DE2643504A1 - METHOD OF COATING DRY OR WET SURFACES OR SURFACES SUBMERGED IN WATER - Google Patents

Description

Paints and coating materials which cure under water are known (Drisko "Paint and Varnish Production ", Vol. 58 (1968) 31). These paints and coating materials generally contain terminal amine-substituted polyamide resin and a liquid epoxy resin. However, they cure fairly slowly and have mediocre bond strength and flexibility. New paints that harden under water are desirable and coating materials with improved curing speed, adhesive strength and flexibility.

The invention relates to mixtures of a terminally amine-substituted liquid polymer and one non-cycloaliphatic epoxy resin that is applied to substrates applied and cured under water. The mixtures contain

A) 100 parts by weight of at least one non-cycloaliphatic Epoxy resin and

Telephone: (02 21) 23 4541 - 4 'TVfe> f? 8M 2307 ^ ofa V · fel ^ rMim:

Dotnpalent Cologne

B) about 1 to 2000 parts by weight of at least one terminal amine-substituted liquid polymer containing a C-C polymer main chain.

Final amine-substituted liquid polymers

The terminally amine-substituted liquid polymers suitable for the purposes of the invention have the formula _QQ

H Il

Y-C () C-Y j

wherein Y is a monovalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two primary and / or secondary amine groups, and B is a polymer backbone containing CC bonds . In general, the CC bonds make up at least about 90% by weight, preferably at least 95% by weight, of the total weight of the polymer backbone. The terminally amine-substituted polymers contain on average about 1.7 to 3 primary and / or secondary amine groups, preferably on average about 1.7 to 2.3 primary and / or secondary amine groups in the molecule. The terminal amine-substituted polymers can Brookfield viscosities up to 2 500 000 cps, preferably from about 500 to 500,000 cps / measured with a Brookfield RVT viscometer at 27 ⁰ C, have from about 500th

The terminally amine-substituted liquid polymers can be easily obtained by reacting terminal carboxyl groups or terminal ester groups liquid polymers containing a C-C main chain with at least one aliphatic, alicyclic or heterocyclic amine containing at least two primary and / or secondary amine groups. Terminal amine-substituted liquid polymer

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sate can also by reaction of terminal acid chloride-containing liquid polymers that have a Contain C-C main chain, with at least one aliphatic, alicyclic, heterocyclic or aromatic Amine containing at least two primary and / or secondary amine groups can be easily prepared. ;

The liquid used for the purposes of the invention; Polymers with terminal carboxyl groups can have Brookfield viscosities of about 500 to 500,000 cPs, preferably from about 500 to 250,000 cFs, and contain main polymer chains which contain CC bonds. The functional carboxyl groups are located at least at the ends of a polymer molecule, but _may: also contain one or more additional groups pendent be present in a polymer main chain. 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 polymers containing terminal carboxyl groups and containing C-C main chain bonds can ί polymerized units contain at least one vinylidene monomer which has at least one terminal group of the formula CHp = CtT and from the following group ' is selected:

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) Serves with 4 to 10 carbon atoms, preferably with 4 to 8 carbon atoms, e.g. butadiene, isoprene, 2-isopropyl-l, 3- -: butadiene and chloroprene;

c) Vinyl and allyl esters of carboxylic acids with 2 to 8 carbon atoms, e.g. vinyl acetate, vinyl propionate and allyl

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acetate;

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

e) Acrylic acids and acrylates of the formula

R O

'·' 1 CH ₂ = CCOR,

wherein R is hydrogen or an alkyl radical with 1 to 3

1
Carbon atoms, R 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, 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, ethyl methacrylate and octyl methacrylate. Often, two or more types of these polymerized monomer units are contained in the main polymer chain.

Liquid polymers containing polymerized units of at least one vinylidene monomer are particularly preferred contain, which contains at least one terminal group of the formula CHp = Ci ^ and from the following group is selected;

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

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e) Acrylic acids and acrylates of the formula

R O

ι ti -1

CH ₂ = CCOR,

wherein R is a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms and R is hydrogen or an alkyl radical with 1 to 18 carbon atoms, preferably with 1 to carbon 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 acrylates in which R ■ is hydrogen or an alkyl radical with 1 to 3 carbon atoms is particularly preferred will.

Excellent results have been obtained with dienes containing up to 10 carbon atoms, preferably 4 to 8 carbon atoms.

The vinylidene monomers described above may _be: easy to polymerize to 0 to 5o wt .-% _f preferably 0 to 35 wt .-% of at least one of the following comonomers.

f) vinyl aromatics of the formula

2
wherein R is hydrogen, halogen or an alkyl radical with

1 to 4 carbon atoms, e.g. styrene, α-methylstyrene, Chlorostyrene and vinyl toluene;

g) vinyl nitriles of the formula

CH ₂ = CC = N

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where R " ^{1 is} hydrogen or an alkyl radical having 1 to 3 carbon atoms, for example acrylonitrile and methacrylonitrile;

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

i) Divinyls and diacrylates, e.g. divinylbenzene, divinyl ether and dietary glycol diacrylate;

j) amides of α, ß-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

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
CH ₀ = CC = N.

where R is hydrogen or an alkyl radical having 1 to 3 carbon atoms. Excellent results have been taken Use of styrene and acrylonitrile obtained.

