CA1091995A - Underwater curing of epoxy resin and amine-terminated liquid polymer and product thereof - Google Patents
Underwater curing of epoxy resin and amine-terminated liquid polymer and product thereofInfo
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- CA1091995A CA1091995A CA261,499A CA261499A CA1091995A CA 1091995 A CA1091995 A CA 1091995A CA 261499 A CA261499 A CA 261499A CA 1091995 A CA1091995 A CA 1091995A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C08L57/12—Homopolymers or copolymers containing elements other than carbon and hydrogen containing nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
UNDERWATER CURING OF EPOXY RESIN AND AMINE-TERMINATED
LIQUID POLYMER AND PRODUCT THEREOF
ABSTRACT
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin cures rapidly under water while displacing water on underwater surfaces and bonding strongly thereto. The mixture comprises (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin, (B) from about 1 to about 2,000 parts by weight of at least one amine-terminated liquid polymer having a carbon-carbon backbone, (C) optionally, a chain extender or crosslinker, (D) optionally, a curing agent, and (E) optionally, other compounding ingredients. The mixture is useful as an underwater repair putty, adhesive, coating, or the like.
LIQUID POLYMER AND PRODUCT THEREOF
ABSTRACT
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin cures rapidly under water while displacing water on underwater surfaces and bonding strongly thereto. The mixture comprises (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin, (B) from about 1 to about 2,000 parts by weight of at least one amine-terminated liquid polymer having a carbon-carbon backbone, (C) optionally, a chain extender or crosslinker, (D) optionally, a curing agent, and (E) optionally, other compounding ingredients. The mixture is useful as an underwater repair putty, adhesive, coating, or the like.
Description
L9~.5 BACKGROUND OF THE INVENTION
Underwater-curing coatings are known in the art (Drisko, Paint and Varnish Production ~ol. 58, p.31, July, 1968). ~uch coatings typically ColnpriSe an amine-terminated polyamide resin and a liquid epoxy resin.
These prior art coatings may cure rather slowly and may have mediocre adhesive strength and flexibility. New underwater-curing compositions are desired having improved cure rate, adhesive strength and flexibility.
SUMMARY OF T~E IN~ENTION
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin is applied to a sur-~ace and cured under water. T~le mLxture comprises (A) 100 parts by welght o~ at least one non-cycloaliphatic epoxy resin, and (B) from about 1 to about 2000 parts by weight of` at leas-t one amine-terminated liquid polymer having a carbon-carbon backbone.
DETAILED DESCRIPTION
Amine-Terminated Liquid Polymers The amine-terminated liquid polymers suitable for use in this invention have -the formula O O
Y-C ~ B ~ C-Y
wherein Y is a univalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, he-terocyclic or aromatic amine containing at least two primary and/or secondary amine groups, and B is a polymeric backbone comprising carbon-carbon linkages. Generally the carbon-carbon linkages comprise at least about 90~ by weigh-t of total polymeric backbone weight, more preferably at least about 95% by weight of total polymeric backbone weight. me amine-terminated polymers contain an average from about 1.7 to about 3 primary and/or secondary amine groups per molecule, more preferably frc)m about 1.7 to about 2.3 primary and/or secondary amine groups pèr mole-cule. The amine-terminated polymers may have Brookfield viscosities (measured using a Brookfield RVT viscometer at 27C) from about 500 cps to about 2,500,000 cps, more preferably from about 500 cps to about 500,000 cps.
m e amine-terminated liquid polymers can be prepared easily by reacting a carboxyl~terminated or ester-te~ina-ted liquid polymer having a carbon-carbon backbone with at least one aliphatic, alicycLic or heterocyclic arnine containing a-t least two primary and/or secondary amine groups. Amine-terminated liquid polymers can also be prepared easily by reacting an acid chloride-terminated liquid polymer having a carbon-carbon backbone with a-t least one aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two primary and/or secondary arnine gY~OupS.
The carboxyl-terminated liquid polymers used may have Brookfield viscosities from about 500 cps. to about 500,000 cps., more preferably from a~out 500 cps. to about 250,000 cps., and have polymeric backbones comprising carbon-carbon linkages. The carboxyl functional groups are located at least at the ends of a polymer molecule, but there may also be additional group(s) located pendant to a polymer backbone. The average number of total carboxyl groups typically is from about 1.7 to about 3 groups per molecule, 1~91~9S
more preferably from about 1.7 to 2.3 groups per molecule.
Carboxyl-terminated liquid poly~ers having carbon-carbon backbone linkages may contain polymerized units of at least one ~inylidene monomer having at least one terminal CH2= C< group and selected from the group consisting of (a) monoolefins containing 2 to 1~ carbon atoms, more preferably
Underwater-curing coatings are known in the art (Drisko, Paint and Varnish Production ~ol. 58, p.31, July, 1968). ~uch coatings typically ColnpriSe an amine-terminated polyamide resin and a liquid epoxy resin.
These prior art coatings may cure rather slowly and may have mediocre adhesive strength and flexibility. New underwater-curing compositions are desired having improved cure rate, adhesive strength and flexibility.
SUMMARY OF T~E IN~ENTION
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin is applied to a sur-~ace and cured under water. T~le mLxture comprises (A) 100 parts by welght o~ at least one non-cycloaliphatic epoxy resin, and (B) from about 1 to about 2000 parts by weight of` at leas-t one amine-terminated liquid polymer having a carbon-carbon backbone.
DETAILED DESCRIPTION
Amine-Terminated Liquid Polymers The amine-terminated liquid polymers suitable for use in this invention have -the formula O O
Y-C ~ B ~ C-Y
wherein Y is a univalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, he-terocyclic or aromatic amine containing at least two primary and/or secondary amine groups, and B is a polymeric backbone comprising carbon-carbon linkages. Generally the carbon-carbon linkages comprise at least about 90~ by weigh-t of total polymeric backbone weight, more preferably at least about 95% by weight of total polymeric backbone weight. me amine-terminated polymers contain an average from about 1.7 to about 3 primary and/or secondary amine groups per molecule, more preferably frc)m about 1.7 to about 2.3 primary and/or secondary amine groups pèr mole-cule. The amine-terminated polymers may have Brookfield viscosities (measured using a Brookfield RVT viscometer at 27C) from about 500 cps to about 2,500,000 cps, more preferably from about 500 cps to about 500,000 cps.
m e amine-terminated liquid polymers can be prepared easily by reacting a carboxyl~terminated or ester-te~ina-ted liquid polymer having a carbon-carbon backbone with at least one aliphatic, alicycLic or heterocyclic arnine containing a-t least two primary and/or secondary amine groups. Amine-terminated liquid polymers can also be prepared easily by reacting an acid chloride-terminated liquid polymer having a carbon-carbon backbone with a-t least one aliphatic, alicyclic, heterocyclic or aromatic amine containing at least two primary and/or secondary arnine gY~OupS.
The carboxyl-terminated liquid polymers used may have Brookfield viscosities from about 500 cps. to about 500,000 cps., more preferably from a~out 500 cps. to about 250,000 cps., and have polymeric backbones comprising carbon-carbon linkages. The carboxyl functional groups are located at least at the ends of a polymer molecule, but there may also be additional group(s) located pendant to a polymer backbone. The average number of total carboxyl groups typically is from about 1.7 to about 3 groups per molecule, 1~91~9S
more preferably from about 1.7 to 2.3 groups per molecule.
Carboxyl-terminated liquid poly~ers having carbon-carbon backbone linkages may contain polymerized units of at least one ~inylidene monomer having at least one terminal CH2= C< group and selected from the group consisting of (a) monoolefins containing 2 to 1~ carbon atoms, more preferably
2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, l-butene, l-pentene, l-hexene, l-dodecene and the like~ (b) dienes containing 4 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, such as butadiene, isoprene, 2-iso-propyl-1,3-butadiene, chloroprene, and the like; (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms such as vinyl acetate, vinyl propionate; allyl ace~ate, and the like; (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 carbon atoms such as ~inyl methyl ether, allyl methyl ether, and the like; and (e) acrylic acids and acrylates having the formula CH2=C-C -O-Rl wherein R is hydrogen or an alkyl radical containing 1 to 3 carbon atoms and Rl is hydrogen or an alkyl radical con-taining 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, or an alkoxyalkyl, alkylthioalkyl, or cyano-alkyl radical containing 2 to 12 carbon atoms, more prefer-ably 2 to 8 carbon atoms. E~en more preferably Rl is hydrogen or an alkyl radical containing 1 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 acrulate, hexylthioethyl acrylatea g-cyanoethyl acrylate, cyanooctyl acrylate, methyl methacrylate, ethyl methacrylate, octyl methacrylate and the ]ike. Often -two or more types of these polymerized monomeric units are contained in the polymeric backbone.
