/0902

cis-polybutadiene (CB) ₁ acrylonitrile-butadiene-styrene copolymers (ABS), butadiene-acrylonitrile rubbers (NBR), isoprene-acrylonitrile rubbers, butadiene-styrene rubbers (SBR), isoprene-styrene copolymers (neoprene, polychylene) , and nylon to name a few. Examples of other suitable polymeric materials are isoprene-isobutylene rubber (butyl rubber), copolymers of conjugated dienes with lower alkyl and alkoxy acrylates, ethylene-propylene-diene polymers (EPDM) and polyurethanes, for example those in US Pat. No. 2,871,218 and 2,899,411. Mixtures of organic polymeric materials can also be used.

The thermoplastic, thermosetting compositions according to the invention can before the transition to the B-stage or in the B-stage in so-called "prepregs", i.e. woven or non-woven Fibers, which are impregnated with the masses, are used. Suitable fibrous materials are those made from organic materials Polymers, e.g. Polyesters, "kevlar", nylon, Cotton and wool and of inorganic materials, e.g.

Glass, brass, steel and the like The fibrous materials can be in flat form, as yarn, cord and the like.

A wide variety of substrates can be prepared using the compositions according to the invention before the transition to the B-state or B-state coated, covered, leveled, repaired, etc. As substrates For example, the following are possible: natural rubber, cis-polyisoprene, cis-polybutadiene (CB), acrylonitrile-butadiene-styrene copolymers (ABS), butadiene-acrylonitrile rubbers (NBR), isoprene-acrylonitrile rubbers, butadiene-styrene rubbers (SBR), isoprene-styrene copolymers, polychloroprene (neoprene), nylon and mixtures these materials. Other suitable substrates are isoprene-isobutylene rubber (butyl rubber), Copolymers of conjugated dienes with lower alkyl and alkoxy acrylates, ethylene-propylene-diene-poly

709834/0902

♦ Μ.

merisate (EPDM), polyurethanes, e.g. those in the US patents

2,871,218 and 2,899,411, and mixtures of these polymers. As another suitable Surface materials come the product "Kevlar", Wood, concrete, stainless steel, glass, ceramic tile, tin, and antifouling coatings such as those in the U.S. Patent

3,426,473 in question.

The prepregs described above and / or coated or coated surfaces can be in layers together with the polymer compositions according to the invention (before the B-stage or in the B-stage) between layers pressed to form laminates. The curing of the masses for connecting the layers can take place simultaneously take place during pressing or after pressing.

The laminates can have a very different number of layers (generally 2 to 10 layers), with a B-staged adhesive present between each layer. As an example, consider a Rubber-adhesive-fabric-adhesive-rubber laminate called. It is also possible to use the B-staged adhesive and that described above Compound organic polymeric material prior to lamination to increase the number of layers in the laminate to decrease. For example, a five-layer Laminate (rubber-adhesive-fabric-adhesive-rubber) be replaced by a simpler three-layer laminate with the following structure:

Layer 1: Compounded Rubber with Adhesive Layer 2: Fabric
Layer 3: Compounded rubber with adhesive

These laminates, which contain one or more layers of compounded rubber with adhesive, have generally higher adhesive strength and cohesive strength as laminates in which rubber and adhesive are present separately.

70983W0902

The invention is further illustrated by the following examples.

Examples materials

The terminal amine-substituted liquid polymer, which was used in the experiments described in the following examples, could easily be after Process described in detail above using N- (2-aminoethyl) piperazine in the Prepare reaction to introduce terminal amine groups. The one marked with "ATBN" at the end The amine-substituted liquid polymer was a terminally amine-substituted butadiene / acrylonitrile copolymer with an acrylonitrile content of about 17% by weight of the polymer, a viscosity of about 130,000 up to 250,000 cPs at 27 ° C, a number average molecular weight of about 3000 to 4400 and an amine (-NHp) equivalent weight from about 1500 to 2200.

The "CTBN" designated liquid polymer with terminal carboxyl groups, which is used to produce the ETBN and for comparative purposes in the experiments described in Examples 25 to 27 used was prepared by the process described in U.S. Patent 3,285,949. The CTBN was a terminal one Carboxyl group-containing butadiene / acrylonitrile copolymer with an acrylonitrile content of about 17% by weight of the polymer, a viscosity of about 80,000 to 200,000 cPs at 27 ° C. and a number average molecular weight from about 2500 to 3500.