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Examples of suitable liquid polymer main chains which contain CC bonds include: polyethylene, polyisobutylene, polyisoprene, polybutadiene, vinyl ethyl ether polymers, ethyl acrylate polymers and butyl acrylate polymers, and copolymers of butadiene and acrylonitrile, butadiene vinyl / styrene copolymers, vinyl isopropyl acetate, vinyl vinyl / styrene copolymers, vinyl isoprene / isoprene copolymers, vinyl butadiene / styrene copolymers, vinyl isoprene copolymers, vinyl isoprene copolymers, polybutadiene, polyisoprene copolymers Copolymers, vinyl ethyl ether / diallyl ether copolymers, vinyl ethyl ether / oc-methylstyrene copolymers, vinyl ethyl ether / vinyl bromide copolymers, methyl acrylate / buttadiene copolymers, methyl acrylate / ethyl acrylate / tert-copolymers, methyl acrylate / butyl acrylate copolymers of methyl acrylate / 2-ethylhexyl acrylate copolymers, Athylacrylat / ethylene copolymers, ethyl acrylate / isobutylene copolymers, ethyl acrylate / isoprene copolymers, Xthylacrylat / butadiene copolymers, Athylacrylat / vinyl acetate copolymers, Xthylacrylat / styrene copolymers, Xthylacrylat / chlorostyrene Copolymers, ethyl acrylate / Styrene / butadiene copolymers, ethyl acrylate / n-butyl acrylate copolymers, ethyl acrylate / n-butyl acrylate / 2-ethylhexyl acrylate copolymers7 ~ ethyl acrylate / a-ethylhexyl acrylate copolymers / a-ethylhexyl acrylate copolymers / ethylhexyl acrylate copolymers, ethylhexyl acrylate copolymers, ethylhexyl acrylate copolymers, acrylate copolymers, ethyl acrylate copolymers, acrylate copolymers, ethyl acrylate copolymers, ethyl acrylate copolymers, ethyl acrylate, vinyl acrylate copolymers, ethyl acrylate , Ethyl acrylate / acrylamide copolymers, ethyl acrylate / allyl alcohol copolymers _f 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 may be prepared by free radical polymerization using carboxyl-containing initiators and / or -modifizierenden agents on the ^in: US-PS 3,285,949 and in the DT-PS manner described 1,150,205 and by solution polymerization using lithium metal or organometallic compounds and post-treatment

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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 Containing hydroxyl groups, are prepared by reaction with dicarboxyl compounds or 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 carboxyl groups-containing polyisobutylene, terminal carboxyl groups containing polybutadiene, terminal carboxyl group-containing polyisoprene, terminal carboxyl groups Ethyl acrylate polymer containing and copolymers containing terminal carboxyl groups 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 can be about 50 to 99.6 wt .-% butadiene, about 0 to 40 wt .-% acrylonitrile or styrene and about 0.4 to

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10% 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 acid catalysts For example, organic acids with 1 to 12 carbon atoms, preferably with 1 to 8 carbon atoms, are suitable, e.g. acetic acid, propionic acid, benzoic acid, monoesters and diesters of orthophosphoric acid, alkarylsulfonic acids, e.g. p-toluenesulphonic acid, inorganic acids, e.g. Boric acid, Hydrochloric acid, phosphoric acid and sulfuric acid, and Lewis acids such as tetraisopropyl titanate. It is sufficient already a lot of the acidic catalyst of about 0.01 to 5 wt .-%, based on the total weight of the Respondents. Aliphatic monohydric alcohols are also suitable for the esterification reaction 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms, and boiling points below about 150 ° C, preferably below about 100 ° C. Aliphatic monohydric alcohols are preferred. Suitable as aliphatic monohydric alcohols are for example alkanols with 1 to 6 carbon atoms, e.g. methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-hexanol and 3-hexanol. Other suitable aliphatic ' Monohydric alcohols are, for example, 2-methoxyethanol and 2-ethoxyethanol. Excellent results can ' .With ethanol,! —propane oil or 1-butanol.

The liquid polymers with terminal carboxyl · _; groups can be acylated according to known methods in order to convert liquid polymers with terminal acid chloride

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JfL

to form groups. For example, a terminal Polymer containing carboxyl groups with thionyl chloride to form a polymer with acid chloride end groups implemented. HCl and SO "are mainly used as Gases develop and can be easily separated from the polymer with acid chloride end groups. Any excess Thionyl chloride can be obtained by vacuum distillation or by washing with a solvent, e.g. Methanol, easily remove. Phosphorus trichloride and phosphorus pentachloride are also suitable, but will less preferred as acylating agent.