More preferred liquid polymers contain polymerized units of at least one vinylidene monomer having at least one terminal CH2=C< group and areselected from the group con-sisting of (a) monoolefins containing 2 to 14 carbon atoms, more preferably 2 to 8 carbon atoms; (b) dienes containing ~ to 10 carbon atoms, more preferably 1~ to 8 carbon atoms;
and (e) acrylic acids and acryla-tes having the formula R O
CH2=C -C - O-Rl wherein R is hydrogen or an alkyl radical containing 1 to
More preferred liquid polymers contain polymerized units of at least one vinylidene monomer having at least one terminal CH2=C< group and areselected from the group con-sisting of (a) monoolefins containing 2 to 14 carbon atoms, more preferably 2 to 8 carbon atoms; (b) dienes containing ~ to 10 carbon atoms, more preferably 1~ to 8 carbon atoms;
and (e) acrylic acids and acryla-tes having the formula R O
CH2=C -C - O-Rl wherein R is hydrogen or an alkyl radical containing 1 to
3 carbon atoms and R is hydrogen or an aIkyl radical con-taining 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, or an alkoxyalkyl, alkylthioalkyl, or cyanoalkyl radical containing 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. Even more preferably R1 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms. Excellen-t results were obtained wi-th dienes containing 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.
The vinylidene monomers described above may be polymerized readily with from 0~0 up to about 50~ by weight, more preferably from 0~ up to about 35~o by weight, of at least one comonomer selected from the group consisting of (f) vinyl aroma-tics having the formula ~H2 ~H
R~LR2 wherein R is hydrogen, halogen or an alkyl radical con-taining from l to 4 carbon atoms, such as styrene, ~-methyl styrene, chlorostyrene, vinyl toluene, and the like; (g) vinyl nitriles having the formula R
C~I2=C-C-N
wherein R is hydrogen or an alkyl radical containing l to 3 car.bon atoms, such as acrylonitrile, me-thacrylonitrile and the like; (h) vinyl halides such as vinyl bromide, vinyl chloride and -the like; (i) divinyls and diacrylates such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, and the like; (j) amides of` ~,~-olefinically unsaturated carboxylic acids containing 2 to 8 carbon a-toms such as acrylamide and the like; and (k) allyl alcohol and the like. Liquid polymer compositions comprising polymerized uni-ts of a major amount of at least one vinylidene monomer listed in (a) to (e) with a minor amoun-t of at least one comonomer listed in (f) to (k) are within the scope of this invention.
More preferred comonomers may be selected fro~
the group consisting of (f) vinyl aromatics having the formula 2 R2~ R2 R2--~ R2 1~?9~ S
wherein R is selected from the group consisting o~
hydrogen, halogen and alkyl radicals containing 1 to
The vinylidene monomers described above may be polymerized readily with from 0~0 up to about 50~ by weight, more preferably from 0~ up to about 35~o by weight, of at least one comonomer selected from the group consisting of (f) vinyl aroma-tics having the formula ~H2 ~H
R~LR2 wherein R is hydrogen, halogen or an alkyl radical con-taining from l to 4 carbon atoms, such as styrene, ~-methyl styrene, chlorostyrene, vinyl toluene, and the like; (g) vinyl nitriles having the formula R
C~I2=C-C-N
wherein R is hydrogen or an alkyl radical containing l to 3 car.bon atoms, such as acrylonitrile, me-thacrylonitrile and the like; (h) vinyl halides such as vinyl bromide, vinyl chloride and -the like; (i) divinyls and diacrylates such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, and the like; (j) amides of` ~,~-olefinically unsaturated carboxylic acids containing 2 to 8 carbon a-toms such as acrylamide and the like; and (k) allyl alcohol and the like. Liquid polymer compositions comprising polymerized uni-ts of a major amount of at least one vinylidene monomer listed in (a) to (e) with a minor amoun-t of at least one comonomer listed in (f) to (k) are within the scope of this invention.
More preferred comonomers may be selected fro~
the group consisting of (f) vinyl aromatics having the formula 2 R2~ R2 R2--~ R2 1~?9~ S
wherein R is selected from the group consisting o~
hydrogen, halogen and alkyl radicals containing 1 to
4 carbon atoms; and (g) vinyl nitriles having the formula CH2=C-C_N
wherein R is hydrogen or an aIkyl radical containing 1 to 3 carbon atoms. Excellent results were obtained using styrene and acrylonitrile.
Examples of use~ul liquid polymeric backbones comprising carbon-carbon linkages include polyethylene, polyisobutylene, polyisoprene, polybutadiene, poly (vinyl ethyl ether), poly (ethylacrylate) and poly (butylacrylate) as well as copolymers o~ butadiene and acryloni-trile;
butadiene and styrene; vinyl aceta-te and isoprene; vinyl acetate and chloroprene; vinly ethyl ether and diallyl ether; vinyl ethyl ether and ~-methyl styrene; vinyl ethyl ether and vinyl bromide; methyl acrylate and butadiene;
methyl acrylate and ethyl acrylate; methyl acrylate and butyl acrylatej methyl acrylate and 2-ethyl hexyl acrylate;
ethyl acrylate and ethylene; ethyl acrylate and isobutylene;
ethyl acrylate and isoprene; ethyl acrylate and butadiene;
ethyl acrylate and vinyl acetate; ethyl acryla-te 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 ancl 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 1~9~ 95 acrylate and acrylonitrilej butyl acrylate and vin~l chloride; and the like.
Liquid carboxyl-terminated polymers may be prepared by free-radical polymerization using carboxyl-containing initiators and/or modifiers as disclosed in U.S. Patent 3,285,9~9 and German Pa-tent 1,150,205 and by solutio~ polymerization using lithium metal or organo-metallic compounds and post-treating the polymers to form carboxyl groups as disclosed in U.S. Patents 3,135,716 and 3,~31,235. The polymers can also be prepared by reacting liquid polymers having other than terminal carboxyl groups with compounds so as to yield carboxyl groups. For example, liquid carboxyl-terminated polymers can be prepared from liquid hydroxyl-terminated polymers by reaction with dicar-boxyl compounds or anhydrides. I,iquid halogen--terminated polymers can be reacted with unsaturated anhydrides in the presence of Lewis acids to yield carboxyl groups. Th~s, it is seen that the method of preparing the liquid carboxyl-terminated polymer is not cri-tical to the invention.
The essential features of the polymer are that it have at least terminal carboxyl groups and a polymeric backbone of carbon-carbon linkages.
Examples of preferred liquid carboxyl-terminated polymers include carboxyl-terminated polyethylene, carboxyl-terminated polyisobutylene, carboxyl-terminated polybutadiene, carboxyl-terminated polyisoprene, carboxyl-terminated poly_ (ethylacrylate), as well as carboxyl-terminated copolymers of butadiene and acrylonitrile and of butadiene and styrene.
Carboxyl-terminated copolymers of butadiene with acrylonitrile or styrene were found to be especially useful. mese poly-mers may contain from about 50~ to about 99.6~o by ~eight of 9~
butadiene, from about 0~ to about ~0% by weight of acry-lonitrile or styrene and from about 0.~ to about 10~ by weight of carboxyl, based upon the total weight of polymer.
m e carboxyl-terminated liquid polymers can be esterified with an aliphatic monohydric alcohol by methods well known to the art in order to produce ester-terminated liquid polymers. ~or example, a carboxyl-terminated polymer and an aliphatic monohydric alcohol can be reacted in a distillation column or under reflux in the presence of a small amount of an acid catalyst. Suitable acid ca-talysts include organic acids containing 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as acetic acid, pro-pionic acid, benzoic acid, monoes-ters and dies-ters of orthophosphoric acid, alkarylsulf'onic acids such as p-toluene sulfonic acid, and the like; inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like; and Lewis acids such as tetraisopropyl titanate and the like. The amount of acid catalyst used may be as little as about 0.01~ up to about 5~ by weight based upon total reactant weight. Suitable aliphatic monohydric alcohols for use in the esterif'ication reaction contain f'rom 1 to 12 carbon a-toms, more preferably from 1 to 6 carbon atoms, and have boiling points below abou-t 150~., more preferably below about 100C. Primary aliphatic mono-hydric alcohols are preferred. Examples of suitable aliphatic monohydric alcohols include alkanols containing from 1 to 6 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, l-butanol, 2-hexanol~ 3-hexanol, and the like.
Other suitable aliphatic monohydric alcohols include 2--me-thoxyethanol, 2-ethoxyethanol and the like. Excellent results may be obtained using ethanol, l-propanol or 1-butanol.
m e carboxyl-terminated liquid polymers can be acylated by methods well known to the art in order to produce acid chloride-terminated liquid polymers. For example, a carboxyl--terminated polymer can be reacted with thionyl chloride to produce an acid chloride-terminated polymer. HCl and S02 are e~olved primarily as gases and are separated easily from the acid chloride-terminated poly-mer, and any excess thionyl chloride can be removed easily 'by ~acuum distillation or by washing with a solvent such as methanol. Other suitable but less pref'erred acylation agents include phosphorus trichloride and phosphorus pen-tachloride.
Amines which react well with the carboxyl-termin-ated, ester-terminated and acyl-terminated polymers described heretofore include aliphatic amines containing from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, and at least two, more pref'erably two, primary and/or secondary amine groups. Also suitable are alicyclic amines containing from 4 to 20 carbon atoms, more pref'erably from 4 to 12 carbon atoms, and at least two, more preferably two, primary and/or secondary amine groups. Heterocyclic amines may also be used which contain from 2 -to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, and at least two, more preferably -two, primary and/or secondary amine groups.
