DE2629992A1 - Possibly COVULCANIZED MASSES OF LIQUID POLYMERS WITH TERMINAL AMINE GROUPS AND POLYMERS WITH TERMINAL VINYLIDINE GROUPS, AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

FROM KREISLER SCHÖNWALD MEYER EISHOLD FUES FROM KREISLER KELLER SELTING

PATENT LAWYERS Dr.-Ing. by Kreisler f 1973

Dr.-Ing. K. Schönwald, 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. Selting, Cologne

5 COLOGNE 1 ^{2 July} 1976 AVK / IM

DEICHMANNHAUS AT THE MAIN RAILWAY STATION

The B.F. Goodrich Company, Akron, Ohio / USA

Possibly covulcanized masses of liquid polymers with terminal amine groups and polymers with terminal vinylidene groups and processes for their preparation

Polydienes with terminal vinylidene groups are known. For example, U.S. Patent 3,652,520 teaches manufacture of polymerizable polydiene ethylenically unsaturated Esters with at least one terminal ethylenically unsaturated acyloxy group by esterification of intermediate polyhydroxypolydienes with an unsaturated acyl compound. The polydienes with terminal vinylidene groups may together with certain other materials, for example, reactive vinyl comonomers as taught in U.S. Patent 3,652,520, as sealing compounds, sealing compounds or the like. can be used, however, the addition of a catalyst and / or Crosslinking agent generally required. An example of a known liquid polymer with terminal vinylidene groups with a polyether main chain is the diacrylate ester of the diglycidyl ether of bisphenol A. Neue Dichtungsund Sealing compounds are desirable to incorporate the polymers

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Telephone: (0221) 23 4541-4 Telex: 8 & 3 2307 dopa d Telegram: Dompalent Cologne

terminal vinylidene groups and which are easily vulcanized or cured at room temperature can without having to add catalysts or crosslinking agents.

The invention relates to co-curable or co-curable compositions containing a mixture of (1) 100 parts by weight of at least one amine-terminated liquid polymer with an average from about 1.7 to about 3 amine groups per molecule, with the amine groups being primary, secondary or are a mixture of these and the polymer has the formula 0 0

Il Il

Y-C -4Bf ^ C-Y

in which Y is a monovalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine with 2 - 2o carbon atoms and at least two amine groups have been obtained, where at least two of the amine groups are primary, secondary or a mixture thereof and B is a polymer backbone containing carbon-carbon bonds contains and

(2) about 80 to about 120 parts by weight of at least one vinylidene-terminated polymer the formula

R ⁵ R ⁶ R ⁶ R ⁵

CI | = C-A-p-CI £ -Z - (- G -} - Z-CH -9-A-C = CH

OH ² OH ²

in which Z is a divalent residue derived from the

TT Q

Group is selected that consists of -S-,, "

-N-, -C-O and

-0-, A is a divalent radical with 1 to 10 atoms of at least one atom selected from the group consisting of C, 0, S and N, R and R are hydrogen or alkyl radicals with 1 to 4 carbon atoms and G is a carbon Carbon, polyether or polysulfide polymer backbone. The liquid 709807/1250

Polymers terminated with vinylidene groups can have an average of from about 1.7 to about 3 groups of the formula

f f

CH = C-A-C-CH-Z-2 2

per molecule included in the Z, A, R and R the above

have the meanings mentioned.

Liquid Amine Terminated Polymers Liquid amine terminated polymers useful for the purposes of the invention are of the formula

0 0

Y-C-f-B-4-C-Y

in which Y is a monovalent residue obtained by removing of hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine with at least 2 primary and / or secondary amine groups, and B a polymer main chain that contains carbon-carbon bonds. In general, the carbon-carbon bonds make up at least about 90 weight percent of the total polymer Main chain of and preferably at least 95 wt .-%. The amine-terminated polymers contain an average of from about 1.7 to about 3 primary and / or secondary amine groups per molecule and preferably about 1.7 to about 2.3 primary and / or secondary amine groups per molecule. The polymers with Terminal amine groups can be obtained from Brookfield viscosities (measured using a Brookfield RVT viscometer at 27 ° C) from about 500 cps to about 25,000 cps, preferably from about 500 cps to about 500,000 cps.

The amine-terminated liquid polymers can easily by reacting a liquid polymer

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with terminal carboxyl groups or terminal ester groups with a carbon-carbon main chain with at least one aliphatic, alicyclic or heterocyclic amine with at least two primary and / or secondary amine groups are produced. The amine-terminated liquid polymers can also can be easily prepared by using liquid polymers terminated with a carbon-carbon backbone Acid chloride groups with at least one aliphatic, alicyclic, heterocyclic or aromatic Amine containing at least two primary and / or secondary amine groups can react.

The liquid polymers used according to the invention with terminal carboxyl groups can Brookfield viscosities from about 500 cps to about 500,000 cps, preferably from about 500 cps to about 250,000 cps and have a polymer backbone, the carbon-carbon bonds contains. The carboxyl groups are at least at the ends of a polymeric molecule; it however, additional carboxyl groups can also be present on d = n sides of the main polymer chain. The average The total number of carboxyl groups is typically from about 1.7 to about 3 groups per molecule, preferably from about 1.7 to 2.3 groups per molecule.

The liquid polymers with terminal carboxyl groups and with carbon-carbon main chain bonds can polymerized units of at least one vinylidene monomer containing at least one terminal CH ^ = C \ group and is selected from the group which consists of

(a) Monoolefins with 2-14 carbon atoms, preferably 2-8 carbon atoms such as ethylene, propylene, Isobutylene, 1-butene, 1-pentene, 1-hexene and 1-dodecene;

(b) Serves with 4 - 10 carbon atoms, preferably 4-8 carbon atoms, such as butadiene, isoprene,

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2-isopropyl-1/3-butadiene and chloroprene;

(c) Vinyl and allyl esters of carboxylic acids with 2-8 carbon atoms such as vinyl acetate, vinyl propionate and Allyl acetate;

(d) Vinyl and allyl ethers of alkyl radicals with 1-8 Koh carbon atoms such as vinyl methyl ether and allyl methyl ether; and

(e) Acrylic acids and acrylates of the formula

R 0
CH = CCO-Rl

in which R is hydrogen or an alkyl radical having 1-3 carbon atoms and R is hydrogen or an alkyl radical having 1-18 carbon atoms, preferably 1 to 8 carbon atoms, or an alkoxyalkyl- alkylthioalkyl- or cyanoalkyl radical having 2-12 carbon atoms, preferably 2-8 carbon atoms. More preferred R is hydrogen or an alkyl radical having 2 to 8 carbon atoms. Examples of suitable acrylates include ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, Methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, ß-cyanoethyl acrylate, cyanooctyl acrylate, methyl methacrylate, Ethyl methacrylate and octyl methacrylate. Often times, two or more types of these are polymerized Contain monomer units in the main polymer chain.