One of the cycloaliphatic epoxy resins used to make those in the B-stage and C-stage Compounds used was the 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate with an epoxy equivalent weight of about 137 and a viscose

7019834/0902

did from about 350 to 450 cPs at 25 ° C. This resin is under the name "Bakelite ERL-4221" (manufacturer Union Carbide Corp.) in stores.

Another cycloaliphatic epoxy resin has been used to produce B-staged and C-staged Masses a terminal cycloaliphatic epoxy group containing liquid butadiene / acrylonitrile copolymer used, referred to above as "ETBN" and made as follows: A 12 liter three-necked flask was cleaned well, rinsed and dried with dry nitrogen. The flask was with thermocouples (both in the flask and between the flask and heating mantle) and equipped with a stirrer. The piston was constantly purged with dry nitrogen gas.

6800 g of a terminal carboxyl group-containing liquid polymer (CTBN) of the type described above Art were added to the flask and heated to about 84 ° C with stirring. At this temperature were 1457 g of vinylcyclohexene dioxide ("Bakelite ERL-4206", made by Union Carbide Corp.) was added to the flask. About 5.5 equivalents of vinylcyclohexenedioxide were terminated per equivalent of the liquid polymer Carboxyl groups used. The reaction mixture was stirred for a further 2 hours at about 120 ° C. Direct then a vacuum of 20 mm Hg was applied to the reaction mixture to remove some excess vinylcyclohexenedioxide and other volatiles. The reaction product, a liquid butadiene / Acrylonitrile copolymer with terminal cycloaliphatic epoxy groups had an epoxy equivalent weight of about 1500 and a Brookfield viscosity of about 174,000 cPs (measured with a Brookfield LVT viscometer at 22 ° C). After a storage period of 7 months at room temperature, the viscosity of the ETBN was only increased to about 184,000 (measured at 23 ° C)

709834/0902

Signs of a very long service life.

Apart from the liquid polymers with terminal amine groups or terminal groups described in detail above Cycloaliphatic epoxy groups (ATBN or ETBN) are the materials used in the examples below attempts described were used, known commercially available, readily available materials.

Test methods

The physical testing of the mixtures according to the invention was carried out according to the methods mentioned below. The modulus, tensile strength and elongation at break of the elastomeric materials were determined at 25 ° C. in accordance with ASTM D 412 using dumbbell-shaped samples (Die C), unless stated otherwise. In the latter case, oval samples with a mean circumference of 10.2 cm were used. The Gehman freezing point was determined in accordance with ASTM D 1053. Compression set was measured according to ASTM D395B after holding the samples at 100 ° C for 70 hours. The tear strength was measured according to ASTM D 624 using Form C (Die C). Pico abrasion resistance was measured according to ASTM D 2228 using a 5.5 kg weight at a speed of 60 rpm and 80 revolutions. The abrasion index was calculated according to § 11.3 of the latter method. The durometer hardness was measured according to ASTM D 676 using a Shore A durometer with a pressing time of 1 second. The T 1 and T ₂ values were determined using a dynamic extrusion rheometer from the applicant (J. Elastomerics, Volume 5, p. 222 (October 1973)). The 180 ° tear-off strengths in the case of rubber-rubber laminates or rubber-fabric laminates were determined using samples with a size of 25.4 × 152 mm.

709834/0902

which pulled apart on an Instron tensile tester at a speed of 25.4 mm / minute became.

example 1

300 g ATBN were heated to 120 ° C. in a 0.95 1 vessel under vacuum (about 100 mm Hg) and with stirring. After adding 100 g each of 3,1-epoxy-cyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate ("Bakelite ERL-4221") and molten (60 ° C.) hexahydrophthalic anhydride to the ATBN, stirring was continued for 10 minutes. The mixture was poured into a bowl of 15.2 × 23 cm lined with polytetrafluoroethylene and ^{kept at 150 °} C. for about 15 minutes in a heating cabinet with air circulation. The mixture thickened during this time and reached a viscosity of about 2,000,000 cPs. It was then cooled to room temperature. A dry rubbery material present in the B-stage was obtained. It initially had a T. * Value of -5 ° C and a Tp value of around 75 ° C. After aging for 6 months at room temperature, a T ^ value of about 5 ° C and a T ₂ value of about 85 ° C were found. These data indicate that the B-staged material had excellent shelf life and useful life.

The material was completely cured from the B stage to the C stage by placing it in a bowl and keeping it in the heating cabinet at about 150 ^° C. for about 25 minutes.