Examples of suitable amines just described include aliphatic amines such as ethylenediamine, 1,2-propanediamine~ 1~3-propanediamine, 1,4-butanediamine, 2 me-thyl-1,2-propanedia-1~9~L9~S
mine, 1,5-pentanediamine, 1,6 hexanediamine, 1,7-heptane-diamine, 1,8-octanediamine, l,10-decanediamine, 1,12-dodecanediamine and the like; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, -tetraethylene-pentamine, bis(hexamethylene) triamine, 3~3l-imincbi amine, `and the like; alicyclic diamines and polyamines such as 1,2-diaminocyclohexane, 1,8-p-menthanediamine and the like; and heterocyclic diamines and polyamines such as ~-(aminomethyl) piperidine; piperazine; N-(aminoalkyl) piperazines wherein each alkyl group contains from 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, such as N-(2-aminoethyl)piperazine, N-(3-aminopropyl) piperazine, N,N'-bis (3-aminopropyl)piperazine, and -the like.
More preferably the amines just described contain at least two primary and/or secondary amine groups having different reactivitiesO The presence of amine groups having different reactivities makes the amine-termination reaction more likely than the coupling of the li~uid polymers~ and a smaller amine excess may be used in order to avoid coupling.
Examples of more preferred amines include some alicyclic amines such as 1,8-p-menthanediamine and the like; and some heterocyclic amines such as 4-(aminomethyl)piperidine and N-(aminoalkyl)piperazines wherein the alkyl group contains from 1 to 12 carbon atoms, more pre~erably 1 to 6 carbon atoms, such as N-(2-aminoethyl)piperazine, N-(3-aminopropl) piperazine, and the like. Excellent results were obtained using N-(2-aminoethyl)piperazine.
Aroma-tic diamines and polyamines can be used to produce amine-terminated polymers. The high tempera-ture required for aromatic amine reaction with carboxyl--te~minated :1~9:~L9~5i polymers causes excessive degradation of reactants and products and is therefore much less preferred. However, aromatic amines may react well ~ith the acyl-terminated polymers described heretofore. Suitable aromatic amines contain at least two primary or secondary amine groups bonded directly to at least one aromatic nucleus. Examples of suitable aromatic amines include 4,5-acenaphthenediamine, 3,5-diaminoacridine, 1,4-diaminoanthraquinone, 3,5-dia-minobenzoic acid, 2,7-fluorenediamine, 1,5-naphthalenedia-mine, 1,8-naphthalenediamine, 2,4-toluenediamine, 2,6-toluenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and the like.
A solvent is not required for the amine-termination reaction but may be used. Mixtures of solvents may also be used. Suitable solvents include aliphatic and cycloali-phatic ethers containing from 3 to 10 carbon atoms~ more preferably from 3 to 6 carbon atoms, such as tetrahydrofuran, diethylether and the like; halogenated aliphatic hydrocarbons containing from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, such as chloroform, carbon tetrachloride, 1,2-dichloroethylene, trichloroethylene, tetrachloroe-thylene and the like; and esters containing ~rom 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate, e-thyl propionate and the like.
Also suitable as solvents and more preferred are aromatic compounds having the formula.
~4 R~I~R4 ~'3i~'~S
wherein R is hydrogen, halogen or an alkyl radical contain-ing 1 -to 3 carbon atoms, and at least two R4s are hydrogen.
More preferably R is hydrogen, chlorine, or an alkyl radical containing 1 to 2 carbon atoms, and at least three R~s are hydro~en. Suitable aromatic solvents include benzene, chloro-benzene, toluene, o-, m- and p-xylene, o-, m- and p-diethyl-benzene, cumene, mesitylene and the like.
A suf~icient quantity of at least one amine described heretofore may be reacted with a carboxyl-terminated, ester-terminated or acid-chloride-terminated liquid polymer described heretofore in order to produce an amine-terminated liquid polymer containing from about 1.7 to about 3 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 will be from about 1.7 to about 3 groups per molecule, more preferably from about 1.7 to about 2.3 groups per molecule. In thistypical case, from about 1.2 to about 6 mole equivalents and more, more preferably from about 1.2 to about 3 mole equivalents of at least one amine described heretofore can be used per mole equivalent of carboxylated~ es-terified or acylated liquid polymer de-scribed heretofore. However, when the carboxylated, esteri-fied or acylated liquid polymer also contains polymerized therein appreciable amounts of acrylic acid, acrylates or the like, the amount of amine reacted should be limited so that the amine-terminated liquid polymer contains no more than an average of 1.7 to about 3 primary and/or ~9i~
secondary amine groups per molecule.
No catalyst is required, and many types of mixing apparatus can be used in the amine termination reaction.
For example7 simple mixers can be used, including turbine stirrers as well as propeller mixers. Reaction components can be combined in any order. The reaction mixture may be heated (or refluxed if a solvent is used) at a temperature from about 80C to about 150C, typically ~or about 1 to 6 hours. m e amine-terminated liquid polymer may be purified by vacuum distillation or by washing with a solvent such as a benzene-methanol mixture, followed by drying the polymer. Amine content of the amine-terminated liquid polymers can be analyzed qualitati~ely by infrared spec-troscopy. Amine content can also be analyzed quanti-tatively following the procedure described by Siggia, Quantita-tive Organic Analysis via Functional Groups, N.Y., Wiley and Sons, Inc., 1963, pp. 452-456.
Underwater Curing of Non-Cycloaliphatic Epoxy Resins and Amine-Terminated Liquid Polvmers v m e compositions used in the process of this invention comprise (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin described hereinafter and (B) from about 1 to abou-t 2,000 parts by weight of at least one amine-terminated liquid polymer described here-tofore. Compositional properties may be varied widely by using varying amounts of amine-terminated liquid polymer.
Chain extenders, crosslinkers, and curing agents described hereinafter may also be used in the epoxy compositions but are not required.
Non-cycloaliphatic epoxy resins suitable for use in this invention together with amine-terminated liquid _ lL~ ~
9~5 polymers contain at least an average of about 1.7 epoxy groups per molecule, more preferably from about 1.7 to about 3 epoxy groups per molecule, and even more preferably from about 1.7 to about 2.3 epoxy groups per molecule. The non-cycloaliphatic epoxy resins may be liquids or low~
melting solids but are preferably liquids having a bulk viscosity from about 100 centipoises to about 2,000,000 centipoises (measured using a Brookfield RVT viscometer at 25 C). The epoxy resins can have an epoxy equivalent weight (gram molecular weight per epoxy group) from about 70 to about 6,000,more preferably from about 70 to about 2,000.
Suitable non-cycloaliphatic epoxy resins include epoxidized cyclic silane, epoxidized soybean oil, polyglycidyl es-ters oI` polycarboxylic acids, epoxidized polyolefins, and gly-cidyl ether resins, with glycidyl ether resins being pre-ferred Examples of suitable polyglycidyl esters of poly-carboxylic acids include the diglycidyl ester of linoleic dimer acid, the triglycidyl ester of linoleic trimer acid, and the like. Suitable glycidyl ether resins include poly-allyl glycidyl ether;`the diglycidyl ether of chlorendic diol; -the diglycidyl ether of dioxanediol; the diglycidyl e-ther of endomethylene cyclohexanediol; epoxy novolac resins;
alkanediol diglycidyl ethers; alkanetriol triglycidyl ethers; and the like.
More preferred glycidyl ether resins include alkanediol diglycidyl ethers ha~ing the formula C 2~-CH-CH2 _E_O-X~O-CH2 -(~H-CH2 gS
wherein X is an alkylene or alkylidene group containing from 1 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms, and n is from 1 to 25, more preferably from 1 to 15. Suitable alkanediol diglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol digly-cidyl ether, butanediol diglycidyl ether, and the like.
Other more preferred glycidyl ether resins in-clude alkanetriol triglycidyl ethers wherein the alkane group contains from 2 to 10 carbon atoms, more pre~erably from 3 to 6 carbon atoms, such as glyceryl triglycidyl ether, the triglycidyl ether of trimethylolpropane and the lLke. Ano-ther more preferred class of glycidyl ether resins is the digl~cidyl and polyglycidyl ethers of bi-sphenols, the bisphenols ha~ing the formula HO ~ R5 - ~ OH
wherein R5 is a bi~alent radical containing 1 to 8 atoms of at least one atom selected from the group consisting of C, O, S and N, more preferably an alkylene or alkylidene group containing 1 to 8 carbon atoms, and even more pre-ferably an alkylene or alkylidene group containing 1 to 6carbon atoms. Examples of suitable bisphenols include methylene bisphenol, isopropylidene bisphenol~ butylidene bisphenol, octylidene bisphenol~ bisphenol sulfide, bisphen-ol sulfone, bisphenol ether, bisphenol amine, and the like.
Excellent results were obtained using isopropylidene bi-sphenol (bisphenol A). Examples of suitable di- and poly-glycidyl ethers inclu~e those of isopropylidene bisphenol having the formula S
C~v .
~a [~
o_v o ~ ~ .
s~
~'' o v Pi o ~ .
wherein n is from about O -to about 20, more preferably from about O to about 2.
Cycloaliphatic epoxy resins are much less pre-ferred in the process of this invention because they are substantially uncurable at room tempera-ture ~hen mixed with an amine-terminated liquid polymer. By cycloaliphatic epoxy resin is meant a resin in which an epoxy group is itself part of a cycloaliphatic ring struc-ture. Such cycloaliphatic resins include bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, the bis(epoxydicyclo-pentyl) ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-(3,4-epoxy) -cyclohexane carboxylate, bis(3,4-epox~-6-methylcyclohexylmethyl) adipate and the like. Other cyc-loaliphatic resins are described in Lee et al, EIandbook f Epox~ Resins, McGraw-EIill Book Company, N.Y., 1967, Chapter 4.