More preferred liquid polymers contain polymerized units of at least one vinylidene monomer with at least one terminal CH ₂ = C (group and are selected from the group consisting of

(a) monoolefins with 2-14 carbon atoms, preferably 2-8 carbon atoms,

(b) dienes with 4-1o carbon atoms, preferably 4-8 carbon atoms and

(e) Acrylic acids and acrylates of the formula

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RO
CH ₂ -CCOR ¹

in which R is hydrogen or an alkyl radical having 1-3 carbon atoms and R is hydrogen or an alkyl radical with 1-18 carbon atoms / preferably 1-8 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical having 2-12 carbon atoms, preferably Is 2-8 carbon atoms. R is even more preferably hydrogen or an alkyl radical having 2-8 carbon atoms. Excellent results have been obtained with dienes containing 4-10 carbon atoms, preferably 4-10 Contains 8 carbon atoms.

The vinylidene monomers described above are readily polymerized with up to about 50% by weight of at least one comonomer selected from the group consisting of
(f) vinyl aromatics of the formula

in which R is hydrogen, halogen or an alkyl radical with 1 to 4 carbon atoms, such as styrene, alpha-methylstyrene, Chlorostyrene and vinyl toluene; (g) vinyl nitriles of the formula "" 3 in the R

Is hydrogen or an alkyl radical having 1 to 3 carbon atoms, such as, for example, acrylonitrile and methacrylonitrile; (h) vinyl halides such as vinyl bromide and vinyl chloride;
(i) Divinylene and diacrylates such as divinylbenzene,

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- π ~ -

Divinyl ether and diethylene glycol diacrylate;

(j) Amides of alpha, ß-olefinically unsaturated carboxylic acids with 2-8 carbon atoms such as acrylamide; and

(k) allylic alcohols. Liquid polymer masses that polymerized Units of a larger amount of at least one vinylidene monomer of groups (a) to (e) with a small amount of at least one comonomer from group (f) to (k) are within the range of the present invention.

More preferred comonomers can be selected from the group consisting of
(f) vinyl aromatics of the formula

Ή ²

CH

-R ²

in which R is hydrogen, halogen and / or alkyl radicals 1-4 carbon atoms and (g) vinyl nitriles of the formula

CH ₂ -CC = N

in which R is hydrogen or an alkyl radical having 1-3 carbon atoms is. Excellent results are obtained using styrene and acrylonitrile.

Examples of suitable liquid polymeric backbones containing carbon-carbon bonds include Polyethylene, polyisobutylene, polyisoprene, polybutadiene, poly (vinyl ethyl ether), poly (ethyl acrylate) and poly (butyl acrylate) and also copolymers of butadiene and acrylonitrile, butadiene and styrene, vinyl acetate and isoprene, 709807/1250

Vinyl acetate and chloroprene, vinyl ethyl ether and diallyl ether, Vinyl ethyl ether and alpha-methylstyrene, Vinyl ethyl ether and vinyl bromide, methyl acrylate and butadiene, methyl acrylate and ethyl acrylate, methyl acrylate and butyl acrylate, methyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and ethylene, ethyl acrylate and isobutylene, Ethyl acrylate and isoprene, ethyl acrylate and butadiene, ethyl acrylate and vinyl acetate, ethyl acrylate and styrene, ethyl acrylate and chlorostyrene, ethyl acrylate, styrene and butadiene, ethyl acrylate and n-butyl acrylate, Ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and vinyl bromide, ethyl acrylate and acrylic acid, ethyl acrylate and acrylamide, ethyl acrylate and allyl alcohol, Butyl acrylate, styrene and isoprene, butyl acrylate and styrene, butyl acrylate and acrylonitrile and butyl acrylate and vinyl chloride.

The liquid polymers with terminal carboxyl groups can by free radical polymerization under Use of carboxyl-containing initiators and / or modifiers are prepared, as in of US-PS 3,285,949 and DT-PS 1 15o 2o5 and described by solution polymerization using Lithium metal or organometallic compounds and post-treatment of the polymers to form carboxyl groups, as described in U.S. Patents 3,135,716 and 3,431,235. The polymers can also be made by mixing liquid polymers with terminal groups other than terminal carboxyl groups with compounds reacted in order to obtain terminal carboxyl groups. For example, liquid polymers with terminal Carboxyl groups from liquid polymers with terminal hydroxyl groups by reaction with dicarboxy compounds or anhydrides. Liquid polymers with terminal halogen groups can with unsaturated anhydrides in the presence of

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Lewis acids are reacted to give terminal carboxyl groups. From this it can be seen that the Process for preparing the liquid carboxyl-terminated polymers for the invention does not is essential. The essential characteristics of the polymers are that they have at least terminal carboxyl groups and have a polymeric backbone with carbon-carbon bonds.

Examples of preferred liquid terminal polymers Carboxyl groups include carboxyl-terminated polyethylene, terminally polyisobutylene Carboxyl groups, polybutadiene with terminal carboxyl groups, polyisoprene with terminal Terminal carboxyl groups and poly (ethyl acrylate) Carboxyl groups and also copolymers of butadiene and acrylonitrile and of butadiene and styrene with terminal ends Carboxyl groups. Carboxyl-terminated copolymers of butadiene with acrylonitrile or styrene have been found prove to be particularly suitable. These polymers can contain from about 50 to about 95 weight percent butadiene contain about 5 to about 40% by weight of acrylonitrile or styrene and from about 0.5 to about 10% by weight of carboxyl, based on the total weight of the polymers.

The liquid polymers with terminal carboxyl groups can be mixed with an aliphatic monoalcohol known processes are esterified to form liquid polymers with terminal ester groups. For example can be a carboxyl-terminated polymer and a monohydric aliphatic alcohol in a distillation column or under reflux in the presence of a small amount of an acid catalyst implemented. Suitable acid catalysts include organic acids with 1-12 carbon atoms, preferably 1-8 carbon atoms such as acetic acid, propionic acid, benzoic acid, monoesters and diesters of o-phosphoric acid, alkarylsulfonic acids such as z, B 709807/1250

-1ο-

p-toluenesulphonic acid, inorganic acids such as e.g. Boric acid, hydrochloric acid, phosphoric acid and sulfuric acid and Lewis acids such as tetraisopropyl titanate. The amount of acid catalyst used can be as little as about 0.01% to about 5% by weight, based on i gen on the total weight of the reactants. Suitable aliphatic monohydric alcohols or monoalcohols for use in the esterification reaction contain 1-12 carbon atoms, preferably 1-6 Konlenstoffatome and have boiling points below about 15o C, preferably below about 100 ° C. Primary aliphatic Monoalcohols are preferred. Examples of suitable aliphatic monohydric alcohols include Alkanols with 1-6 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-hexanol and 3-hexanol. Other suitable aliphatic monovalent Alcohols include 2-methoxyethanol and 2-ethoxyethanol. Excellent results can be obtained using ethanol, 1-propanol, or 1-butanol.