The amines which react well with the polymers described above with terminal carboxyl groups, terminal ester groups and terminal acyl radicals include aliphatic amines with 1 to 20 carbon atoms, preferably with 1 to 12 carbon atoms and at least two, preferably two primary and / or secondary amine groups. Also suitable are alicyclic amines with 4 to 20 carbon atoms, preferably with 4 to 12 carbon atoms and at least two, preferably two, primary and / or secondary amine groups. Heterocyclic amines which contain 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 are: aliphatic amines, for example 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 _f 8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine; aliphatic polyamines, for example diethylenetriamine, triethylenetetramine, tetraethylene pentamine, bis (hexamethylene) triamine and S ^ '- iminobispropylamine; alicyclic diamines and polyamines, e.g. 1,2-diaminocyclohexane and 1,8-p-menthediamine, and heterocyclic diamines and polyamines, e.g. 4- (aminomethyl) piperidine, piperazine, N- (aminoalkyl) piperazines with 1 to 12 carbon atoms

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men, preferably with 1 to 6 carbon atoms in each alkyl \ radical, for example N- (2-aminoethyl) piperazine, N- (3-aminopropyl) -; piperazine and N, N'-Eisi3-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 reactivities makes the reaction of the addition of terminal amine groups more likely than the coupling of the liquid polymers, and a smaller excess of amine can be used to avoid the coupling. The particularly preferred amines include, for example, some alicyclic amines, for example 1,8-p-menthediamine, and some heterocyclic amines, for example 4- (aminomethyl) piperidine and N- (aminoalkyl) piperazines with 1 to 12 carbon atoms, preferably with 1 to 6 carbon atoms in the alkyl radical, for example N- (2-aminoethyl) piperazine and N- (3-aminopropyl) piperazine. Excellent results have been obtained using N- (2-aminoethyl) piperazine,

Aromatic diamines and polyamines can be used to produce terminally amine-substituted polymers. The high temperature required for the implementation of the aromatic amine with polymers having terminal carboxyl groups, cause higher than normal '' severe degradation of reactants and products and is therefore far less preferred. On the other hand ^! aromatic amines react well with the above-mentioned: Polymers with terminal acyl radicals. Aromatic amines which contain at least two primary or secondary amine groups which are bonded directly to at least one aromatic ring are suitable. Examples of suitable aromatic amines are 4,5-acenaphthenediamine, 3,5-diaminoacridine, 1,4-diaminoanthra-

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quinone, 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 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, ζ.B. ■ ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate and ethyl propionate. Aromatic compounds of the formula

4th
wherein R is hydrogen, halogen or an alkyl radical with

1 to 3 carbon atoms and at least two of the radicals R Are hydrogen are also suitable as solvents and are particularly preferred. Preferably R is Hydrogen, chlorine or an alkyl radical having 1 to 2 carbon atoms, at least three of the radicals R being hydrogen are. 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

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Λ *

described amines can be reacted with one of the liquid polymers described above with carboxyl end groups, ester end groups or acid chloride end groups to produce a terminal amine-substituted liquid polymer containing about 1.7 to 3 primary and / or secondary amine groups in the molecule . In general, the average number of total carboxyl, ester or acid chloride groups in a liquid polymer prior to the reaction is from about 1.7 to 3 groups per molecule, preferably from about 1.7 to 2.3 groups per ″ molecule. In this typical case, j about 1.2 to 6 molar equivalents and more, preferably about 1.2 to 3 molar equivalents, of at least one of the abovementioned amines are used per molar equivalent of the carboxylated, esterified or acylated liquid polymer described above esterified or acylated · liquid polymer also substantial amounts of acrylic acid, acrylates or the like. copolymerized form, the amount of unreacted amine must be limited so that the terminally amine-substituted polymer liquid is not more than an average of 1.7 ^ to 3 primary and / or contains secondary amine groups in the molecule.

A catalyst is not required and various types of mixing devices can be used for the amine-terminated reaction. For example, simple mixers including the turbine stirrer and propeller mixers can be used. The reaction components can be combined in any order. The reaction mixture to a temperature of about 80 heated to 15O ⁰ C j (or, if a solvent is used, heated at reflux) will, wherein the time is generally about 1 to 6 hours. The terminally amine-substituted liquid polymers can be

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distillation or washing with a solvent such as a benzene-methanol mixture and then Drying the polymer are cleaned. The amine content of the terminally amine-substituted liquid polymers can be analyzed qualitatively by infrared spectroscopy. The amine content can also according to the Method described by Siggia in "Quantitative Organic Analysis via Functional Groups", Wiley and Sons, Inc., 1963, Pages 452 to 456, can be quantified.

Underwater hardening of non-cycloaliphatic epoxy resins and terminally amine-substituted liquids Polymers

Contain the paints and coating materials used in the method according to the invention

A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin of the type described below and

B) about 1 to 2000 parts by weight of at least one terminally amine-substituted liquid polymer of type described above.

The properties of paints and coating materials can be made by using different amounts of the terminally amine substituted liquid Polymer can be varied within wide limits. Chain extenders, crosslinking agents and hardeners, the described below can also be used in the epoxy resin compositions, but are not necessary.