Other reactive additives are not required in the compositions comprising an amine terminated liquid polymer and an epoxy resin. However, chain extenders and/or cross-linkers may be used. The amount of chain extender and/or cross-linker used may vary wiclely depending on relative weights and reactive functionalities of epoxy resins and amine-terminated liquid polymers. The amount of chain extender and/or cross-linker used also depends on properties desired in the compositions of -this invention. Typical amounts of chain extender and/or cross-linker used may vary from about O to about 60 parts by weight, more preferably from about O to about 35 parts by weight pèr 100 parts by ~reight of epoxy resin.
Suitable chain extenders and/or cross-linkers can be any of the difunctional materials known by those ~o~
skilled in the art to be reactive with epoxy compounds, including dibasic acids such as azelaic acid, phthalic acid and the like~ and dimercap-tans such as 1,6-hexan-edithiol, 1,8-octanedithiol and the like. Also sui-table as chain extenders are anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride and the like; diisocyanates such as 4,4'-dicyclo-pentyl methylene diisocyanate, 4,4'-diphenylmethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolyl.ene diiso-cyanate, 1,4-phenylene diisocyanate and the like; di- and polyamines described in detail hereto~ore in connection with preparation o~ -the a~ine-term~.nated liquid polymer and lncluding the dlamine made by reacting linoleic acid dimer with a diamine, ethylene diamlne, N-(2-aminoethyl)piperazine and the like; and alipha-tic dihalides con-taining ~rom 1 to 12 carbon atoms, more pre~erably aliphatic dihalides con-taining ~rom 1 to 8 carbon atoms wherein the halide is bromide and/or chloride, such as 1,4-dibromobutane, 1,3-dibromobutane, l,~-dichlorobu-tane, 1,2-dichloroethane, l,l~-diiodobutane, 1,6-dichlorohexane, and the like.
Also suitable as chain extenders and/or cross-linkers and more pre~erred ln this invention are dihydric aromatic compounds con-taining from 6 to 24 carbon atoms, more pre~erably ~rom 6 to 18 carbon atoms. Suitable di-hydric aroma-tic compounds include catechol, resorcinol, 3-hydroxybenzyl alcohol, ~-hydroxybenzylalcohol, l,3-dihy-~roxynaphthalene, 1,5-dihydroxynaphthalene, 1~7~dihydroxy-naphthalene, and, even more pre~erably, bisphenols having -the ~ormula ~1995i H ~ R5 ~ - OH
wherein R5 is a bivalent radical containing 1 -to 8 atoms of C, O, S and/or N, more preferably an alkylene or alkylidene group containing 1 to 8 carbon atoms, and even more preferably an alkylene or alkylidene group containing 1 to 6 carbon atoms. Examples of suitable bisphenols include methylene bisphenol3 isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, bisphenol amine, and the like. E~cellent results were obtained using isopropylidene bisphenol (bisphenol A).
Curing agents may be used to accelera-te and/or supplement the reaction between the epoxy resin and amine-terminated liquid polymer described heretofore but are not required. Suitable curing agents include BF3-amine complexes, hexahydrophthalic anhydride, dicyandiamide, imidazoles such as 2-ethyl-~-methyl-imidazole, triethylenetetraamine, and the like.
In addition to the -two essential components (an amine-terminated liquid polymer and an epox~ resin) and the two optional components (a chain extender or a curing agent) described heretofore, the compositions may contain a broad range of other compounding ingredients. These ingredients are typical ingredients used in rubber and/or epoxy com-pounding. Standard levels of these ingredients are used, such levels being well known in the art. For example, re-inforcing fillers and other ingredients which thicken the liquid composition may be used at levels up to about 250 parts by weight and more at room temperature based upon 100 i~915~9S
parts by weight of the mixture of epoxy resin and amine-terminated liquid polymer.
Examples of compounding ingredients include re-inforcing fillers such as carbon blacks, metal carbonates and silicates, and glass, asbestos, and tex-tile fibers;
non-reinforcing fillers such as titanium dioxide, silica and the like; colorants such as metal oxides and metal sul-fides, and organic colorants; lubricants and plasticizers such as petroleum oils, cas-tor oil, glycerin, silicones, aromatic and paraffinic oils, and alkyl and aromatic phthalates, sebacates, trimellitates, and the like; and antioxidants and stabilizers such as phenyl-~-naphthylam-ine, 2,6-di-t-butyl paracresol, 2,2~-methylenebis-(4-ethyl-6-t-butyl phenol), 2,2'-thiobis-(4-methyl-6-t-butyl phenol), 4,4~-butylidenebis-(6--t-butyl-m-cresol), tris-(3,5-di-t-bu~yl-4-hydroxybenzyl) isocyanurate, hexahydro-1,3,5-tris-~-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl triazine, tetrakis-methylene-3(3',5~-di-t-butyl-4'-hydroxyphenyl)propionate methane, distearyl thiodipropionate, tri(nonylated phenyl) phosphite, and the like. Wetting agents such as blown fish oil and the li.ke can also be used. Other suitable com-pounding ingredients include anti-fouling toxic agents such as bis~-tri-n-butyltin)oxide described in U.S. Patent 3,426,473.
m e epoxy resin compositions usable in the process of this invention comprise (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin described heretofore, (B) from about 1 to about 2,000 parts by weight, more pre-10919'r35 ferably from about 300 to about 1,500 parts by weight, of at least one amine-terminated liquid polymer described heretofore, (C) optionally, a chain extender and/or cross-linker, (D) optionally, a curing agent and (E) optionally, other compounding ingredients described heretofore. The composition components can be mixed using mixing kettles, Henschel mixers, ink mills, Banbury mixers, or the like.
Standard mixing techniques can be used. A curing agent, if used, is preferably mixed first with the amine-terminated liquid polymer. Pot life of the underwater-curing com-positions after mixing typically is from about 2 hours to about 4 hours. Heating the mixture up to about 100C. may be helpful to obtain dissolution and uniform dispersion of` the materials, but such heating causes the compositions to cure much more rapidly.
A wide variety of surface materials may be coated, puttied, patched or the like using the underwater-curing materials described heretofore. Such materials include natural rubber, c~s-polyisoprene, cis-polybutadiene (CB), acrylonitrile-butadiene-styrene copolymers (ABS), butadiene-acrylonitrile rubbers (NBR), isoprene-acrylonitrile rubbers, butadiene-styrene rubbers (SBR), isoprene-styrene copolymers, polychloroprene and the like. Other suitable surface materials include isoprene-isobutylene (butyl) rubbers~
copolymers of conjugated dienes with lower alkyl and alkoxy acrylates, ethylene-propylene-diene polymers (EPD~), poly-urethanes such as those described in Schollenberger U.S.
Patents 2,871,218 and 2,899,411, and the like. Still other suitable surface materials include wood, concrete, s-tainless steel, glass, ceramic tile, -tin, and antifouling coverings 9~S
such as those described in U. S. Patent 3,426,473.
Underwater surfaces or substrates to be contacted with the compositions described heretofore are preferably cleaned prior to contacting in order to promote adhesion of the compositions to the surfaces or substrates. Rust, fouling, oil and other contaminants shoulcl be removed as completely as possible~ Cleaning methods known to the art may be used, such as sandblasting, wire brushing, water blasting, hand buffing and the like. When patching a damaged coating area, it is advisable to clean the fouled surface about 0.5 to 1 inch beyond the spot to be patched and to coat the latter area as well. This precaution insures good bonding at the overlap area of the patch.
Application methods well known to the art may be used. For example, more viscous compositions can be picked up with wet hands or gloves and applied manually to a cleaned substrate. A ball of the composition may be pressed firmly by hand against the substrate and forced slowly from the center to the outer edges in order to displace water and give a coating thickness of about 1/8 to 1/4 inch. There-after the coating may be smoothed and feathered at its edges. Alternatively~ the underwater-curable compositions of this invantion may be applied by brushing or rolling using a pressure feed system~ Yet another application method involves use of an inverted cofferdam fitted tightly against the structure to be coated. Water i9 displaced by pumping air in order to produce an air pocket between the _ 23 -S
cofferdam and the surface to be coated~ which is coated while damp. m e cofferdam can be removed immediately after coating or left in place until compositional curing is complete.
Adhesive and coating thicknesses of the underwater-curing compositions described heretofore may vary widely but are typically from about 0.001 inch to about 0.250 inch and more, preferably from about 0.005 inch to abou-t 0.100 inch. When used as a repair putty, thickness may vary widely up to several inches if the compositions are used to fill cracks, holes or the likeO The compositions may cure at temperatures from about 35F to about 100F
and more, with cure time decreasing as tempera-ture increases.
Underwater cure time generally may range from about 1 hour to about 20 hours, more typically from about 3 hours to 12 hours.
m e compositions described heretofore can be applied to dry, wet or water-submerged surfaces and cured while dry, wet or under water. By a wet surface is meant one containing, covered with or soaked with water. It was both surprising and unexpected to find that the compositions cured rapidly while displacing water on wet or underwater sur-faces~ bonding strongly thereto and developing excellent adhesive strength and flexibility. Water is believed to reac-t to some extent with the compositions described hereto-fore and to act as an-accelerator.