The liquid polymers with terminal carboxyl groups can be acylated by methods known to those skilled in the art in order to obtain liquid polymers with terminal acid chloride groups. For example, a carboxyl terminated polymer can be reacted with thionyl chloride to obtain an acid chloride terminated polymer. HCl and SO ₂ are mainly evolved as gases and are easily removed from the acid chloride-terminated polymer. In addition, any excess thionyl chloride can be easily removed by vacuum distillation or by washing with a solvent such as methanol. Other suitable but less preferred acylating agents include phosphorus trichloride and phosphorus pentachloride.

Amines that work well with the polymers with terminal carboxyl groups and / or terminal ester groups and / or

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terminal acyl groups of the type described above include aliphatic amines having 1 to 20 carbon atoms, preferably 1-12 carbon atoms and at least two, preferably two, primary and / or secondary amine groups. Alicyclic amines having 4-20 carbon atoms, preferably 4-12 carbon atoms and at least two, preferably two, primary and / or secondary amine groups are also suitable. Heterocyclic amines containing 2-20 carbon atoms, preferably 2-12 carbon atoms and at least 2, preferably 2, primary and / or secondary amine groups can also be used. Examples of suitable amines include aliphatic amines such as 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, 1,1c-decanediamine and 1,12-dodecanediamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylene pentamine, bis (hexamethylene) triamine and 3,3'-iminobispropylamine; alicyclic diamines and polyamines such as 1,2-diaminocyclohexane and 1,8-p-menthediamine; heterocyclic diamines and polyamines such as 4- (aminomethyl) piperidine, piperazine, N- (aminoalkyl) piperazines, in which each alkyl group contains 1-12 carbon atoms, preferably 1-6 carbon atoms, such as N (2-aminoethyl) piperazine, N- ( 3-aminopropyl) piperazine and N, N ¹ -bis (3-aminopropyl) piperazine.

More preferably, the amines mentioned contain at least two primary and / or secondary amine groups with different ones Reactivities or different reactivities. The presence of amine groups with different ^: Reactivity makes the conversion to terminal amine groups more likely than coupling of liquid polymers. A slight excess of amine is required to avoid knocking. Examples of preferred amines include some alicyclic amines such as

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e.g. 1,8-p-menthediamine and some heterocyclic amines such as 4- (aminomethyl) piperidine and N- (aminoalkyl) piperazines, in which the alkyl radicals 1-12 carbon atoms, preferably 1-6 carbon atoms, such as N- (2-aminoethyl) piperazine and N- (3-aminopropyl) piperazine. Excellent results have been obtained when using N (2-aminoethy1) piperazine.

Aromatic diamines and polyamines can be used to make amine-terminated polymers. The ones for the reaction of aromatic amines with polymers with terminal carboxyl groups required high temperatures cause excessive degradation of the Reactants and products, which is why they are less preferred. However, aromatic amines react well with the acyl-terminated polymers described above. Suitable aromatic amines contain at least 2 primary and / or secondary amine groups bonded directly to at least one aromatic nucleus are. Examples of suitable aromatic amines include 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 not required for the conversion to terminal amine groups, but can be used. Mixtures of solvents can also be used. Suitable solvents include aliphatic and cycloaliphatic ethers having 3 to 10 carbon atoms, preferably 3-6 carbon atoms, such as tetrahydrofuran and diethyl ether; halogenated aliphatic hydrocarbons with 1 to 10 carbon atoms, preferably 1-6 carbon atoms such as chloroform, Carbon tetrachloride, 1,2-dichloroethylene, trichlorethylene and tetrachlorethylene; and esters with 3 - 1o

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Carbon atoms, preferably 3-6 carbon atoms such as ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate and ethyl propionate. Just if suitable as a solvent and more preferred are aromatic compounds of the formula

R-

-R

in which R is hydrogen, halogen or an alkyl radical

4 is 1-3 carbon atoms and at least two R's are hydrogen. R is preferably hydrogen or chlorine or an alkyl radical with 1-2 carbon atoms and

at least three of the R's are hydrogen. Suitable aromatic solvents include 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 amines described above can be mixed with one of those described above liquid polymers reacted with terminal carboxyl and / or ester and / or acid chloride groups to obtain an amine-terminated liquid polymer containing about 1.7 to about 3 contains primary and / or secondary amine groups per molecule. Typically the average number of total carboxyl, ester, or acid chloride groups in a liquid polymer before reaction is about 1.7 to about 3 groups per molecule, preferably about 1.7 to about 2.3 groups per molecule. In this

and more. Typically, about 1.2 to about 6 molar equivalents / preferably about 1.2 to about 3 molar equivalents of at least one of the amines described above can be used per molar equivalent of the carboxylated, esterified, or acylated liquid polymer described above 709807/1250

will. However, if the carboxylated, esterified or acylated liquid polymer also contains a significant amount of acrylic acid, acrylates or the like. polymerized with it contains, the amount of amine to be reacted must be limited, so that the liquid polymer with terminal Amine groups contain no more than about 1.7 to about 3 primary and / or secondary amine groups per molecule.

A catalyst is not required. Many types of; Mixing equipment can be used to form the terminal amine groups. For example, simple mixers including turbine stirrers and propeller mixers can be used. The reactants can be combined in any order. The reaction mixture can be heated to a temperature of from about 80 ° C ^: to about 150 ° C (or refluxed if a solvent is used), typically for about 1-6 hours. The liquid amine-terminated polymer can be purified by vacuum distillation or by washing with a solvent such as a benzene-methanol mixture and then drying. The amine content of the liquid amine-terminated polymers can be analyzed qualitatively by infrared spectroscopy. The amine content can also be analyzed quantitatively using the method described by Siggia in "Quantitative Organic Analysis via Funtional Groups" Wiley and Sons, Inc., NY 1963, pp. 452-456.