The non-cycloaliphatic epoxy resins, which in the context of the invention together with the terminally amine-substituted liquid polymers can be used contain an average of at least about 1.7 epoxy groups, preferably about 1.7 to 3.0 epoxy

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groups per molecule, with about 1.7 to 2.3 epoxy groups in the molecule being particularly preferred. The non-cycloaliphatic Epoxy resins can be liquids or low melting point solids, however liquids will with a Brookfield viscosity (bulk viscosity) of about 1θΟ to 2,000,000 cPs (measured with

a Brookfield RVT viscometer at 25 ° C) is preferred. > The epoxy resins can have an epoxy equivalent weight (g-molar weight per epoxy group) of about 70 to 6000, preferably of about 70 to 2000. Suitable non-cycloaliphatic epoxy resins are, for example, epoxidized cyclic silane, epoxidized soybean oil, polyglycidyl esters of polycarboxylic acids, epoxidized polyolefins and glycidyl ether resins, with glycidyl ether resins being preferred. Examples of suitable polyglycidyl esters of polycarboxylic acids are the diglycidyl ester of dimeric linoleic acid and the triglycidyl ester of trimeric linoleic acid. Suitable glycidyl ether resins are, for example, the polyallyl glycidyl ether, the diglycidyl ether of chlorendic diol, the diglycidyl ether of dioxanediol, the diglycidyl ether of endomethylene cyclohexanediol, epoxy novolak resins, alkanediol diglycidyl ether and alkanediol triglycidyl ether.

More preferred glycidyl ether resins include alkanediol diglycidyl ethers of the formula

CH -CH-CH

• 0-X

-0-CH -CH-CH

wherein X is an alkylene or alkylidene radical with 1 to 10 carbon atoms, preferably with 2 to 6 carbon atoms and h represents a number from 1 to 25, preferably from 1 to 15. Suitable alkanediol diglycidyl ethers are, for example Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and butanediol diglycidyl ether.

Further particularly preferred glycidyl ether resins are

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for example the alkanetriol triglycidyl ethers with 2 to 10, preferably with 3 to 6 carbon atoms in the alkane radical, for example the glyceryl triglycidyl ether and the triglycidyl ether of trimetlylolpropane. Another particularly preferred class of Glycidylätherharzen form the diglycidyl and polyglycidyl ethers of bisphenols, wherein _the: bisphenols of the formula

have, in which R is a divalent radical with 1 to 8 C and / or 0 and / or S and / or N atoms, preferably an alkylene or alkylidene radical with 1 to 8 carbon atoms, in particular an alkylene or alkylidene radical with 1 to 6 carbon atoms. Examples of suitable bisphenols are methylenebisphenol, isopropylxdenebisphenol, butylidenebisphenol, Octylidenebisphenol, bisphenol sulfide, bisphenol sulfon, bisphenol ether and bisphenolamine. Excellent honors Results were obtained with isopropylidene bisphenol (bisphenol A). Examples of suitable diglycidyl and polyglycidyl ethers are those of isopropylidenebisphenol of the formula

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on

ο — oö

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where η has a value from about 0 to 2O, preferably from has about 0 to 2.

Cycloaliphatic epoxy resins are far less preferred for the process according to the invention because they are in Mixture with a terminal amine-substituted liquid polymer practically not curable at room temperature are. Cycloaliphatic epoxy resins are to be understood as meaning resins in which an epoxy group is itself part of a cycloaliphatic ring structure is. Examples of such cycloaliphatic resins are bis (2,3-epoxycyclopentyl) ethers, Dicyclopentadiene dioxide, the ice-cepoxydicyclopentyl) ether of ethylene glycol, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexane carboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. Further cyclo- 'aliphatic resins are by Lee and coworkers in "Handbook of Epoxy Resins", McGraw-Hill Book Company, New York 1967, Chapter 4.

Other reactive additives are in the paints and coating materials that are a terminal Amine-substituted liquid polymer and an epoxy resin are not required, but chain extenders can be used and / or crosslinking agents can be used. The amount of chain extender used and / or Crosslinking agent can be used depending on the weight ratio and the reactive functionalities of the epoxy resins and terminally amine-substituted liquid polymers are within wide limits. It also depends on the desired properties of the paints and coating materials according to the invention. In general the amount of chain extender and / or crosslinking agent is about 0 to 60 parts by weight, preferably about 0 to 35 parts by weight per IOD part by weight of epoxy resin.