The following examples illus-trate the present invention more fully.
_ 21~ -319~5 EXAMPLES
General Mixing Procedure and Sample Preparation The underwater-curing compositions were prepared following a general mixing procedure. A filler (if used) was mixed with an epoxy resin on an ink mi:ll. Additional filler (if used) was mixed with an amine-terminated liquid polymer on an ink mill. The two mixtures were stirred to-gether in a beaker using a spatula, and the final mixture was used within about 2 hours after mixing was complete"
The components of System X were mixed by stirring in a beaker at room temperature.
Test samples were prepared as follows. Neoprene rubber compound strips were prepared containing an anti-fouling agent and measuring about 25 mm x 200 mm x 2.2 mm.
The strips had the following composition:
MATERIAL WT. PARTS
Neoprene WRT 100 2-Mercaptoimidazoline Magnesium Oxide 4 Phenyl-~-naphthylamine 2 Zinc Oxide 5 Mercaptobenzothiazole Carbon Black 14.5 Bis(tri-n-butyltin)oxide 8 Lauric Acid 3 - 13~.5 Each rubber strip was suspended in a 29-gallon aquarium containing synthetic ocean water and aged for at least 24 hours at 70-80 F. Each strip was then removed from the tank, buffed lightly and returned immediately to the tank.
An underwater-curing composition was applied underwater onto the 25 mm x 200 mm surface of a strip. Application was made by hand or using a putty knife. Composi-tional thickness on the rubber strip was about 0.25 inch.
~9:~9~45 Immediately thereafter, the buffed surface of a second strip was pressed onto the underwater-curing composition while underwater to form a sandwich. The two strips were pressed firmly toge-ther in order to eliminate water be-tween them and allowed to cure underwater.
Materials The amine-terminated liquid polymers used in the following examples were prepared readily by following the procedures described in detail heretofore using N-(2-aminoethyl)-piperazine in the amine-termination reaction.
me amine-terminated liquid polymers~ identified as ATBN, were amine-terminated poly(butadiene/acrylonitrile) co~
polymers having an acrylonitrile content of about 9.5 by weight of polymer and a viscosity at 27C of about 90,000 cps. and a molecular weight of about 3,600.
The non-cycloaliphatic epoxy resin most fre-quently used was a liquid diglycidyl ether of bîsphenol A (DGEBA) having an epoxy equivalent weight of about 185 to 192 and a viscosity at 25 C of about 10,000 to 16,000 cps. The DGEBA resin is sold under the trademark "Epon 828" by Shell Chemical Company. Another non-cycloaliphatic epoxy resin used was the triglycidyl ether of glycerol having an epoxy equivalent weight of about 140 to 160 and a viscosity at 25C of about 100 to 170 cps., this resin being sold under the trademark "Epon 812" by Shell Chemical Company. Yet another non-cycloalipha-tic epoxy resin used was a liquid diglycidyl ether of bisphenol A
(DGEBA) having an epoxy equivalent weight of about 180 to 200 and a viscosity at 25C of about lO,000 -to 16,000 cps.
~919~5 The latter material is sold under the trademark "Epi-Rez 510" by Celanese Corp.
Polyamide resins used in preparing compositions for comparison with the underwater-curing compositions used in the process of this invention included two materials sold under the tradem~rks "Versamid 115" and "Versamid 140" 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 1~0'l is the reaction pro-duct of a dimer dibasic acid and a polyamine and has an approximate amine value of 385 and a reactive equi~alent weight of about 1~6. Amine value is defined as the number of milligrams of potassium hydroxide equivalent to the am~ne alkalinity present in one gram of polyamide resin sample. Reactive equivalent weight is defined as 56,100 (the milligram equivalent weight of potassium hydroxide) divided by the amine value of the polyamide resin sample.
Also used for comparison purposes was a com-mercially available underwater-curing system sold as a two-part system and identified hereinafter as "System X".
Part #l comprised a liquid diglycidyl ether of bisphenol A (DGEBA), and about 52 wt~o of a silica filler. Part #2 comprised a polyamide resin believed to be "Versamide 115", described heretofore,and about 57 wt.~ of a silica filler. Both parts were mixed thoroughly by stirring to-gether just before testing.
~xcept for the amine-terminated liquid polymers described in detail here-tofore, the non-cycloaliphatic epoxy resins, polyamide resins and other materials used in the following examples are known commercial materials and are readily available.
S
Test Methods Peel adhesion strength was tested using the procedure in ASTM D-903. Flexibility was e~aluated by bending up to 360 and by stretching by hand.
Examples 1 - 3 Underwater-curing compositions in each of the following examples were prepared following the general mixing and sample preparation procedure described hereto-fore. ~esting was done after about 48 hours exposure to 10 water at 23C. Test results are summarized in Table 1.
TABLE I
Example 1 2 3 Recipe Epon 828, Wt. Parts 100 100 ATBN, Wt. Parts 800 800 System X, Par-t 1, Wt. Parts - - 30 System X, Part 2, Wt. Parts - ~ L~o Fumed Colloidal Silica, Wt. Parts 135 135 N-550 Carbon Black, Wt. Parts - 90 Test Data Cure time, hours 8-12 8~12 2L~
Average Adhesion Range, lbs/in. 18-30 27-35 3-5 Flexibility Excel- Excel- Very lent lent Poor Samples in examples 1 and 2 cured rapidly and demons-tra-ted superior peel adhesion strength and ~lexi-bility without sagging. In clear contrast, the prior art composition of Example 3 cured slowly and both adhesion and flexibility were ~ery poor.
Exam~es 4 - 8 Under~ater curing compositions in each of the following examples were prepared following -the general mixing and sample preparation procedure described hereto-_ 28 -~L~9~
fore. Testing was done after 72 hours exposure to water at 25 C. Test results are summarized in Table II.
TABLE II
Example 4 5 6 7 8 Reci~
Epon 828, Wt. Parts 100 100 100 - -Epi-Rez 510, Wt. Parts - - - 100 ~TBN, Wto Parts 500 Sys-tem X, Part 1, Wt.Parts - - - - 30 10 System X, Part 2, Wt.Parts - - - - 40 Versamid 115, Wt.Parts - 100 ~ lQ0 ~ersamid 140, Wt.Parts ~ - 100 TiO2,Wt.Parts 250 50 75 5 Test Data -Cure time, Hours ~3 ~24 ~ ~24 ~2l~
Average ~dhesion, lbs/in. 8-9 7-8 5-6 7-8 3_L~
Maximum Adheslon, lbs/in. 12 8.5 6.5 9.5 5 ~lexibili-ty Very Fair Poor Fair Very Good Poor The sample in example 4 cured rapidly and demonstrated superior peel adhesion strength and flexi-bility. In contrast, the prior art compositions o~
examples 5-8 cured more slowly, demonstrated lower peel adhesion strengths and had only very poor to fair flexi bilities.
Compositions described heretofore, comprising at least one non-cycloaliphatic epoxy resin and at least one amine-terminated liquid polymer having a carbon-carbon backbone, cure rapidly and have excellent adhesive strength, with flexibility improving with increasing amount of amine-terminated liquid polymer. The compositions cure underwater in the process of this inven-tion and are useful as underwater repair putties, adhesives, coatings and the like for ship hulls, sonar domes, wooden or concrete piers, and the like.
wherein R is hydrogen or an aIkyl radical containing 1 to 3 carbon atoms. Excellent results were obtained using styrene and acrylonitrile.
Examples of use~ul liquid polymeric backbones comprising carbon-carbon linkages include polyethylene, polyisobutylene, polyisoprene, polybutadiene, poly (vinyl ethyl ether), poly (ethylacrylate) and poly (butylacrylate) as well as copolymers o~ butadiene and acryloni-trile;
butadiene and styrene; vinyl aceta-te and isoprene; vinyl acetate and chloroprene; vinly ethyl ether and diallyl ether; vinyl ethyl ether and ~-methyl styrene; vinyl ethyl ether and vinyl bromide; methyl acrylate and butadiene;
methyl acrylate and ethyl acrylate; methyl acrylate and butyl acrylatej methyl acrylate and 2-ethyl hexyl acrylate;
ethyl acrylate and ethylene; ethyl acrylate and isobutylene;
ethyl acrylate and isoprene; ethyl acrylate and butadiene;
ethyl acrylate and vinyl acetate; ethyl acryla-te 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 ancl 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 1~9~ 95 acrylate and acrylonitrilej butyl acrylate and vin~l chloride; and the like.
Liquid carboxyl-terminated polymers may be prepared by free-radical polymerization using carboxyl-containing initiators and/or modifiers as disclosed in U.S. Patent 3,285,9~9 and German Pa-tent 1,150,205 and by solutio~ polymerization using lithium metal or organo-metallic compounds and post-treating the polymers to form carboxyl groups as disclosed in U.S. Patents 3,135,716 and 3,~31,235. The polymers can also be prepared by reacting liquid polymers having other than terminal carboxyl groups with compounds so as to yield carboxyl groups. For example, liquid carboxyl-terminated polymers can be prepared from liquid hydroxyl-terminated polymers by reaction with dicar-boxyl compounds or anhydrides. I,iquid halogen--terminated polymers can be reacted with unsaturated anhydrides in the presence of Lewis acids to yield carboxyl groups. Th~s, it is seen that the method of preparing the liquid carboxyl-terminated polymer is not cri-tical to the invention.