Polymers with terminal vinylidene introduction polymers having terminal vinylidene groups which are suitable for the purposes of the invention, solid polymers can be, but are preferably liquid polymers having Brookfield viscosities (measured using a Brookfield RVT viscometer at 27 ° C) of about 4oo cps to about 1,000,000 cps, preferably from about 400,000 cps to about 500,000 cps. Solid vinylidene polymers

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can be mixed directly with the liquid amine-terminated polymers described above, are, however, preferably first with at least one> solvent or diluent / preferably with a reactive diluent such as styrene and the diglycidyl ether of butanediol. Responsive Diluents can and must harden or vulcanize into the compositions according to the invention therefore not be evaporated or otherwise removed from the masses. Excellent results were obtained using styrene.

Polymers with terminal vinylidene groups that are useful for the purposes of the invention can be according to various Methods are made.

(A) For example, liquid polymers with terminal vinylidene groups can be produced by reacting

(1) a liquid polymer with at least functional terminal groups from the group consisting of amine, carboxyl, hydroxyl and mercaptan and

(2) a compound having both an oxirane group (CH ₂ -CH-) and a vinylidene group

getting produced. The latter reaction can be catalyzed.

(B) Another method of making vinylidene-terminated polymers involves reacting of a liquid polymer having at least terminal epoxy groups with acrylic acid or methacrylic acid. For example, a diglycidyl ether can be a Bisphenol compound can be reacted with acrylic acid or methacrylic acid to form a diacrylate ester. The reaction products contain two terminal vinyl groups per molecule. This reaction can be catalyzed will. It has thus been shown that the process of preparing the polymers with terminal

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Vinylidene groups is not critical. The essential characteristics of the polymers are that they are at least terminal Have vinylidene groups and a polymer main chain, the carbon-carbon, polyether or have polysulfide bonds.

Production of liquid polymers with terminal ends

Vinylidene groups

The following describes in detail the production of liquid polymers with terminal vinylidene groups Implementation of

(1) a liquid polymer with at least terminal functional groups selected from the group which consists of amine, carboxyl, hydroxyl and mercaptan and

(2) a compound that has both oxirane groups (CH ₀ -CH -)

as well as containing vinylidene groups.

Liquid polymers with terminal vinylidene groups, which are prepared by the latter method, can have the following formula

r5 e ⁶ ff

CH ₂ = CAC-CH ₂ -Z- (G) -Z-CH ₂ -CAC = CH ₂ OH OH

in which Z is a divalent radical selected from the group consisting of H 0

t "_S- _a -N-, -CO- and -0-

consists; A is a divalent radical with 1 - 1o atoms of at least one atom selected from the group consisting of C, O, S and N; and R and R are hydrogen or alkyl radicals with 1 - 4 carbon atoms. The radicals Z are given above in the order in which they are preferred i.e. from more preferred to less preferred.

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The remainder Z is the remaining fragment that is made up of

an amine group of an amine-H terminated polymer

-N-

TJ

groups, results from a carboxyl group of

Il

Polymers with terminal carboxyl groups -C-O- yields, that results from the hydroxyl group of polymers with terminal hydroxyl groups -0- or that from the mercaptan group of polymers terminated with mercaptan groups -S- yields. The remainder A comes from a Compound containing both an oxirane group and a vinylidene group and will be described in more detail below described.

Polymers with terminal vinylidene groups made by the latter method a theoretical functionality of 2, o, i.e. a group of the formula

r5 r ⁶

1 I.

CH ₀ = CAC-CH ^ -Z-OH

at each end of the polymer molecule. The actual mean However, functionality can be from about 1.7 to about 3, preferably from about 1.7 to about 2.3 such groups

r5 r ⁶

! J

CH = CAC-CH ₂ -Z-OH

be per molecule. For example, some of the groups mentioned can also be on the side of the polymer molecules and are polymerized into the main chain G of the polymer by the reaction of the oxirane-vinylidene compound Acrylic acid or the like. educated. If the polymeric main chain G has significant amounts of polymerized Contains acrylic acid or the like, the amount of the oxirane-vinylidene compound that reacts must be limited

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so that the vinylidene-terminated polymer has an average of from about 1.7 to about 3

R ⁵ E ⁶

I!

CH = C-A C-CH -Z-

2 ι 2

OH

Contains groups per molecule in which Z, A, R ⁵ and R have the meanings given above. Up to 50 additional vinylidene groups (CH ₂ = C ^) can be attached to the main polymer chain directly or via alkylene, alkylidene or similar groups.

The polymer main chain G in the above formula is the polymer main chain of a liquid polymeric reactant (1) with functional end groups and can have carbon-carbon, polyether or polysulfide bonds. A preferred backbone has carbon-carbon bonds that comprise at least about 90% by weight of the total polymer backbone weight, and preferably at least about 95% by weight of the total polymer backbone weight. The carbon-carbon bonds contain polymerized units of at least one vinylidene monomer with at least one terminal CH ₂ = C C group and are selected. from the group of (a) monoolefins having 2-14 carbon atoms, preferably 2-8 carbon atoms, such as, for example, ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene and 1-dodecene; (b) dienes with 4-10 carbon atoms, preferably 4-8 carbon atoms, such as, for example, butadiene, isoprene, 2-isopropyl-1,3-butadiene and chloroprene; (e) vinyl and allyl esters of carboxylic acids having 2-8 carbon atoms such as vinyl acetate, vinyl propionate and allyl acetate; (d) vinyl and allyl ethers of alkyl radicals with 1-8 carbon atoms such as vinyl methyl ether and allyl methyl ether; and (e) acrylic acids and acrylates of the formula

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R O ι "

CHp = CCO- ?. ¹

in which R is a hydrogen or an alkyl radical with 1-3 Carbon atoms and R is hydrogen or an alkyl radical having 1-18 carbon atoms, preferably 1 up to 8 carbon atoms or an alkoxyalky1-, alkylthioalkyl- or cyanoalkyl radical having 2-12 carbon atoms, preferably 2-8 carbon atoms. More preferably, R is hydrogen or an alkyl radical having 1-8 carbon atoms. Examples of suitable acrylates include ethyl acrylate, butyl acrylate, hexyl acrylate, 2-iithylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, Methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, ß-cyanoethyl acrylate, cyanoctyl acrylate, Methyl methacrylate, ethyl methacrylate and octyl methacrylate ■ Latin. Often two or more types of these polymerized monomer units are contained in the main polymer chain.