Example 2

1800 g ATBN were heated to 145 ° C. in a 3.8 l vessel with occasional stirring. After adding each 600 g of S ^ -epoxy-cyclohexylmethyl-O ^ -epoxy / cyclohexane carboxylate ("Bakelite ERL-4221") and molten (60 ° C) hexahydrophthalic anhydride to ATBN was added

70983A / 0902

Stirred at about 120 ° C. for 2.5 minutes. Three such approaches were prepared and successively poured onto casting paper, which is heated to about 150 to 145 ° C Covered conveyor belt. The thickness of the mixture after casting was about 4.2 mm and the total residence time on the hot conveyor belt for about 12 minutes. The mixture was cooled by placing it on the conveyor belt was passed through a cooling zone. A dry, rubbery, B-staged material has been received.

Examples 3 to 6

In each case, 360 g of AIBN were heated in a 0.95 1 vessel under vacuum (about 100 mm Hg) with stirring to 80 ⁰ C. After adding 120 g of 3,4-epoxy-cyclohexyl-

15 methyl-O ^ -epoxyicyclohexanecarboxylate ("Bakelite

ERL-4221 ") and molten (60 ° C) hexahydrophthalic anhydride The stirring was continued for the various times given in Table I to give the ATBN. The mixture was then immediately poured into a centrifugal casting machine at 120 ° C and spun at about 120 rpm, until it was cool. A dry, rubber-like B-state material with the in T ^ and T «values, shown in Table I, were obtained.

Immediately after mixing was complete, small samples of each batch were also placed in an air circulating oven heated to 150 ° C until complete hardening (C-state) was reached. The curing times are listed in Table I.

709834/090?

Table I.

Example mixing time

Testing of the material in the B-state in the dynamic extrusion rheometer of the Applicant

Time to hardening (C-state) at 150 ⁰ C after mixing

3 5 Min .: no oil bath reached
to the 4 · 7th Min .: Exotherm
120 ° C
to water reached
to the 7098 5 · 20th Min. Exotherm
130 ⁰ C before
to water reached
to the CJ
**
O 6 ·· 30th Min .: Exotherm
140 ⁰ C before
to water CO

0 ⁰ C

48 ° C

50 ° C

49 ° C

75 ° C

50 minutes 40 minutes 35 minutes 20 minutes

• The mixing vessel was immersed in an oil bath kept at 120 ° C. •• Sample 6 was kept at 65 ° C for 30 minutes during the spinning and then cooled.

Examples 7 to 12

Examples 7 to 12 illustrate the properties of the final cured (C-stage) compositions according to the invention. The general mixing and pouring procedure described in Example 1 was followed.

Specifically, Examples 7 to 12, summarized in Table II, illustrate the influence of different ones ATBN quantities on the properties of the masses in the C-state. In general it was found that the module, the tensile strength, the compression set, the tear strength and the hardness becomes lower as the amount of ATBN increases, while the elongation, the Gehman solidification point and the abrasion resistance increase.

709834/0902

Tabel

II

O
(O
QO

example Recipe

"Bakelite ERL-4221", parts by weight ATBN, parts by weight
Hexahydrophthalic anhydride, parts by weight

Results of the exams

Cure, ° C / hours
100% modulus, psi
200% modulus, psi
Tensile strength, psi
Elongation at break,%

Gehman solidification point, ⁰ C deformation rest,%
Tear Strength, lbs / in. Pico abrasion index
Durometer hardness, type A

100% modulus, kg / cm,
200% modulus, kg / cnr
Tensile strength, kg / cm
Tear Strength, kg / cm

100

300

ICO

1592

1651
104

-55
35.3
228
21
95
112

116
40.7

100

350

100

1053

1350 135

-56

21.4 209

95 37.3

100 400 100

758

1138 135

-55 10.7 191 15 90

53.3

80 34.1

11 *

100

450

100

465 892 9i4

204

-49

14.3

141

84

32.7 62.7 64.3 25.2

* ■ *

208 369

484

-47 25.7 94 ■ ** ■ * * *

75 14.6 26 34 16.8

• Tested using oval specimens.
·· Two-stage curing, whereby the sample is first 2 hours at 120 ^° C. and then

Was hardened at 150 ^{° C. for 2 hours.}
'· Two-stage curing, with the sample first 2 hours at 120 ^° C. and then

Was hardened at 160 ^{° C. for 2 hours.} ·· Sample rubbed through.

"Bakelite ERL-4221" "3,4-Epoxy-Cyclohexy! Methyl- (3,4-epoxy) -cyclohexanecarboxylate

Examples 13 to 16

Examples 13 to 16 compiled in Table III show that the influence of curing times of more than 4 hours - with the exception of the compression set - is only minimal, a sign that it is optimal
Cures to C-stage in less than 4 hours
can be reached. The general mixing and pouring procedure of Example 1 was followed.