The essential features of the polymer are that it have at least terminal carboxyl groups and a polymeric backbone of carbon-carbon linkages.
Examples of preferred liquid carboxyl-terminated polymers include carboxyl-terminated polyethylene, carboxyl-terminated polyisobutylene, carboxyl-terminated polybutadiene, carboxyl-terminated polyisoprene, carboxyl-terminated poly_ (ethylacrylate), as well as carboxyl-terminated copolymers of butadiene and acrylonitrile and of butadiene and styrene.
Carboxyl-terminated copolymers of butadiene with acrylonitrile or styrene were found to be especially useful. mese poly-mers may contain from about 50~ to about 99.6~o by ~eight of 9~
butadiene, from about 0~ to about ~0% by weight of acry-lonitrile or styrene and from about 0.~ to about 10~ by weight of carboxyl, based upon the total weight of polymer.
m e carboxyl-terminated liquid polymers can be esterified with an aliphatic monohydric alcohol by methods well known to the art in order to produce ester-terminated liquid polymers. ~or example, a carboxyl-terminated polymer and an aliphatic monohydric alcohol can be reacted in a distillation column or under reflux in the presence of a small amount of an acid catalyst. Suitable acid ca-talysts include organic acids containing 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as acetic acid, pro-pionic acid, benzoic acid, monoes-ters and dies-ters of orthophosphoric acid, alkarylsulf'onic acids such as p-toluene sulfonic acid, and the like; inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like; and Lewis acids such as tetraisopropyl titanate and the like. The amount of acid catalyst used may be as little as about 0.01~ up to about 5~ by weight based upon total reactant weight. Suitable aliphatic monohydric alcohols for use in the esterif'ication reaction contain f'rom 1 to 12 carbon a-toms, more preferably from 1 to 6 carbon atoms, and have boiling points below abou-t 150~., more preferably below about 100C. Primary aliphatic mono-hydric alcohols are preferred. Examples of suitable aliphatic monohydric alcohols include alkanols containing from 1 to 6 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, l-butanol, 2-hexanol~ 3-hexanol, and the like.
Other suitable aliphatic monohydric alcohols include 2--me-thoxyethanol, 2-ethoxyethanol and the like. Excellent results may be obtained using ethanol, l-propanol or 1-butanol.
m e carboxyl-terminated liquid polymers can be acylated by methods well known to the art in order to produce acid chloride-terminated liquid polymers. For example, a carboxyl--terminated polymer can be reacted with thionyl chloride to produce an acid chloride-terminated polymer. HCl and S02 are e~olved primarily as gases and are separated easily from the acid chloride-terminated poly-mer, and any excess thionyl chloride can be removed easily 'by ~acuum distillation or by washing with a solvent such as methanol. Other suitable but less pref'erred acylation agents include phosphorus trichloride and phosphorus pen-tachloride.
Amines which react well with the carboxyl-termin-ated, ester-terminated and acyl-terminated polymers described heretofore include aliphatic amines containing from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, and at least two, more pref'erably two, primary and/or secondary amine groups. Also suitable are alicyclic amines containing from 4 to 20 carbon atoms, more pref'erably from 4 to 12 carbon atoms, and at least two, more preferably two, primary and/or secondary amine groups. Heterocyclic amines may also be used which contain from 2 -to 20 carbon atoms, more preferably from 2 to 12 carbon atoms, and at least two, more preferably -two, primary and/or secondary amine groups.
Examples of suitable amines just described include aliphatic amines such as ethylenediamine, 1,2-propanediamine~ 1~3-propanediamine, 1,4-butanediamine, 2 me-thyl-1,2-propanedia-1~9~L9~S
mine, 1,5-pentanediamine, 1,6 hexanediamine, 1,7-heptane-diamine, 1,8-octanediamine, l,10-decanediamine, 1,12-dodecanediamine and the like; aliphatic polyamines such as diethylenetriamine, triethylenetetramine, -tetraethylene-pentamine, bis(hexamethylene) triamine, 3~3l-imincbi amine, `and the like; alicyclic diamines and polyamines such as 1,2-diaminocyclohexane, 1,8-p-menthanediamine and the like; and heterocyclic diamines and polyamines such as ~-(aminomethyl) piperidine; piperazine; N-(aminoalkyl) piperazines wherein each alkyl group contains from 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, such as N-(2-aminoethyl)piperazine, N-(3-aminopropyl) piperazine, N,N'-bis (3-aminopropyl)piperazine, and -the like.
More preferably the amines just described contain at least two primary and/or secondary amine groups having different reactivitiesO The presence of amine groups having different reactivities makes the amine-termination reaction more likely than the coupling of the li~uid polymers~ and a smaller amine excess may be used in order to avoid coupling.
Examples of more preferred amines include some alicyclic amines such as 1,8-p-menthanediamine and the like; and some heterocyclic amines such as 4-(aminomethyl)piperidine and N-(aminoalkyl)piperazines wherein the alkyl group contains from 1 to 12 carbon atoms, more pre~erably 1 to 6 carbon atoms, such as N-(2-aminoethyl)piperazine, N-(3-aminopropl) piperazine, and the like. Excellent results were obtained using N-(2-aminoethyl)piperazine.
Aroma-tic diamines and polyamines can be used to produce amine-terminated polymers. The high tempera-ture required for aromatic amine reaction with carboxyl--te~minated :1~9:~L9~5i polymers causes excessive degradation of reactants and products and is therefore much less preferred. However, aromatic amines may react well ~ith the acyl-terminated polymers described heretofore. Suitable aromatic amines contain at least two primary or secondary amine groups bonded directly to at least one aromatic nucleus. Examples of suitable aromatic amines include 4,5-acenaphthenediamine, 3,5-diaminoacridine, 1,4-diaminoanthraquinone, 3,5-dia-minobenzoic acid, 2,7-fluorenediamine, 1,5-naphthalenedia-mine, 1,8-naphthalenediamine, 2,4-toluenediamine, 2,6-toluenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and the like.
A solvent is not required for the amine-termination reaction but may be used. Mixtures of solvents may also be used. Suitable solvents include aliphatic and cycloali-phatic ethers containing from 3 to 10 carbon atoms~ more preferably from 3 to 6 carbon atoms, such as tetrahydrofuran, diethylether and the like; halogenated aliphatic hydrocarbons containing from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, such as chloroform, carbon tetrachloride, 1,2-dichloroethylene, trichloroethylene, tetrachloroe-thylene and the like; and esters containing ~rom 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as ethyl acetate, n-butyl acetate, hexyl acetate, benzyl acetate, methyl propionate, e-thyl propionate and the like.
Also suitable as solvents and more preferred are aromatic compounds having the formula.
~4 R~I~R4 ~'3i~'~S
wherein R is hydrogen, halogen or an alkyl radical contain-ing 1 -to 3 carbon atoms, and at least two R4s are hydrogen.
More preferably R is hydrogen, chlorine, or an alkyl radical containing 1 to 2 carbon atoms, and at least three R~s are hydro~en. Suitable aromatic solvents include benzene, chloro-benzene, toluene, o-, m- and p-xylene, o-, m- and p-diethyl-benzene, cumene, mesitylene and the like.
A suf~icient quantity of at least one amine described heretofore may be reacted with a carboxyl-terminated, ester-terminated or acid-chloride-terminated liquid polymer described heretofore in order to produce an amine-terminated liquid polymer containing from about 1.7 to about 3 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 will be from about 1.7 to about 3 groups per molecule, more preferably from about 1.7 to about 2.3 groups per molecule. In thistypical case, from about 1.2 to about 6 mole equivalents and more, more preferably from about 1.2 to about 3 mole equivalents of at least one amine described heretofore can be used per mole equivalent of carboxylated~ es-terified or acylated liquid polymer de-scribed heretofore. However, when the carboxylated, esteri-fied or acylated liquid polymer also contains polymerized therein appreciable amounts of acrylic acid, acrylates or the like, the amount of amine reacted should be limited so that the amine-terminated liquid polymer contains no more than an average of 1.7 to about 3 primary and/or ~9i~
secondary amine groups per molecule.
No catalyst is required, and many types of mixing apparatus can be used in the amine termination reaction.
For example7 simple mixers can be used, including turbine stirrers as well as propeller mixers. Reaction components can be combined in any order. The reaction mixture may be heated (or refluxed if a solvent is used) at a temperature from about 80C to about 150C, typically ~or about 1 to 6 hours. m e amine-terminated liquid polymer may be purified by vacuum distillation or by washing with a solvent such as a benzene-methanol mixture, followed by drying the polymer. Amine content of the amine-terminated liquid polymers can be analyzed qualitati~ely by infrared spec-troscopy. Amine content can also be analyzed quanti-tatively following the procedure described by Siggia, Quantita-tive Organic Analysis via Functional Groups, N.Y., Wiley and Sons, Inc., 1963, pp. 452-456.
Underwater Curing of Non-Cycloaliphatic Epoxy Resins and Amine-Terminated Liquid Polvmers v m e compositions used in the process of this invention comprise (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin described hereinafter and (B) from about 1 to abou-t 2,000 parts by weight of at least one amine-terminated liquid polymer described here-tofore. Compositional properties may be varied widely by using varying amounts of amine-terminated liquid polymer.