Suitable as a chain extender and / or crosslinking agent

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are all difunctional materials known to those skilled in the art to be reactive with epoxy compounds are, for example, dibasic acids such as azelaic acid and phthalic acid, and dimercaptans such as 1,6-hexanedithiol and 1,8-octanedithiol. Suitable as a chain extender also include, for example, anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride and Hexahydrophthalic anhydride, diisocyanates, e.g. 4,4'-dicyclopentylmethylene diisocyanate, 4,4'-diphenylmethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 1,4-phenylene diisocyanate, diamines and polyamines, which are detailed above in connection with the Preparation of the terminal amine-substituted liquid polymers have been described, e.g. that by reaction made from dimeric linoleic acid with a diamine Diamine, ethylenediamine, N- (2-aminoethyl) piperazine, and aliphatic dihalides with 1 to 12 carbon atoms, preferably aliphatic dihalides with 1 to 8 carbon atoms and contain bromide and / or chloride as halide, e.g. 1,4-dibromobutane, 1,3-dibromobutane, 1,4-dichlorobutane, 1,2-dichloroethane, 1,4-diiodobutane and 1,6-dichlorohexane.

Suitable as chain extenders and / or crosslinking agents'

furthermore, the special for the purposes of the invention. preferred aromatic compounds with two OH groups

with 6-24 carbon atoms, preferably with 6-18 carbon atoms. ! Examples of suitable aromatic compounds are

Catechin, resorcinol, 3-hydroxybenzyl alcohol, 4-hydroxy-!

benzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxy- -!

naphthalene, 1,7-dihydroxynaphthalene and the particularly ', preferred bisphenol of the formula!

wherein R is a divalent radical having 1 to 8 atoms from the group consisting of C, 0, S and N atoms

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contains, preferably an alkylene radical or alkylidene radical having 1 to 8 carbon atoms, with alkylene or alkylidene radicals having 1 to 6 carbon atoms being particularly preferred. Examples of suitable bisphenols are methylenebisphenol, isopropylidenebisphenol, butylidenebisphenol, octylidenebisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether and bisphenolamine. Excellent results have been obtained using isopropylidene bisphenol ^bis phenol A).

Crosslinking or hardening agents can be used to stop the reaction between the epoxy resin and the terminal to accelerate and / or complete the amine-substituted liquid polymer described above: permanent, but not required. Examples of suitable crosslinking agents and hardeners are BF ^ amine complexes, hexahydrophthalic anhydride, dicyandiamide, Imidazoles, e.g., 2-ethyl-4-methylimidazole and triethylenetetraamine.

The paints and coating materials can apart from the two essential components (a terminally amine-substituted liquid polymer and an epoxy resin) and the two optional components (a chain extender or a hardener), which have been described above contain a wide variety of other components of the mixture. this are the typical ingredients used in compounding rubber and / or epoxy resins. These ingredients are used in the usual concentrations, which are well known. For example can reinforce fillers and other ingredients that thicken the liquid mass, in concentrations up to about 250 parts by weight and more at room temperature per 100 parts by weight of the mixture of epoxy resin and terminal amine-substituted liquid polymer can be used.

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Examples of possible mixing additives include: Reinforcing fillers, e.g. carbon blacks, metal carbonates and silicates and glass, asbestos and textile fibers, non-reinforcing fillers, e.g. titanium dioxide and Silica, dyes, e.g., metal oxides and metal sulfides, and organic dyes, lubricants and Plasticizers, e.g. oils from petroleum, castor oil, glycerine, silicones, aromatic and paraffinic oils and alkyl and aromatic phthalates, sebacates and trimellitates, and antioxidants and stabilizers, e.g. phenyl-ßnaphthylamine, 2,6-di-t-butyl-p-cresol, 2,2'-methylene ' bis (4-ethyl-6-t-butylphenol), 2,2 · -Thiobis- (4-methyl-6- | t-butylphenol), 4,4'-butylidene-bis-Ce-t-butyl-m-cresol), Tris- (3,5-di-t-butyl-4-hydroxybenzy1) isocyanurate,: Hexahydro-1,3,5-tris-ß- (3,5-di-t-buty1-4-hydroxyphenyl) - ι propionyltriazine, tetrakis-methylene-3 (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate methane, BistearyIthiodipropionate and TrMnonylated phenyl) phosphite. Wetting agents such as blown fish oil and the like can also be used. As further suitable ingredients in the mixture For example, there are poisonous antifouling agents such as bis (tri-n-butyltin) oxide described in U.S. Patent 3,426,473 to be described in question «

Those suitable for the method according to the invention Epoxy resin compositions contain A) at least 100 parts by weight one of the non-cycloaliphatic described above Epoxy resins, B) about 1 to 2000 parts by weight, preferably about 300 to 1500 parts by weight of at least one of terminal amine-substituted liquid polymers described above, C) optionally a chain extender and / or a crosslinking agent, D) optionally a curing agent and E) optionally others Mixture constituent that have been described above. The components of the paint and coating ι materials can be mixed in mixing kettles, Henschel mixers, paint mills, Banbury mixers, and the like.

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Usual mixing methods can be used. If a curing agent is used, it is preferably first mixed with the terminally amine-substituted liquid polymer. The useful life of the underwater curing paints and coating materials is generally about 2 to 4 hours. Heating the mixture up to about 100 ^° C. can be advantageous in order to achieve dissolution and uniform dispersion of the materials, but this heating causes the coating materials to cure much more quickly.