709834/0902

T a b e 1 le

III

-4 O CD OO Ca »

CD CD O

Example recipe

"Bakelite ERL-4221", parts by weight ATBN, parts by weight Hexahydrophthalic anhydride,

Parts by weight

Results of the exams

° C / hour psi (kg / cm '

Curing, 100% module, 100% module, psi (kg / crO 200% module, psi (kg / cm?) 200% module, psi (kg / cnTl tensile strength, psi ( kg / cm ^Z ) Tensile strength, psi * «(kg / cm ² ) Elongation at break,% · Elongation at break,% ··

Gehman solidification point, ° C compression set,% tear strength, lbs / in. (Kg / cm) Pico abrasion index durometer hardness, type A

At Bei

25 ° C tested, 80 ° C tested,

13th

100 300 100

150/3 982

227

I394

465 1772

490

253

205

(69)

(16) (98) (32.7) (124.6) (34.5)

-61 39.5 2.Ββ'.7 (51.2)

30 97

100 300

100

150/4 ιοι4

255 1504

520 1386

555 250

207

71.3)

(17.9)
(106)
(36.6)
(132.6)
(39)

304.7 (54.4)

100

300

100

150/5 1011 (71.1

243 (17.1) iLLj (101.7)

(34.9) (127.7) (37.8)

-97 1817

537

251 207

-67

AQ -ι

298.4 (53.3) 30 96

100 300 100

150/6

1021 (72)

271 (19)

1,453 (102.2)

κ? 3 (37.5) 1826 (128.4) _:

575 (40.4)

252

210

-62

18.6

301.1 (53.8) 30

35

♦ η.

Examples 17-21

Examples 17 to 19 and 20-21 compiled in Table IV illustrate the influence of different ones Amounts of hexahydrophthalic anhydride or dioctyl phthalate on the properties of the masses im C-state. The general mixing and pouring procedure described in Example 1 was followed.

709834/0902

Table IV

Example . _ ± L 1§_ 19 20_ 21 recipe

"Bakelite ERL-4221, parts by weight 100

ATBN, parts by weight 300

Hexahydrophthalic anhydride, parts by weight 60 dioctyl phthalate, parts by weight

Results of the exams

Hardening, ° C / hours psi Module at 100% elongation, psi α »" 200% ", (O Tensile strength, psi 00 Elongation at break,% , "C Gehman freezing point ^^
O Compression set,% /in. CO Tear Resistance, lbs.

162 245 631 410

32.6

72.9 Pico Abrasion Resistance ***

Modulus at 100% elongation, kg / cm ^ 11.4

Modulus at 200% elongation, kg / cnC 17.2

Tensile Strength, kg / cnT 44.4

Tear strength, kg / cm 13

• Two-stage curing: the sample was initially

and then hardened ^{at 150 °} C. for 2 hours.
·· Two-stage curing: The sample was cured first and then for 2 hours at 160 ^° C.

* ·· sample rubbed through.

U) r ^J
CDO O
IOOO 100
300
120 100
150
100
10 100
150
100
20th * I *
i63o ** ■ * · * 1609
392 1366
123 2906
28 2576
26th -60
44.0
277.5
45 59.4
283.4
28 100
153.2
33 100
100.6
28 - 118 - - 113
49.6 131
50.6 204
27.4 181
18th 2706693 t 2 hours . at 120 ^° C 2 hours. at 120 ^° C

Examples 22-27

Examples 22-27 compiled in Table V illustrate the influence of ATBN in comparison to CTBN to the C-state compositions according to the invention. Masses containing CTBN could not can be used to produce B-staged material. Instead, they hardened CTBN containing masses directly to the C-stage. As an accelerator in the case of Examples 25-27 N, N-dimethylbenzylamine used. That in example 1 general mixing and pouring procedures described were used.