More preferred liquid polymers contain polymerized units of at least one vinylidene monomer with at least one terminal CH ₂ = Cn group. The monomers are selected from the group consisting of (a) monoolefins with 2-14 carbon atoms, preferably 2-8 carbon atoms, (b) dienes with 4-10 carbon atoms, preferably 4-8 carbon atoms, and (e) acrylic acids and acrylates the formula

■ ^S ι

CH ₂ = CCOR- ¹

in which R is hydrogen or an alkyl radical with 1-3

1 ■

Carbon atoms and R is hydrogen or an alkyl radical with 1-18 carbon atoms, preferably 1 to 8 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical with 2-12 carbon atoms,

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is preferably 2-8 carbon atoms. It is even more preferred if R is hydrogen or an alkyl radical is with 1-8 carbon atoms. Excellent results have been obtained when dienes with 4 - 10 carbon atoms, preferably 4-8 carbon atoms were used.

The vinylidene monomers described above are easily 0 to about 5o wt .-%, preferably 0 polymerized to about 3o wt .-% of at least one comonomer selected from the following group is (f) vinyl aromatics of the formula

2
in which R is hydrogen, halogen or an alkyl radical having 1-4 carbon atoms, such as, for example, styrene, alpha-methylstyrene, chlorostyrene and vinyltoluene; (g) vinyl nitriles of the formula

R ³
CH ^ = CC = N

in which R is hydrogen or an alkyl radical having 1-3 carbon atoms is such as acrylonitrile and methacrylonitrile; (h) vinyl halides such as vinyl bromide and Vinyl chloride; (i) divinyls and diacrylates such as e.g. Divinylbenzene, divinyl ether and diethylene glycol diacrylate; (j) amides of alpha, ß-olefinically unsaturated Carboxylic acids with 2-8 carbon atoms such as acrylamide and (k) allyl alcohol and the like. Liquid

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Polymer compositions, the polymerized units of a major amount of at least one vinylidene monomer of the compounds (a) to (e) listed above with a smaller amount of at least one comonomer of the compounds (f) to (k) listed above are within the scope of the present invention.

More preferred comonomers are selected from the following group (f) vinyl aromatics of the formula

R ²

in which R is selected from the group consisting of hydrogen, halogen and alkyl radicals having 1-4 carbon atoms and (g) vinyl nitriles of the formula

R ³

CH ₀ = C - C = N
2.

in which R is hydrogen or an alkyl radical having 1-3 carbon atoms.

Examples of suitable liquid polymer backbones with carbon-carbon bonds include polyethylene, Polyisobutylene, polyisoprene, polybutadiene, poly (vinyl ethyl ether), Poly (ethyl acrylate) and poly (butyl acrylate) as well as copolymers of butadiene and acrylonitrile, butadiene and styrene, vinyl acetate and isoprene, vinyl acetate and chloroprene, vinyl ethyl ether and diallyl ether, vinyl ethyl ether and alpha-methylstyrene, vinyl ethyl ether and Vinyl bromide, methyl acrylate and butadiene, methyl acrylate and ethyl acrylate, methyl acrylate and butyl acrylate, Methyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and Ethylene, ethyl acrylate and isobutylene, ethyl acrylate and

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Isoprene / ethyl acrylate and butadiene, ethyl acrylate and vinyl acetate, ethyl acrylate and styrene, ethyl acrylate and Chlorostyrene, ethyl acrylate, styrene and butadiene, ethyl acrylate and n-butyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, ethyl acrylate and vinyl bromide, Ethyl acrylate and acrylic acid, ethyl acrylate and acrylamide, ethyl acrylate and allyl alcohol, butyl acrylate, '· Styrene and isoprene, butyl acrylate and styrene, butyl acrylate and acrylonitrile, and butyl acrylate and vinyl chloride.

Preferred amine-terminated liquid polymers for the purpose of making liquid vinylidene-terminated polymers are above has been described in detail.

Liquid polymers with terminal carboxyl groups can undergo free radical polymerization Use of carboxyl-containing initiators and / or modifiers as in US Pat. No. 3,285,949 and DT-PS 1 15o 2o5 and described by solvent polymerization using lithium metal or organometallic compounds and post-treatment of the Polymers for forming carboxyl groups as described in U.S. Patents 3,135,716 and 3,431,235 will. The polymers can also be prepared by using liquid polymers, the other being terminal Have groups as carboxyl groups, reacts with compounds to terminal carboxyl groups to build. For example, carboxyl-terminated polymers can be derived from liquid-terminated polymers Hydroxyl groups are produced by reacting with dicarboxy compounds or anhydrides. From it It is found that the method of preparing the liquid carboxyl-terminated polymers is not is critical. The main characteristics of the polymers

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are that they have at least terminal carboxyl groups and one polymer backbone, the carbon-carbon bonds contains.

Examples of preferred liquid carboxyl terminated polymers include terminated polyethylene Carboxyl groups, polyisobutylene with terminal carboxyl groups, polybutadiene with terminal Carboxyl groups, polyisoprene with terminal carboxyl groups, poly (ethyl acrylate) with terminal carboxyl groups and also copolymers of butadiene and acrylonitrile and of butadiene and styrene with terminal carboxyl groups. The copolymers of butadiene and acrylonitrile with terminal carboxyl groups were found to be special suitable. These polymers can contain from about 50 to about 95 weight percent butadiene, from about 5 to about 4o % By weight acrylonitrile and from about 0.5 to about 10% by weight carboxyl, based on the total polymer weight.

Liquid polymers with terminal hydroxyl groups can be produced by post-reaction of polymers with terminal carboxyl groups as described in U.S. Patents 3,551,471 and 3,551,472, by free radical polymerization of monomers under Use of hydroxyl-containing initiators as described in US Pat. No. 2,844,632 and by solvent polymerization using lithium or organometallic catalysts and post-treatment of the products to form hydroxyl groups as described in U.S. Patents 3,135,716 and 3,431,235. From this it can be seen that the method of preparing the liquid polymers having terminal hydroxyl groups is not critical. The essential characteristics of the polymers are that they have at least terminal hydroxyl groups and a polymer chain, the carbon-carbon bonds contains. Examples of preferred liquid polymers with terminal hydroxyl groups

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include hydroxyl-terminated polyethylene, Hydroxyl-terminated polyisobutylene, hydroxyl-terminated polybutadiene, polyisoprene with terminal hydroxyl groups, poly (ethyl acrylate) * with terminal hydroxyl groups and copolymers with terminal hydroxyl groups of butadiene and acrylonitrile and of butadiene and styrene. S.