A wide variety of substrates can be coated with the above-described, underwater-curing paints and Coating materials are coated, cemented, sealed, repaired, etc. To these substrates include 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 and polychloroprene. as other substrates are isoprene / isobutylene rubbers (butyl rubber), copolymers of conjugated Serving with lower alkyl and alkoxy acrylates, ethylene / propylene / diene polymers (EPDM) and polyurethanes, as described, for example, in U.S. Patents 2,871,218 and 2,899,411. As another suitable Wood, concrete, stainless steel, glass, ceramic tiles, tin and antifouling coatings are used on substrates Questions such as those described in U.S. Patent 3,426,473.

The underwater surfaces or substrates to be coated with the coating materials described above are preferably cleaned prior to application of the compound in order to ensure that the compounds adhere to the surfaces or to improve substrates. Rust, growth, oil and other impurities should be as complete as possible.

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dig to be removed. Well-known cleaning methods such as sandblasting, treatment with a wire brush, blasting '. with water and sanding by hand can be applied. To repair a damaged area of a coating, it is useful to clean the damaged surface about 13 to 25 mm beyond the area to be repaired and also to cover this additional area; coat. This precautionary measure ensures good adhesion in the transition area of the repaired area. :

Known application methods can be used. For example, more viscous masses can be picked up with wet hands or gloves and applied by hand to a cleaned surface. A ball of the mass can be pressed firmly against the ground by hand and slowly spread under pressure from the center to the outer edges to displace the water and form a layer approximately 3.2 to 6.4 mm thick. The layer can then be smoothed and leveled at the edges. The underwater curable coating materials according to the invention can also be applied by brush or roller using a pressure delivery system. Another coating method uses an inverted box dam or caisson, which is placed tightly against the substrate to be coated. The water is displaced by pumping in air, with an air pocket between the caisson and the one to be coated . Surface is formed, whereupon the surface is coated in the wet state. The caisson can be un-; removed indirectly after coating or left in its position until the mass has hardened completely.

The layer thickness of the above-described, under. When used as an adhesive, water-hardening compounds

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The composition and coating composition lie within wide limits, but are generally about 25 to about 6.4 mm and more, preferably about 0.13 to 2.5 mm. When using al ^s touch-up and sealing compound, the thickness may be up to several inches vary widely if the materials for filling cracks, holes, etc. are used.. The masses can harden at temperatures of about 2 ° to 38 ° C. and more, the hardening time becoming shorter as the temperature rises. The hardening time under water is generally about 1 to 20 hours. A hardening time of around 3 to 12 hours is typical.

The coating materials described above can be applied to dry, wet or submerged Surfaces can be applied and cured in dry or wet condition or under water. Under "wet surface" a surface is understood that is both covered with water and soaked with water. was surprising the finding that the masses are rapidly displacing water on wet surfaces or underwater surfaces harden, adhere firmly to the substrate and develop excellent adhesive strength and flexibility. It is believed, that water reacts to a certain extent with the masses described above and acts as an accelerator is effective.

The invention is further illustrated by the following examples.

Examples General mixing procedure and sample preparation

The underwater hardening compositions were prepared by a general mixing process. A filler (optionally used) was mixed with an epoxy resin on a paint mill. Additional (if necessary ^! Used) filler was mixed with a terminally amine-substituted liquid polymer on a paint mill. The two mixtures were stirred together in a beaker with a spatula. The final

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The mixture was used within about 2 hours of complete mixing. The components of the Systems X were mixed by stirring in a beaker at room temperature.

Test samples were prepared as follows: strips off

a polychloroprene rubber compound which is an anti-fouling agent were made. The strips were approximately 25 mm 200 mm in size 2.2mm and the following composition:

Polychloroprene "Neoprene WRT" 100 parts by weight

2-mercaptoimidazoline 1 part by weight

Magnesium oxide 4 parts by weight

Phenyl-ß-naphthylamine 2 "

Zinc oxide 5 "

Mercaptobenzothiazole 1 part by weight

Carbon black 14.5 parts by weight

Bis (tri-n-butyltin) oxide 8 "

Lauric acid 3 "

138.5 "

Each rubber strip was hung in a 110 1 aquarium, containing artificial sea water, and aged for at least 24 hours at 21 to 27 ° C. The strips were then taken out of the container, lightly rubbed and immediately hung back in the container. One under water hardening mass was applied under water to the 25 mm 200 mm surface of a strip. The order' was done by hand or with a putty knife. The layer thickness of the mass on the rubber strip was about 6.4 mm. Immediately afterwards, the ' flat surface of a second strip under water pressed against the under water hardening mass, whereby a · Layered structure was obtained »The two strips were pressed tightly against one another to keep the water between them to be displaced and left to harden under water.

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materials

The terminally amine-substituted liquid polymers which are described in the examples below Experiments used were easily carried out following the procedure detailed above using N- (2-aminoethyl) piperazine in the reaction to introduce terminal amine groups. The terminally amine-substituted liquid polymers were butadiene / acrylonitrile copolymers with terminal amine groups, an acrylonitrile content of about 9.5% by weight of the polymer, a viscosity of about 90,000 cPs at 27 ° C and a molecular weight of about 3,600.