709834/0902

Table V

Example 22 * 2g * 24 * 25 * 26 * 27 * recipe

"Bakelite ERL-4221", parts by weight 100 100 100 100 100 100

ATBN, parts by weight 200 300 400 -

CTBN, parts by weight - 200 300 400

Hexahydrophthalic anhydride, parts by weight 100 100 100 100 100 100

Ethylene glycol, parts by weight - 1.5 1.5

Ν, Ν-dimethylbenzylamine, parts by weight - 1.0 1.0

Results of the exams

^ J curing. ° C / hours ** ** ** ** ** **

σ modulus at 100% elongation, psi - 1592 758 - _ 1592

<o "200%" psi - -

? J Tensile strength psi 2400 I65I 1133 2241 1476 IO51

"Elongation at break,% 36 104 135 35 77 104 ·

ο Gehman freezing point, ⁰ C -63 -55 -55 -59 -54 -55 *? *

«Ö Compression set,% 31.8 35.3 10.7 25.9 45.0 35.3 '

ο Tear Resistance, lbs / in. II9 228 191 219 130 228

** Pico abrasion index 28 21 15 23 *** 21

Durometer hardness, type A 96 95 90 95 95 95

Modulus at 100% elongation, kg / cm ^ - 112 53.3 - - 112

¹¹ "200%", kg / cm ² - - -

Tensile strength, kg / cm ² 169 116 80 158 104 116

Tear Strength, kg / cm 21.3 40.8 34.1 39.1 23.2 40.7

• Tested using oval specimens. ¹ ^

·· Two-stage curing: The sample was first cured for 2 hours at 120 ^° C. and then for 2 hours at ο

Cured 160 ^{0 C.} CD

··· Sample rubbed through. T ^?

Examples 28-31

Examples 28-30, compiled in Table VI, illustrate the effect of different amounts of bicyclo / 2.2.l7hept-5-en-methyl-2,3-dicarboxylic anhydride on the properties of masses in the B-state. The general mixing and pouring procedure described in Example 1 was followed. An excellent one The result was also obtained when using dodecenylsuccinic anhydride in place of bicyclo / 2 ~ .2. ^ 7hept-5-en-methyl-2,3-dicarboxylic anhydride, such as Show values for Example 31 in Table VI.

example

"Bakelite ERL-42 15 parts

ATBN, parts by weight Bicyclo / 2 ". 2 .j7-hept-5-en-

methyl-2,3-dicarboxylic acid an-

hydride, parts by weight 104 117 130

Dodecenyl succinic acid

anhydride, parts by weight - - - 175

Results of the tests

Tabel VI 100 29 _30 H 300 100 100 100 ¹¹ , wt. 300 300 300

Curing time until
B-state at 120 ° C, hours Examples 32-37 2 1.25 1.1 0.9 Hardening from the B stage at
150 ° C to C-state, hrs. 0.75 0.75 0.5 0.1 T.j value for the material im B state, ⁰ C -15 - 30th - T ₂ value for the material im B state, ⁰ C 83 101 92 -

Examples 32-37, compiled in Table VII, illustrate the effect of different amounts of ATBN and ETBN on the properties of the compositions according to the invention in the B-state and C-state.

709834/0902

Tabel

VII

example Recipe

"Bakelite ERL-4221 ¹ , ¹ , parts by weight ATBN, parts by weight hexahydrophthalic anhydride, parts by weight ETBN, parts by weight

Test values of the material in the B state

Curing, ° C / hour T ^ after 3 months at T "after 3 months at

22 ° C 22 ° C

Test values for the material in the C-state curing, ^c C / hour module at 100% elongation, psi module at 200% elongation, psi tensile strength, psi elongation at break,%

Gehman freezing point, ⁰ C compression set,% tear strength, lbs./in. P ico abrasion index
Durometer hardness, type A

2 module at 100% elongation, kg / cm

Module at 200% elongation, kg / cm ² tensile strength, kg / cm * tear strength, kg / cm

100
100
100
200

120/1

111

1194
1740

l44

53 _r
27.6
162

20th
89

122
28.9

100 100 100

300

120/1

-18

442

1132

34 35 36

208

-49 22.2

84

70

31

79.6

86.5

15th

150

120/1
102

*
1171

1869

I67

-58
26.7

82.3

131
34.8

100 200 100 100

103

1030

1700

1909

214

-62 29.7

229 24 92

72 120 134

40.9

100 200 100 200

394

696 I 1225 296

-46 ₍

29.5

116 10

76

28 49 86 20.7

100

300

100

100

120/1 120/1 12G / 1

92

427 * 661 1344

366

-46

29

163

• Two-stage curing: The sample was first 1 h at 120 ° C and then cured for 2 hours at 150 ⁰ C..

•• Sample rubbed through. 30th

46.5 ^ 94 ^

² 9, icn

Examples 38 to 40

Examples 38-40, summarized in Table VIII illustrate the influence of partial and complete replacement of 3,4-epoxy-cyclohexylmethyl- (3,4-epoxy) -cyclohexanecarboxylate ("Bakelite ERL-4221") with greater amounts of ETBN than in the case of Examples 32-37. The products had sticky surfaces in the B stage, while in the C-stage they were dry and non-sticky.