Mercaptan terminated liquid polymers can be prepared by free radical poly; polymerization of monomers in the presence of _{Dixanthpgen-:} disulphide and subsequent after-reaction to form mercaptan as disclosed in US-PS 3 449 3o1 58o 83o and 3: described. Examples of preferred liquid polymers terminated with mercaptan groups include mercaptan terminated polyethylene, mercaptan terminated polyisobutyls, mercaptan terminated polybutadiene, mercaptan terminated polyisoprene, mercaptan terminated poly (ethyl acrylate), and mercaptan terminated copolymers of and acrylonitrile adolescents Butadiene and styrene. The liquid polymer reactants can have more than one type of functional group. "For example, the polymers can have terminal carboxyl groups and internal epoxy groups derived from interpolymerized units of glycidyl acrylate monomer, or the polymers can have terminal mercaptan groups and pendant carboxyl groups derived from interpolymerized units of acrylic acid are derived.

Suitable oxirane vinylidene compounds for production of the polymers with terminal vinylidene groups according to the invention have the formula

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t
CH ₀ -CAC = CHo

^x7

t ι

in which R is hydrogen or an alkyl radical with 1-4 carbon: fuel atoms, preferably hydrogen or methyl; and A is a divalent radical containing 1 to 10 atoms of at least one atom selected from the group is composed of C, O, S and N. More preferably, the compounds contain a glycidyl radical and have the formula

^R I

CH ₂ -CH ₂ -CH ₂ -DC = CH ₂

\ q / I

in which R is hydrogen or a methyl radical and D is a divalent radical containing 1-9 atoms of at least one atom selected from the group consisting of C, O, S and N, preferably 1-4 carbon atoms and / or Oxygen atoms. Examples of the preferred compounds include isopropenyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate. Glycidyl acrylate and glycidyl methacrylate are even more preferred. D is -0- when the oxirane-vinylidene compound is isopropenylglycidyl _{ether, -CH 2} -O- when the oxirane-vinylidene compound is allyl glycidyl ether or methallyl glycidyl ether and "when the oxirane-vinylidene compound is -CO-

dung is glycidyl acrylate or glycidyl methacrylate.

The carboxyl-terminated polymers described above are excellent polymeric reactants for reaction with the compound containing both oxirane groups and vinylidene groups. The liquid ones

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- Often

Carboxyl terminated polymers have an average carboxyl functionality of about 1.7 to about 3, preferably from about 1.7 to about 2.3. This means that some carboxyl groups can stand as side chains on the polymer molecules. The average Carboxy functionality can be determined by multiplying the polymer molecular weight by the equivalent parts per 100 of the carboxyl groups (ephr) can be determined. Molecular weight can be measured by having a Mechrolab vapor pressure osmometer (Mechrolab Vapor Pressure Osmometer) is used. The equivalent parts per 100 of the carboxyl groups are determined by taking the weight percentage of the carboxyl groups in the polymer determined (by titration of a polymer solution up to a Phenolphthalein endpoint using alcoholic KOH) and the number obtained by 45, the gram molecular weight a carboxyl group (-COOH) shares. The carboxyl-terminated liquid polymers can have molecular weights from about 1000 to about 6000, preferably from about 2000 to about 5000. The liquid ones Carboxyl-terminated polymers have Brookfield viscosities (measured using a Brookfield RVT viscometer at 27 ° C) of about 500 cps up to about 5oo ooo cps.

The liquid polymers with terminal carboxyl groups can with a compound containing both an oxirane group and a vinylidene group in a ratio from about 1 to about 3 equivalents and more of epoxy per equivalent of carboxyl are reacted. However that is Use of more than 3 equivalents of epoxy per equivalent of carboxyl is unnecessary for excellent results .

The reaction can be carried out in bulk, preferably using an excess of the oxirane-vinylidene compound. The reaction is preferably carried out in

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carried out in a solvent. The choice of solvent is made by the solubility of the particular one used influenced liquid polymers with terminal functional groups. Examples of common solution ' Agents include aliphatic ketones and ethers such as acetone, methyl ethyl ketone and tetrahydrofuran. More preferred are chlorinated hydrocarbons such as;

Chloroform and aromatic solvents such as benzene, toluene and xylene. It was found that j Benzene is an excellent solvent for a variety of the liquid polymers described above! with terminal functional groups.

The reaction temperature can _f from about 0 to about 2oo ° C! preferably from about 50 to about 150 ° C. The total reaction time varies directly with temperature and the amount of catalyst, but is generally from about 4 hours to about 24 hours. The reaction is preferably carried out in the absence of air or oxygen.

The carboxyl-oxirane reaction rate can be increased by using a catalyst in an amount; from about 0.05 to about 2 parts by weight, preferably from about 0.1 to about 1 part by weight of catalyst per 100 parts by weight liquid polymer with terminal functional groups are accelerated. Suitable catalysts include triphenylphosphine and p-toluenesulfonic acid.

Production of polymers with terminal vinylidene

groups - ;

The following describes the production of polymers with terminal vinylidene groups, by means of which Implementation of

(1) a diglycidyl ether of a bisphenol compound the formula

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-OH

in which R is a divalent radical containing 1-8 atoms of at least one atom selected from the Group is selected consisting of C, O, S and N, preferably an alkylene or alkylidene group having 1-8 carbon atoms, and more preferably an alkylene or alkylidene group with 1-6 carbon atoms, with (2) acrylic acid or methacrylic acid. Examples of suitable ones Bisphenols include methylenebisphenol, isopropylidenebisphenol, butylidenebisphenol, Octylidenebisphenol, bisphenol sulfide, bisphenol sulfone and bisphenol ether. Excellent results have been obtained using isopropylidene bisphenol (bisphenol A).

Polymers with terminal vinylidene groups, which according to The latter method are preferred examples of polymers of the foregoing given formula

OH

OH

■ ι 5

in which X is -0-, A is -C-O, R is hydrogen or Is methyl, R is hydrogen and the main polymer chain G is in the polyether residue of the diglycidyl ether of a bisphenol the formula

has, in which R is as defined above and η 0 to 2o, is preferably 0-2. In other words, they can be produced by the method just described

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Polymers terminated with vinylidene groups have the following formula

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-3ο-

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Γ Q

in which R is hydrogen or methyl and R and η
have the meaning given above.

The vinylidene-terminated polymers used in accordance with the invention have highly reactive vinylidene-terminated groups. Therefore they are preferably mixed with an antioxidant / to prevent premature oxidation. The antioxidant will! to about 5 parts by weight in an amount of about o _f 1, '■ pre preferably from about o, 5 up to 2 parts by weight per 1oo by weight \ parts of polymer used. Suitable antioxidants include phenyl-ß-naphthylamine, di-ß-naphthyl-p-phenylene- ■ diamine, 2,6-di-t-butylparacresol, 2,4,6-trihexylphenol,!

1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate. j

Co-vulcanized or co-hardened masses I.