The most commonly used non-cycloaliphatic Epoxy resin was a liquid diglycidyl ether of bisphenol A (DGEBA) with an epoxy equivalent weight of about 185 to 192 and a viscosity of about 10,000 to 16,000 cPs at 25 ° C. The DGEBA resin is under the Designation "Epon 828" (manufactured by Shell Chemical Co.) is commercially available. Another non-cycloaliphatic Epoxy resin was the triglycidyl ether of glycerin with an epoxy equivalent weight of about 140 to 160 and a viscosity of about 100 to 170 cPs at 25 ° C. This resin is under the name "Epon 812" (manufactured by Shell Chemical Co.) is commercially available. It was also considered a non-cycloaliphatic Epoxy resin is a liquid diglycidyl ether of bisphenol A (DGEBA) with an epoxy equivalent weight of about 180 up to 200 and a viscosity of about 10,000 to 16,000 cPs at 25 ° C. This material is under the Designation "Epi-Rez 510" available commercially (made by Celanese Corporation).

For comparison with the underwater curing coating materials used in the method according to the invention coating materials were using

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made of two polyamide resins commercially available under the designations "Versamid 115" and "Versamid 140" (made by General Mills, Inc.). "Versamid 115" is the reaction product of a dimer dibasic acid and a polyamine and has an approximate amine value of 238 and a reactive equivalent weight of about 236. "Versamid 140" is the reaction ^; product of a dimer dibasic acid and a polyamine and has an approximate amine value of 385 and a reactive equivalent weight of about 146. Amine value is defined as the number of milligrams of potassium hydroxide equivalent to the amine alkalinity present in 1 gram of polyamide resin sample. "Reactive equivalent weight" is defined as 56,100 (equivalent weight of potassium hydroxide in mg) divided by the amine value of the polyamide resin sample.

For comparison purposes, a commercially available underwater curing system was also used, which is known as Two-component system is commercially available and is hereinafter referred to as "System X". The component 1 consisted of a liquid diglycidyl ether of bisphenol A (DGEBA) and about 52% by weight of a silicon dioxide filler. Component 2 was made of a polyamide resin which is believed to be that described above The product is tradename "Versamide 115" and is about 57 weight percent silica filler. The two , Components were mixed well by stirring together just prior to testing.

In addition to the terminal amine-substituted liquid polymers described in detail above, the .bei the experiments described in the following examples | used non-cycloaliphatic epoxy resins, poly-j amide resins and other materials, well-known commercial products and readily available «,!

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Test methods

The adhesive strength (peel strength) was after
Method ASTM D-903 tested. Flexibility was assessed by folding up to 360 ° and stretching by hand.

Examples 1 to

In each case, underwater curing coating materials were prepared according to the general method of mixing and sample preparation described above. The test was made after the
Samples had been held in 23 ° C water for about 48 hours. The test results are summarized in Table I below.

Table I Example 1 2 3

Recipe

Diglycidyl ether of bisphenol A »Epon 828",

Parts by weight 100

Terminal amine-substituted liquid polymer, parts by weight 800

System X, component 1

Parts by weight - -

System X, component 2

Parts by weight

Vapor phase colloidal silica, parts by weight 135

Carbon black N-550, parts by weight - 90 test results

Hardening time, hours 8-12 8-12

Area of average

Small bond strength, kg / cm 3.2-5.36 4.8-6.25 0.54-0.89

Flexibility is very good

draws draws poorly

Samples 1 and 2 cured quickly and showed excellent

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Excellent tear-off or peel strength and flexibility without sagging. In marked contrast to this, hardened the known coating material of Example 3 slowly, and both the adhesive strength and the Flexibility were very bad.

Examples 4 to 8

In each case, underwater curing coating materials were prepared according to the general mixing method and Sample preparation procedures described above have been produced. The test was carried out after 72 hours of exposure to water at 25 ° C. The test results are summarized in Table II below.

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Table II

ι

Example 4 5 6 7 8

Diglycidyl ether of bisphenol A

"Epon 828", parts by weight 100 100 100

Diglycidyl ether of bisphenol A

"Epi-Rez 510", parts by weight - 100

Terminally amine-substituted
"S" liquid polymer, parts by weight 5.00 - - - -

£ 0 System X, component 1, parts by weight - - - -

^m »," 2, parts by weight

tn polyamide resin "Versamid 115",

"^ Parts by weight - 100 - 100 -

~ α polyamide resin "Versamid 140",

e> parts by weight - - 100 - -

TiO ₂ , parts by weight 250 50 75 50

Test results

Hardening time, hours approx. 3 approx. 24 approx. 7 approx. 24 approx.