Table VIII

example 38 39 40 Recipe "Bakelite ERL-4221", parts by weight - - 500 ATBN, parts by weight 300 300 300 Hexahydrophthalic anhydride,
Parts by weight 100 100 550 ETBN, parts by weight 1200 1400 800 Test values for the material in
B-state

Curing, ° C / hour Surface condition

Test values for the material in the C-state

Hardening to the C-stage from the B-stage, ° C / hour.

Surface condition

120 / 0.25 120 / 0.25 120 / 0.3 sticky sticky sticky

150 / 0.4
dry

150 / 0.4
dry

150 / 0.4 dry

Example 41

This example illustrates the benefit of a product according to the invention compounded with rubber and used as an adhesive in a rubber fabric Rubber laminate is used. A B-staged adhesive was made from the following ingredients:

7O9834 / 0S02

"Bakelite ERL-4221" 100 parts by weight

ATBN 300 "

Hexahydrophthalic anhydride 100 "

The general mixing, pouring, and heating procedure described in Example 1 was used to prepare the im B-stage existing adhesive applied.

The adhesive described above was with an ethylene-propylene-butadiene polymer (EPDM) with a Compounded Mooney viscosity of 50-62 (ML-8 at 100 ° C). The following recipe was used:

B-stage adhesive 100 parts by weight EPDM copolymer 40 ^M

Nt-Butyl-2-benzothiazolesulfenamide 1 "Sulfur treated _{with MgCO 3} 0.5"

141.5 parts by weight

The mix was made on a 15.2 cm three roll mixer at 52 ° C, mixing until the mix was homogeneous. A skin about 3.2 mm thick was removed from the three-roll mixer and used with a hydraulic press, the plates of which were coated with polytetrafluoroethylene, at about 120 ^° C. and about

2 703 kg / cm for about 1 minute to about 1.9 mm thick plate pressed. The adhesive film was cooled and taken from the press.

25 A 25.4 χ 152 mm laminate was made from a

Tevlar fabric, which was enclosed on both sides by the adhesive film described above, produced. The laminate was made in a hydraulic press, the plates of which were coated with polytetrafluoroethylene,

30 cured by leaving it at 150 ° C and about 30 minutes

5.6 kg / cm ^{2 was} pressed. The 180 ° tear strength of the laminate was about 1.43 kg / cm width.

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Examples 42-45

These examples illustrate the advantages of the rubber compound compounded and used as adhesives for rubber-fabric-rubber laminates according to the invention. The compounded Rubber compound itself has adhesive properties, so that no separate adhesive layer is required. The test according to Example 42 is a comparative test without adhesive in the rubber mixture; the glue in the B-stage is alone between Kautschukmi research and fabric used. Example 43 shows that it is possible to increase the 180 ° tear-off strength of the comparative sample by compounding a nitrile-SBR rubber mixture with the adhesive present in the B-stage to be at least doubled according to the invention, but in the case of Examples 44 and 45, improved adhesive strength can also be seen.

The B-staged adhesive was used in these trials compounded in the manner described in Example 41, and laminated with the difference that the kneading temperature was 43 ° C and the pellet from the three-roll mixer a sheet about 1.9 mm thick was calendered. The compositions of the mixtures and the results of the tests are given in Table IX below.

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100 100 100 100 300 3OO 300 300 1OO 100 1OO 100

Table IX

Example 42 43 44 45_

Composition of the adhesive in the B-stage

"Bakelite ERL-4221", parts by weight ATBN, parts by weight hexahydrophthalic anhydride, parts by weight

"3 Composition of the adhesive-rubber mixture * B-stage adhesive, parts by weight <* butadiene-acrylonitrile rubber, parts by weight ^ styrene-butadiene rubber, parts by weight carbon black N-550, parts by weight Sulfur, parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide. Parts by weight -

1OO 1OO 100 21.25 42.5 85 3.75 7.5 15th 12.5 15th 20th 1.25 1.5 2 1.25 1.5 2

Total weight 100 140 168 224

Test values for the hardened laminate

180 ° tear-off resistance using Kevlar fabric, lbs./inch width

kg / cm width 1.8 3.57 2.5 1.6 -J

180 ° tear-off strength using ^

Polyester fabric, lbs./inch width 7 17 12 9 q ^

kg / cm width 1.25 3.04 2.14 1.6 ^

■ si. —_

Examples 46 to 49

These examples illustrate the advantages of compounded with two different rubbers and other blending additives and used as adhesives in rubber-fabric-rubber laminates, in the B- State of the present polymer compositions according to the invention. The rubber compound itself has adhesive properties, so that no separate adhesive layer is required. The runs of Examples 46 and 48 are comparative try where the rubber itself doesn't have any glue substance contains; the B-stage adhesive is used solely between the rubber mixture and the fabric. Example 47 shows that it is possible to achieve the 180 ° tear-off strength of the comparative sample of Example 46 Compounding polychloroprene rubber with the B-staged adhesive according to the invention more than triple. Example 49 shows that the 180 ° tear-off strength of the comparative sample of the example 48 by compounding an EPDM rubber with the B-staged adhesive according to the invention

7O983Ä / 0902

can be more than doubled.