The co-vulcanized masses can easily be made from one
Mixtures are prepared from (1) 100 parts by weight
at least one liquid described above
Polymers with. terminal amine groups and (2) about
8o to about 12o parts by weight, preferably about 90 to about 11o parts by weight of at least one previously described polymer with terminal vinylidene groups. the
Compounds vulcanize or cure easily at room temperature, without the addition of a catalyst or a
Crosslinking agent. So can be a desired high
Main chain weight concentration can be obtained without
Dilution with unnecessary reactive third ^{consideration:} components and without undesirable side reactions; caused by some catalyst residues or crosslinkers ^[ . The new compounds according to the invention are suitable as sealing compounds, sealing compounds, investment compounds and the like.

In addition to the two essential components previously described (an amine-terminated liquid polymer and a vinyli-terminated polymer 709807/1250

dengruppen), the co-hardened compositions can contain a wide range of other processing materials. These substances are typical ingredients that are used in the processing of sealants and sealants. The usual standard amounts of these ingredients are used, which are well known to those skilled in the art. A preferred limit on the amounts of processing ingredients is that the compositions containing them should be flowable without substantial sagging or sagging at temperatures from about 20 to about 100 ° C. This generally limits the amount of reinforcing fillers and other ingredients which will thicken the liquid compositions from low levels up to about 50 parts by weight at room temperature per 100 parts by weight of co-cured composition. If a ^; Plasticizers such as dioctyl phthalate are used _: higher amounts of processing aids can be used. The components of the masses can be mixed using mixing kettles, Hensehe! Mixers, printing ink rollers (ink mills), Banbury mixers and the like. Standard mixing techniques can be used and no particular order of addition is required.

Examples of processing ingredients include reinforcing fillers such as carbon blacks, metal carbonates and metal silicates, glass, asbestos and textile fibers, coloring agents such as metal oxides and metal sulfides and organic dyes, lubricants and lubricants and plasticizers such as petroleum-based oils, .Castor oil, glycerin, silicones, aromatic and paraffinic Oils, alkyl and aromatic phthalates, sebacates and trimellites and antioxidants and stabilizers such as phenyl-ß-naphthylamine, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-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-hydroxy-

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benzyl) isocyanurate, hexahydro-1, 3,5-tris-ß- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyltriazine, Tetrakis-methylen-3 (3 ', 5' -di-t-butyl-4'-hydroxyphenyl) propionate methane, Distearyl thiodipropionate and tri (nonylated phenyl) phosphite.

The following examples further illustrate the present invention.

Examples
Materials:

The amine-terminated polymers and terminated polymers used in the following examples Vinylidene groups are easily produced by the following procedures detailed above have been described. The liquid polymers used were as follows:

(1) A liquid poly (butadiene / acrylonitrile) terminated Amine groups, referred to as ATBN, had a butadiene content of about 67.2 wt .- ^ of the polymer, an acrylonitrile content of about 16.4 percent by weight of the polymer and an amine end group content of about 13.4% by weight of the polymer and a Brookfield viscosity at 27 ° C of about 270,000 cps and a molecular weight of (M-) of about 3556. The ATBN was prepared by reacting N- (2 ~ aminoethyl) / - piperazine with a liquid carboxyl-terminated polymer in a reaction leading to terminal amine groups, prepared by the method described above.

(2) A vinylidene-terminated poly (butadiene / acrylonitrile) called VTBN had one Butadiene content of about 69.5% by weight of the polymer, an acrylonitrile content of about 16.2% by weight of the polymer Polymers and a vinylidene end group content of about 14.3% by weight of the polymer and a Brookfield

7098Ü7 / 1 250

viscosity at 27 ° C of about 320,000 cps and a molecular weight (M-) of about 3556. The VTBN was by reacting glycidyl acrylate with a liquid carboxyl-terminated polymer such as prepared as described above.

(3) A diacrylate ester of diglycidyl ether of bisphenol A was used. The diacrylate ester is given below referred to as compound D and was used as a 55% strength by weight solution in styrene, the Solution had a viscosity of about 500 cps and a specific gravity of about 1.04.

All other processing ingredients used in the following examples are known, commercially available materials and readily available.

Example 1

The following recipe was used: material parts by weight

ATBN 5ο

VTBN 5ο

Dioctyl phthalate 5o.

The new co-cured compositions were prepared as follows: All materials were placed in a 19 ounce & 2 jug and stirred vigorously with a spatula for 35 minutes at room temperature (about 25 ° C). The mixture was then poured into a Teflon-coated pan and left to harden at room temperature. A soft cured product suitable for sealing compounds was obtained in about 17 days depending on the processing additives. Examples were removed from the pan at this time and examined immediately.

The mass was measured to durometer using 709807/1250

of a Shore type durometer A and a loose indentation hardness time interval. The 3oo% module! the tensile strength and the elongation at break were determined according to ASTM D-412-68 using dumbbell test pieces (Die ■ C dumbbells). The percentage set was tested at 25 ° C by placing a 1/8 "χ 1/4"

χ 3 "sample stretched to 2oo% and at the same time 2. \

Minutes after which the sample was released j

and left to rest for 2 minutes before being | has been checked. The test results are in Table I.

listed:;

Table I. Test results

Durometer A hardness

(immediately / 10 seconds) 5/0

Elongation at break% at 25 ° C 1100%

Deformation rest,% 25

The physical test data show that the co-cured composition according to the invention has a good balance having physical properties that make them suitable for use as a sealant and Sealing compound makes.

Example 2

The following two parts Recipe was used material Weight .-Parts Recipe 1 recipe 2 ATBN 5o - VTBN - 5o Dioctyl phthalate 25th 25th Calcium carbonate powder 13o 13o Thickener 1o 1o

Each of these approaches was separated by violent 709807/12 50

Mix mixed with a spatula for 3 minutes. Immediately thereafter, both approaches were converted into a 19 ounce
^ 2 jug and vigorously stirred for 3-5 minutes at room temperature. The mass was reduced to durometer hardness; Use of a Shore-type durometer A and a loose-! oral impression hardening time interval checked. The ; Durometer A hardness after 2 days was 6/0 (immediately / 1 ο
Seconds) and after 7 days 12 / o (immediately / 1 ο seconds). j The co-hardened mass showed a soft, sticky hardening between 3 and 16 hours after mixing and
was for use as a sealing and sealing | suitable for mass. j

Example 3

material D (55% by weight
Styrene) Parts by weight ATBN 6o link
Solution in 1oo ^x)

x) total weight of component D and styrene

The new co-cured compositions were prepared as follows: Both materials were placed in a 19 ounce "^ jug and vigorously stirred with a spatula for 10 minutes at room temperature (about 25 ° C). The mixed
Sample was divided into 2 parts and each sample into one
poured separate pan. A trial was about 48
Cured for hours at room temperature and developed a soft, sticky cure that made it suitable for use as an embedding, sealing or sealing compound. The second sample was cured first at 70 ° C for 2 hours and then at 12o ° C for 2 hours, resulting in a
cheese-like rubber with a non-sticky surface.