Chain extenders, crosslinkers, and curing agents described hereinafter may also be used in the epoxy compositions but are not required.
Non-cycloaliphatic epoxy resins suitable for use in this invention together with amine-terminated liquid _ lL~ ~
9~5 polymers contain at least an average of about 1.7 epoxy groups per molecule, more preferably from about 1.7 to about 3 epoxy groups per molecule, and even more preferably from about 1.7 to about 2.3 epoxy groups per molecule. The non-cycloaliphatic epoxy resins may be liquids or low~
melting solids but are preferably liquids having a bulk viscosity from about 100 centipoises to about 2,000,000 centipoises (measured using a Brookfield RVT viscometer at 25 C). The epoxy resins can have an epoxy equivalent weight (gram molecular weight per epoxy group) from about 70 to about 6,000,more preferably from about 70 to about 2,000.
Suitable non-cycloaliphatic epoxy resins include epoxidized cyclic silane, epoxidized soybean oil, polyglycidyl es-ters oI` polycarboxylic acids, epoxidized polyolefins, and gly-cidyl ether resins, with glycidyl ether resins being pre-ferred Examples of suitable polyglycidyl esters of poly-carboxylic acids include the diglycidyl ester of linoleic dimer acid, the triglycidyl ester of linoleic trimer acid, and the like. Suitable glycidyl ether resins include poly-allyl glycidyl ether;`the diglycidyl ether of chlorendic diol; -the diglycidyl ether of dioxanediol; the diglycidyl e-ther of endomethylene cyclohexanediol; epoxy novolac resins;
alkanediol diglycidyl ethers; alkanetriol triglycidyl ethers; and the like.
More preferred glycidyl ether resins include alkanediol diglycidyl ethers ha~ing the formula C 2~-CH-CH2 _E_O-X~O-CH2 -(~H-CH2 gS
wherein X is an alkylene or alkylidene group containing from 1 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms, and n is from 1 to 25, more preferably from 1 to 15. Suitable alkanediol diglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol digly-cidyl ether, butanediol diglycidyl ether, and the like.
Other more preferred glycidyl ether resins in-clude alkanetriol triglycidyl ethers wherein the alkane group contains from 2 to 10 carbon atoms, more pre~erably from 3 to 6 carbon atoms, such as glyceryl triglycidyl ether, the triglycidyl ether of trimethylolpropane and the lLke. Ano-ther more preferred class of glycidyl ether resins is the digl~cidyl and polyglycidyl ethers of bi-sphenols, the bisphenols ha~ing the formula HO ~ R5 - ~ OH
wherein R5 is a bi~alent radical containing 1 to 8 atoms of at least one atom selected from the group consisting of C, O, S and N, more preferably an alkylene or alkylidene group containing 1 to 8 carbon atoms, and even more pre-ferably an alkylene or alkylidene group containing 1 to 6carbon atoms. Examples of suitable bisphenols include methylene bisphenol, isopropylidene bisphenol~ butylidene bisphenol, octylidene bisphenol~ bisphenol sulfide, bisphen-ol sulfone, bisphenol ether, bisphenol amine, and the like.
Excellent results were obtained using isopropylidene bi-sphenol (bisphenol A). Examples of suitable di- and poly-glycidyl ethers inclu~e those of isopropylidene bisphenol having the formula S
C~v .
~a [~
o_v o ~ ~ .
s~
~'' o v Pi o ~ .
wherein n is from about O -to about 20, more preferably from about O to about 2.
Cycloaliphatic epoxy resins are much less pre-ferred in the process of this invention because they are substantially uncurable at room tempera-ture ~hen mixed with an amine-terminated liquid polymer. By cycloaliphatic epoxy resin is meant a resin in which an epoxy group is itself part of a cycloaliphatic ring struc-ture. Such cycloaliphatic resins include bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, the bis(epoxydicyclo-pentyl) ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-(3,4-epoxy) -cyclohexane carboxylate, bis(3,4-epox~-6-methylcyclohexylmethyl) adipate and the like. Other cyc-loaliphatic resins are described in Lee et al, EIandbook f Epox~ Resins, McGraw-EIill Book Company, N.Y., 1967, Chapter 4.
Other reactive additives are not required in the compositions comprising an amine terminated liquid polymer and an epoxy resin. However, chain extenders and/or cross-linkers may be used. The amount of chain extender and/or cross-linker used may vary wiclely depending on relative weights and reactive functionalities of epoxy resins and amine-terminated liquid polymers. The amount of chain extender and/or cross-linker used also depends on properties desired in the compositions of -this invention. Typical amounts of chain extender and/or cross-linker used may vary from about O to about 60 parts by weight, more preferably from about O to about 35 parts by weight pèr 100 parts by ~reight of epoxy resin.
Suitable chain extenders and/or cross-linkers can be any of the difunctional materials known by those ~o~
skilled in the art to be reactive with epoxy compounds, including dibasic acids such as azelaic acid, phthalic acid and the like~ and dimercap-tans such as 1,6-hexan-edithiol, 1,8-octanedithiol and the like. Also sui-table as chain extenders are anhydrides such as maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride and the like; diisocyanates such as 4,4'-dicyclo-pentyl methylene diisocyanate, 4,4'-diphenylmethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolyl.ene diiso-cyanate, 1,4-phenylene diisocyanate and the like; di- and polyamines described in detail hereto~ore in connection with preparation o~ -the a~ine-term~.nated liquid polymer and lncluding the dlamine made by reacting linoleic acid dimer with a diamine, ethylene diamlne, N-(2-aminoethyl)piperazine and the like; and alipha-tic dihalides con-taining ~rom 1 to 12 carbon atoms, more pre~erably aliphatic dihalides con-taining ~rom 1 to 8 carbon atoms wherein the halide is bromide and/or chloride, such as 1,4-dibromobutane, 1,3-dibromobutane, l,~-dichlorobu-tane, 1,2-dichloroethane, l,l~-diiodobutane, 1,6-dichlorohexane, and the like.
Also suitable as chain extenders and/or cross-linkers and more pre~erred ln this invention are dihydric aromatic compounds con-taining from 6 to 24 carbon atoms, more pre~erably ~rom 6 to 18 carbon atoms. Suitable di-hydric aroma-tic compounds include catechol, resorcinol, 3-hydroxybenzyl alcohol, ~-hydroxybenzylalcohol, l,3-dihy-~roxynaphthalene, 1,5-dihydroxynaphthalene, 1~7~dihydroxy-naphthalene, and, even more pre~erably, bisphenols having -the ~ormula ~1995i H ~ R5 ~ - OH
wherein R5 is a bivalent radical containing 1 -to 8 atoms of C, O, S and/or N, more preferably an alkylene or alkylidene group containing 1 to 8 carbon atoms, and even more preferably an alkylene or alkylidene group containing 1 to 6 carbon atoms. Examples of suitable bisphenols include methylene bisphenol3 isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, bisphenol amine, and the like. E~cellent results were obtained using isopropylidene bisphenol (bisphenol A).
Curing agents may be used to accelera-te and/or supplement the reaction between the epoxy resin and amine-terminated liquid polymer described heretofore but are not required. Suitable curing agents include BF3-amine complexes, hexahydrophthalic anhydride, dicyandiamide, imidazoles such as 2-ethyl-~-methyl-imidazole, triethylenetetraamine, and the like.
In addition to the -two essential components (an amine-terminated liquid polymer and an epox~ resin) and the two optional components (a chain extender or a curing agent) described heretofore, the compositions may contain a broad range of other compounding ingredients. These ingredients are typical ingredients used in rubber and/or epoxy com-pounding. Standard levels of these ingredients are used, such levels being well known in the art. For example, re-inforcing fillers and other ingredients which thicken the liquid composition may be used at levels up to about 250 parts by weight and more at room temperature based upon 100 i~915~9S
parts by weight of the mixture of epoxy resin and amine-terminated liquid polymer.
Examples of compounding ingredients include re-inforcing fillers such as carbon blacks, metal carbonates and silicates, and glass, asbestos, and tex-tile fibers;
non-reinforcing fillers such as titanium dioxide, silica and the like; colorants such as metal oxides and metal sul-fides, and organic colorants; lubricants and plasticizers such as petroleum oils, cas-tor oil, glycerin, silicones, aromatic and paraffinic oils, and alkyl and aromatic phthalates, sebacates, trimellitates, and the like; and antioxidants and stabilizers such as phenyl-~-naphthylam-ine, 2,6-di-t-butyl paracresol, 2,2~-methylenebis-(4-ethyl-6-t-butyl phenol), 2,2'-thiobis-(4-methyl-6-t-butyl phenol), 4,4~-butylidenebis-(6--t-butyl-m-cresol), tris-(3,5-di-t-bu~yl-4-hydroxybenzyl) isocyanurate, hexahydro-1,3,5-tris-~-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl triazine, tetrakis-methylene-3(3',5~-di-t-butyl-4'-hydroxyphenyl)propionate methane, distearyl thiodipropionate, tri(nonylated phenyl) phosphite, and the like. Wetting agents such as blown fish oil and the li.ke can also be used. Other suitable com-pounding ingredients include anti-fouling toxic agents such as bis~-tri-n-butyltin)oxide described in U.S. Patent 3,426,473.
m e epoxy resin compositions usable in the process of this invention comprise (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin described heretofore, (B) from about 1 to about 2,000 parts by weight, more pre-10919'r35 ferably from about 300 to about 1,500 parts by weight, of at least one amine-terminated liquid polymer described heretofore, (C) optionally, a chain extender and/or cross-linker, (D) optionally, a curing agent and (E) optionally, other compounding ingredients described heretofore. The composition components can be mixed using mixing kettles, Henschel mixers, ink mills, Banbury mixers, or the like.