In these experiments, the adhesive B-stage was compounded in the manner described in Example 41 manner and laminated with the difference that the kneading temperature of the polychloroprene 120 ° C and the EPDM copolymer was 52 ⁰ C. The composition of the
Mixtures and the results of the tests are given in Table X below.

Table X
Example 46 47 48 49

Composition of the adhesive in the B-stage

"Bakelite ERL-4221", parts by weight 100 100 100 100 ATBN, parts by weight 300 300 300 300

Hexahydrophthalic anhydride,

Parts by weight 100 100 100 100

Composition of the mixture of adhesive and rubber mixture

B-stage adhesive,

Parts by weight 100

Polychloroprene rubber, parts by weight

Ethylene propylene diene rubber,
Parts by weight

Carbon black N-550, parts by weight sulfur, parts by weight

N-cyclohexyl-2-benzothiazolesulfenamide, Parts by weight -

Total weight 100 140 100 140

Test values for the laminate hardened to the C-state

Rubber in the laminate Poly- Mi- EPDM Mi-

chlorination schung pren

100 100 100 25th - _ _ 25th 12.5 - 12.5 1.25 - 1.25 1.25 - 1.25

180 ° tear-off strength below 3 11 3 8th Use of Kevlar fabric, 0.54 1.96 0.54 1.43 lbs./inch width kg / cm

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example

180 ° tear-off resistance using polyester fabric, lbs./inch width

kg / cm

46

47

3 11 3 6 0.54 1.96 0.54 1.07

The polymer compositions according to the invention are advantageous as solvent-free adhesives (alone or compounded with rubber mixtures or the like) for conveyor belts, hoses, shoes, pieces of sheet metal on items of clothing, etc. The polymer compositions are also suitable as paints, powder coating materials, binders for woven or non-woven Fibers and cords and the like.

709834/0902

Claims (22)