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Claims (1)

Claims Masses containing
(1) 100 parts by weight of at least one liquid polymer with terminal amine groups, which is an average! contains from about 1.7 to about 3 amine groups per molecule, the amine groups being primary and / or secondary! and the polymer is the formula! ο ο; Il I! Y-C-4-B-4-C-Y; in which Y is a monovalent radical which, by removing hydrogen from an amine group, is a aliphatic, alicyclic, heterocyclic or aromatic amine with 2 - 2o carbon atoms and at least two amine groups, at least two of the amine groups being primary and / or secondary and _B is a polymer backbone containing carbon-carbon bonds, and (2). about 8o to about 12o parts by weight of at least one; Polymers with terminal vinyl groups of the formula _R 5 riS ro r5 ^; CH ₂ = CAC-CH ₂ -ZfGfZ-CH ₂ -CAC = CH ₂ OH - OH HO I H I in which Z is selected from the group consisting of -S-, -N-, -CO and -0-, A is a divalent radical containing 1-10 atoms of at least one atom selected from the group consisting of C, O, S and N, R ⁵ and R ^{6 are} hydrogen or alkyl radicals with 1-4 carbon atoms, and G is a polyether or polysulfide polymer main chain or a polymer main chain which is carbon-carbon | 709807/1250 contains bonds, and the vinylidene-terminated polymer has an average of about 1.7 to about 3 _ CH ₂ = CAC-CH ₂ -Z- OH
Contains groups per molecule, wherein the main chain containing carbon-carbon bonds contains polymerized units of at least one vinylidene monomer which contains at least one terminal CH ₂ = C \ group and is selected from the group consisting of (a) monoolefins with 2-14 carbon atoms, (b) Serving with 4 - 10 carbon atoms, < (c) Vinyl and allyl esters of carboxylic acids with 2-8 Carbon atoms (d) vinyl and allyl ethers of alkyl radicals with 1-8 carbon atoms and (e) Acrylic acids and acrylates of the formula RO ^! " 1
. CH ₂ = CCOR, in which R is hydrogen or an alkyl radical with 1-3 Carbon atoms and R is hydrogen, an alkyl radical with 1-18 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical with 2-12 Is carbon atoms. 2. Composition according to claim 1, wherein the carbon-carbon bonds make up at least 9o wt .-% of the total weight of the polymer main chain and the vinyl ^! lidenmonomer is selected from the group consisting of (a) monoolefins with 2-8 carbon atoms, (b) dienes having 4-8 carbon atoms and (e) acrylic acids and acrylates of the formula 709807/1250 R O t "1
CH ^ CCO-IT ₅
2 in which R is hydrogen or an alkyl radical with 1-3 carbons · ^ ι
material atoms and R is hydrogen, an alkyl radical with 1-8 carbon atoms or an alkoxyalkyl, alkylthioralkyl or cyanoalkyl radical with 2-8 carbon atoms' is. 3. Composition according to claim 2, wherein the vinylidene mono-; up to about 50% by weight copolymerizes less with it ι contains at least one comonomer which is selected from the group consisting of
(f) vinyl aromatics of the formula in which R is hydrogen, halogen or an alkyl radical having 1-4 carbon atoms is (g) vinyl nitriles of the formula CH ₂ = CC = N in which R is hydrogen or an alkyl radical with 1 - 3! Carbon atoms is, ι (h) vinyl halides, j (i) divinyls and diacrylates, (j) Amides of alpha-ß-olefinically unsaturated carboxylic acids with 2-8 carbon atoms and 709807/1250 (k) allyl alcohol. ''. 4. Compounds according to claims 1-3, wherein the amine groups of the amine have different reactivity, and the comonomer from the group consisting of (f) vinyl aromatics and (g) vinyl nitriles is selected. 5. compositions according to claims 1-4, wherein the amine j is at least one N- (aminoalkyl) piperazine its amino; alkyl groups contain 1-12 carbon atoms, the vinylidene monomer at least one of the said dienes; and the comonomer is at least one of the above; Is vinyl nitrile. [ 6. Compositions according to claim 5, wherein the amine is N- (2-; aminoethyl) piperazine, the vinylidene monomer butadiene; and the comonomer are acrylonitrile. 7. The compositions of claim 1, wherein the carbon-carbon bonds make up about 9o wt .-% of the total weight of the polymeric main chain B and that Vinylidene monomer is selected from the group consisting of (a) monoolefins with 2-8 carbon atoms, (b) Serving with 4-8 carbon atoms and (e) acrylic acids and acrylates of the formula R 0
CH ^ CCOR ¹ J in which R is hydrogen or an alkyl radical with 1-3 carbon atoms and R is hydrogen, an alkyl radical with; 1-8 carbon atoms or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical with 2-8 carbon atoms. , 8. The compositions of claim 7 wherein the vinylidene monomer copolymerizes therewith up to at least about 50 weight percent contains a comonomer selected from group 709807/1250 is selected which consists of (f) vinyl aromatics of the formula in which R is hydrogen, halogen or an alkyl radical 1 -. Is 4 carbon atoms, (g) vinyl nitriles of the formula CH = C-C = N 9. Compounds according to claims 1-8, wherein Z is -O-, O "5 6 -C is -O-, R is hydrogen or methyl and R is water is substance and the main polymer chain G is a polyether residue of the diglycidyl ether of a bisphenol with the formula ^; 0-CH ₂ -CH-CH ₂ -O is, in which R is a divalent radical containing 1 - 8 atoms of at least one atom selected from the group is selected consisting of C, O, S and N, and η is 0 to 2o. 1o. Compositions according to claims 1-9, wherein the amine groups of the amine have different reactivities have, the comonomer is selected from the group consisting of (f) vinyl aromatics and (g) vinyl nitriles, R is an alkylene or alkylidene radical with 1-8 709807/1250 Carbon atoms and η are 0 to 2. 11. masses according to claims 1 - 1o, wherein the amine N- (2-AminoäthyUpiperazin, the vinylidene monomer buta- diene, the comonomer acrylonitrile and R an isopropylidene radical are. 12. Hardened compositions according to claims 1-11. 709807/1250