Average Adhesion Strength, kg / cm 1.43-1.6 1.25-1.43 0.89-1.1 1.43-1.6 0.54-0.71

lbs / in. 8-9 7-8 5-6 7-8 3-4

Maximum bond strength, kg / cm 2.14 1.52 1.16 1.7 0.89

Flexibility very good pretty much. bad pretty very

good good bad

The sample of Example 4 cured quickly and exhibited excellent tear and peel strength and flexibility. In contrast, the known coating materials of Examples 5 to 8 cured more slowly. she showed poorer tear and peel strength and only very bad to; Äass.ige flexibility.

The coating materials described above that contain at least one non-cycloaliphatic epoxy resin and at least one terminally amine-substituted liquid; contain total polymer with a C-C polymer main chain, cure quickly and have excellent adhesive strength and bond strength, the flexibility with increasing Amount of terminal amine-substituted liquid polymer is better. These coating materials harder in the method according to the invention under water and / advantageous as a sealing to be used under water, Filling and repair compounds, adhesives, coatings, paints and the like for ship floors, underwater locating devices, Underwater structures made of wood and concrete and the like.

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Claims (9)

Claims ! ^ Method of coating dry or wet Surfaces or surfaces submerged in water an underwater curing coating material with subsequent curing of the coating material on the wet or immersed surface, characterized in that that a coating material is used which contains the following components: A) 100 parts by weight of at least one non-cycloaliphatic Epoxy resins ^ which contain an average of at least about 1.7 epoxy groups in the molecule and a Has epoxy equivalent weight of about 70 to 6000, and B) about 1 to 2000 parts by weight of at least one terminal amine-substituted liquid polymer, the average of about 1.7 to 3 primary and / or secondary Contains amine groups in the molecule and the formula where Y is a monovalent radical which can be removed by removing from hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic Amine containing 2 to 20 carbon atoms and at least two amine groups, of which at least two primary and / or secondary, and B is a polymer backbone, the C-C bonds and polymerized units containing at least one vinylidene monomer having at least one terminal Group of the formula CHp = CCl contains and from the group is selected from a) monoolefins with 2 to 14 carbon atoms, b) serving 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 709815/0795 ORIGINAL IHSPEOTSD 1 to 8 carbon atoms and e) Acrylic acids and acrylates of the formula R O I It A CH ₂ = CCOR ^χ , where R is hydrogen or an alkyl group having 1 to 3 carbon atoms and R is hydrogen, an alkyl group having 1 bi ^s 18 carbon atoms or an alkoxy ■ alkyl, alkylthioalkyl or cyanoalkyl radical is of 2 to 12 carbon atoms. 2) Method according to claim 1, characterized in that the C-C bonds are at least 90 wt .-% of the total weight make up the main polymer chain and the monomer is selected from the following group of compounds: 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 H -1 CH ₂ = CCOR, wherein R is hydrogen or an alkyl radical having 1 to 3 carbon atoms and R is hydrogen, an alkyl radical having 1 to 8 carbon atoms or an alkoxyalkyl radical, alkylthioalkyl radical or cyanoalkyl radical with 2 to 8 carbon atoms. 3) Method according to claim 1 and 2, characterized in that the epoxy resin has an epoxy equivalent weight from about 70 to 2000 has. 4) Method according to claim 1 to 3, characterized in that the epoxy resin is a glycidyl ether resin. 5) Method according to claim 1 to 4, characterized in that the coating material is an epoxy resin a) an alkanediol diglycidyl ether of the formula 709815/0795 CH-CH-CH ₂ - • Ο-Χ- -0-CH-CH-CH wherein X is an alkylene radical or alkylidene radical with 1 to ί ¹ O C atoms and η is a number from 0 to 20, or J b) a di- or polyglycidyl ether of a bisphenol, that the formula; where R is a divalent radical having 1 to 8 C and / or O and / or S and / or N atoms, or c) contains an alkanetriol triglycidyl ether with 2 to 10 carbon atoms in the alkane radical. 6) Method according to claim 1 to 5, characterized in that with the vinylidene monomers 0% to about 50 wt .-% at least one of the following comonomers is copolymerized: ' f) vinyl aromatics of the formula ^[ wherein R is hydrogen, halogen or an alkyl radical. with , Is 1 to 4 carbon atoms, g) vinyl nitriles of the formula 709815/0795 where R is hydrogen or an alkyl radical with 1 to C atoms, h) vinyl halides, i) divinyls and diacrylates, j) amides of α, β-olefinically unsaturated carboxylic acids with 2 to 8 carbon atoms and k) allyl alcohol. 7) Method according to claim 1 to 6, characterized in that the amine groups have different reactivities and one of the vinyl aromatics (f) and / or a vinyl nitrile (g) is present as comonomerL 8. The method according to claim 1 to 7, characterized in that a coating material is used which a diglycidyl ether of isopropylidenebisphenol as the epoxy resin, and at least one N- (aminoalkyl) piperazine as the amine with 1 to 12 carbon atoms in the aminoalkyl radical, as vinylidene monomer at least one diene and as Comonomer contains at least one vinyl nitrile. 9. The method according to claim 1 to 8, characterized in that the coating material as diene butadiene, contains acrylonitrile as vinyl nitrile and N- (2-aminoethyl) piperazine as amine. 709815/0795