Claims 1) Mixtures of substances containing A) 1 equivalent weight of at least one cycloaliphatic epoxy resin, which is at least average contains about 1.7 epoxy groups in the molecule and an epoxy equivalent weight of about 70 to 6000 Has, B) about 0.05 to 0.5 equivalent weight of at least one terminal amine-substituted liquid Polymer which contains an average of about 1.7 to 3 primary and / or secondary amine groups and the formula in which Y is a monovalent radical obtained by removing a hydrogen atom from an amine group of an aliphatic, alicyclic, hetero- π »Λ 2-2o carbon atoms of cyclic or aromatic amine ⁷ which contains at least two amine groups, of which at least two are primary and / or secondary, and B is a polymer main chain which has CC bonds and polymerized units of at least one vinylidene monomer contains, the at least one terminal group of the formula CH ₂ = Cv. and is selected from the following group: a) monoolefins with 2 to 14 carbon atoms, b) Serves with 4 to 10 carbon atoms, c) vinyl and allyl esters of carboxylic acids with 2 to 8 carbon atoms, d) vinyl and allyl ethers of alkyl radicals with 1 to 8 carbon atoms and 709894/0902 ORIGINAL INSPECTED e) Acrylic acids and acrylates of the formula R O ι »» λ
CH ₂ = CCOR wherein R is hydrogen or an alkyl radical having 1 to 3 carbon atoms and R is hydrogen, an alkyl radical with 1 to 18 carbon atoms or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with Is 2 to 12 carbon atoms, and C) about 0.4 to 1.5 equivalent weight of at least one anhydride with 4 to 24 carbon atoms in the molecule. 2) mixtures of substances according to claim 1, characterized in that that the C-C bonds make up at least 90% by weight of the total polymer main chain and the monomer is selected from the following group: a) monoolefins with 2 to 8 carbon atoms, b) Serves with 4 to 8 carbon atoms and e) Acrylic acids and acrylates of the formula R 0 I Ι » Λ CH ₂ = CCOR wherein R is hydrogen or an alkyl radical with 1 to 1
3 carbon atoms and R is hydrogen or an alkyl radical with 1 to 8 carbon atoms or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with 2 to 8 carbon atoms. 3) mixtures of substances according to claim 1 and 2, characterized in that that the epoxy resin has an epoxy equivalent weight of about 70-2000. 4) mixtures of substances according to claim 1 to 3, characterized in that that with the vinylidene monomer 0% to about 50% by weight of at least one comonomer from the following Group is copolymerized: 709834/0902 f) vinyl aromatics of the formula 2
wherein R is hydrogen, halogen or an alkyl radical with 1 to 4 carbon atoms, g) vinyl nitriles of the formula R ³ CH ₂ = CC = N where R is hydrogen or an alkyl radical with 1 to 3 carbon atoms, h) vinyl halides, i) divinyls and diacrylates, j) amides of cx, ß-olefinically unsaturated carboxylic acids with 2 to 8 carbon atoms and k) allyl alcohol. 5) mixtures of substances according to claim 1 to 4, characterized in that that the amine groups have different reactivities and the comonomer from the f) the vinyl aromatics mentioned and g) the vinyl nitriles mentioned is selected. 6) mixtures of substances according to claim 1 to 5, characterized in that that they contain at least one N- (Amino_alkyl) piperazine as amine, the aminoalkyl radical of the Amine contains 1 to 12 carbon atoms, as vinylldene monomer at least one of the dienes mentioned and as Comonomer at least one of the vinyl nitriles mentioned is present. 7) substance mixtures according to claim 1 to 6, characterized in that the cycloaliphatic epoxy resin 709834/0902 liquid polymer of the formula containing terminal cycloaliphatic epoxy groups OH M 0 0 M OH , ι μ ti ι ι L-C-C-O-C-4-B-) -C-O-C-C-L Il I ' MM MM is where L is a monovalent radical obtained by removal of a non-cycloaliphatic epoxy group of an epoxy resin which is at least one non-cycloaliphatic Contains epoxy group and at least one cycloaliphatic epoxy group, has been obtained, M is hydrogen or an alkyl radical having 1 to 4 carbon atoms and B has the meaning given above. 8) mixtures of substances according to claim 1 to 7, characterized in that L is a monovalent radical, which by Removal of a non-cycloaliphatic epoxy group from an epoxy resin that is non-cycloaliphatic Contains epoxy group and a cycloaliphatic epoxy group, has been obtained 9) mixtures of substances according to claim 1 to 8, characterized in that that the liquid polymer containing terminal cycloaliphatic epoxy groups, the formula OH 0 0 OH (Q PCH-CH ₂ -OC (■ B ■) CO-CH ₂ -CHT TN) 10) mixtures of substances according to claim 6, characterized in that that they are 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate as cycloaliphatic epoxy resin contain. 709834/0902 11) mixtures of substances according to claim 1 to 10, characterized in that that they are butadiene as diene, acrylonitrile as vinyl nitrile and N- (2-aminoethyl) piperazine as amine contain. 12) mixtures of substances according to claim 1 to 11, characterized in that that they contain hexahydrophthalic anhydride as the anhydride. 13) mixtures of substances according to claim 1 to 11, characterized in that they are dodecenylsuccinic anhydride as the anhydride contain. 14) mixtures of substances according to claim 1 to 11, characterized in that that they are bicyclo / 2 ~ .2._l7hept-5-en-methyl-2,3-dicarboxylic anhydride as the anhydride contain. 15) Mixture of substances cured to B-stage according to claim 1 to 14. 16) mixtures of substances according to claim 15, characterized in that that they are mixed with 0 to about 1000 parts by weight of at least one other organic polymeric material are compounded per 100 parts by weight of the substance mixture present in the B-stage. 17) mixtures of substances according to claim 15 and 16, characterized in that that they are natural rubber, cis-polyisoprene, cis-polybutadiene, an ethylene-propylene-diene polymer Styrene-butadiene polymer, polychloroprene, a butadiene-acrylonitrile copolymer or a mixture these polymers contain. 18) Mixtures of substances cured to the C-state according to claim 1 to 17. 19) Use of the substance mixtures according to claims 1 to 17 as adhesives for the manufacture of laminates. 709834/0902 20) Use according to claim 19, wherein the mixtures of substances hardens to the C-state. 21) Process for the production of mixtures of substances according to
Claims 15 to 17, characterized in that components (A), (B) and (C) according to Claim 1
mixes and the mixture hardens to the B-stage. 22) Method according to claim 21, characterized in that the mixtures of substances present in the B state transferred to the C-state through hardening. 709834/0902