Standard mixing techniques can be used. A curing agent, if used, is preferably mixed first with the amine-terminated liquid polymer. Pot life of the underwater-curing com-positions after mixing typically is from about 2 hours to about 4 hours. Heating the mixture up to about 100C. may be helpful to obtain dissolution and uniform dispersion of` the materials, but such heating causes the compositions to cure much more rapidly.
A wide variety of surface materials may be coated, puttied, patched or the like using the underwater-curing materials described heretofore. Such materials include natural rubber, c~s-polyisoprene, cis-polybutadiene (CB), acrylonitrile-butadiene-styrene copolymers (ABS), butadiene-acrylonitrile rubbers (NBR), isoprene-acrylonitrile rubbers, butadiene-styrene rubbers (SBR), isoprene-styrene copolymers, polychloroprene and the like. Other suitable surface materials include isoprene-isobutylene (butyl) rubbers~
copolymers of conjugated dienes with lower alkyl and alkoxy acrylates, ethylene-propylene-diene polymers (EPD~), poly-urethanes such as those described in Schollenberger U.S.
Patents 2,871,218 and 2,899,411, and the like. Still other suitable surface materials include wood, concrete, s-tainless steel, glass, ceramic tile, -tin, and antifouling coverings 9~S
such as those described in U. S. Patent 3,426,473.
Underwater surfaces or substrates to be contacted with the compositions described heretofore are preferably cleaned prior to contacting in order to promote adhesion of the compositions to the surfaces or substrates. Rust, fouling, oil and other contaminants shoulcl be removed as completely as possible~ Cleaning methods known to the art may be used, such as sandblasting, wire brushing, water blasting, hand buffing and the like. When patching a damaged coating area, it is advisable to clean the fouled surface about 0.5 to 1 inch beyond the spot to be patched and to coat the latter area as well. This precaution insures good bonding at the overlap area of the patch.
Application methods well known to the art may be used. For example, more viscous compositions can be picked up with wet hands or gloves and applied manually to a cleaned substrate. A ball of the composition may be pressed firmly by hand against the substrate and forced slowly from the center to the outer edges in order to displace water and give a coating thickness of about 1/8 to 1/4 inch. There-after the coating may be smoothed and feathered at its edges. Alternatively~ the underwater-curable compositions of this invantion may be applied by brushing or rolling using a pressure feed system~ Yet another application method involves use of an inverted cofferdam fitted tightly against the structure to be coated. Water i9 displaced by pumping air in order to produce an air pocket between the _ 23 -S
cofferdam and the surface to be coated~ which is coated while damp. m e cofferdam can be removed immediately after coating or left in place until compositional curing is complete.
Adhesive and coating thicknesses of the underwater-curing compositions described heretofore may vary widely but are typically from about 0.001 inch to about 0.250 inch and more, preferably from about 0.005 inch to abou-t 0.100 inch. When used as a repair putty, thickness may vary widely up to several inches if the compositions are used to fill cracks, holes or the likeO The compositions may cure at temperatures from about 35F to about 100F
and more, with cure time decreasing as tempera-ture increases.
Underwater cure time generally may range from about 1 hour to about 20 hours, more typically from about 3 hours to 12 hours.
m e compositions described heretofore can be applied to dry, wet or water-submerged surfaces and cured while dry, wet or under water. By a wet surface is meant one containing, covered with or soaked with water. It was both surprising and unexpected to find that the compositions cured rapidly while displacing water on wet or underwater sur-faces~ bonding strongly thereto and developing excellent adhesive strength and flexibility. Water is believed to reac-t to some extent with the compositions described hereto-fore and to act as an-accelerator.
The following examples illus-trate the present invention more fully.
_ 21~ -319~5 EXAMPLES
General Mixing Procedure and Sample Preparation The underwater-curing compositions were prepared following a general mixing procedure. A filler (if used) was mixed with an epoxy resin on an ink mi:ll. Additional filler (if used) was mixed with an amine-terminated liquid polymer on an ink mill. The two mixtures were stirred to-gether in a beaker using a spatula, and the final mixture was used within about 2 hours after mixing was complete"
The components of System X were mixed by stirring in a beaker at room temperature.
Test samples were prepared as follows. Neoprene rubber compound strips were prepared containing an anti-fouling agent and measuring about 25 mm x 200 mm x 2.2 mm.
The strips had the following composition:
MATERIAL WT. PARTS
Neoprene WRT 100 2-Mercaptoimidazoline Magnesium Oxide 4 Phenyl-~-naphthylamine 2 Zinc Oxide 5 Mercaptobenzothiazole Carbon Black 14.5 Bis(tri-n-butyltin)oxide 8 Lauric Acid 3 - 13~.5 Each rubber strip was suspended in a 29-gallon aquarium containing synthetic ocean water and aged for at least 24 hours at 70-80 F. Each strip was then removed from the tank, buffed lightly and returned immediately to the tank.
An underwater-curing composition was applied underwater onto the 25 mm x 200 mm surface of a strip. Application was made by hand or using a putty knife. Composi-tional thickness on the rubber strip was about 0.25 inch.
~9:~9~45 Immediately thereafter, the buffed surface of a second strip was pressed onto the underwater-curing composition while underwater to form a sandwich. The two strips were pressed firmly toge-ther in order to eliminate water be-tween them and allowed to cure underwater.
Materials The amine-terminated liquid polymers used in the following examples were prepared readily by following the procedures described in detail heretofore using N-(2-aminoethyl)-piperazine in the amine-termination reaction.
me amine-terminated liquid polymers~ identified as ATBN, were amine-terminated poly(butadiene/acrylonitrile) co~
polymers having an acrylonitrile content of about 9.5 by weight of polymer and a viscosity at 27C of about 90,000 cps. and a molecular weight of about 3,600.
The non-cycloaliphatic epoxy resin most fre-quently used was a liquid diglycidyl ether of bîsphenol A (DGEBA) having an epoxy equivalent weight of about 185 to 192 and a viscosity at 25 C of about 10,000 to 16,000 cps. The DGEBA resin is sold under the trademark "Epon 828" by Shell Chemical Company. Another non-cycloaliphatic epoxy resin used was the triglycidyl ether of glycerol having an epoxy equivalent weight of about 140 to 160 and a viscosity at 25C of about 100 to 170 cps., this resin being sold under the trademark "Epon 812" by Shell Chemical Company. Yet another non-cycloalipha-tic epoxy resin used was a liquid diglycidyl ether of bisphenol A
(DGEBA) having an epoxy equivalent weight of about 180 to 200 and a viscosity at 25C of about lO,000 -to 16,000 cps.
~919~5 The latter material is sold under the trademark "Epi-Rez 510" by Celanese Corp.
Polyamide resins used in preparing compositions for comparison with the underwater-curing compositions used in the process of this invention included two materials sold under the tradem~rks "Versamid 115" and "Versamid 140" 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 1~0'l is the reaction pro-duct of a dimer dibasic acid and a polyamine and has an approximate amine value of 385 and a reactive equi~alent weight of about 1~6. Amine value is defined as the number of milligrams of potassium hydroxide equivalent to the am~ne alkalinity present in one gram of polyamide resin sample. Reactive equivalent weight is defined as 56,100 (the milligram equivalent weight of potassium hydroxide) divided by the amine value of the polyamide resin sample.
Also used for comparison purposes was a com-mercially available underwater-curing system sold as a two-part system and identified hereinafter as "System X".
Part #l comprised a liquid diglycidyl ether of bisphenol A (DGEBA), and about 52 wt~o of a silica filler. Part #2 comprised a polyamide resin believed to be "Versamide 115", described heretofore,and about 57 wt.~ of a silica filler. Both parts were mixed thoroughly by stirring to-gether just before testing.
~xcept for the amine-terminated liquid polymers described in detail here-tofore, the non-cycloaliphatic epoxy resins, polyamide resins and other materials used in the following examples are known commercial materials and are readily available.
S
Test Methods Peel adhesion strength was tested using the procedure in ASTM D-903. Flexibility was e~aluated by bending up to 360 and by stretching by hand.
Examples 1 - 3 Underwater-curing compositions in each of the following examples were prepared following the general mixing and sample preparation procedure described hereto-fore. ~esting was done after about 48 hours exposure to 10 water at 23C. Test results are summarized in Table 1.
TABLE I
Example 1 2 3 Recipe Epon 828, Wt. Parts 100 100 ATBN, Wt. Parts 800 800 System X, Par-t 1, Wt. Parts - - 30 System X, Part 2, Wt. Parts - ~ L~o Fumed Colloidal Silica, Wt. Parts 135 135 N-550 Carbon Black, Wt. Parts - 90 Test Data Cure time, hours 8-12 8~12 2L~
Average Adhesion Range, lbs/in. 18-30 27-35 3-5 Flexibility Excel- Excel- Very lent lent Poor Samples in examples 1 and 2 cured rapidly and demons-tra-ted superior peel adhesion strength and ~lexi-bility without sagging. In clear contrast, the prior art composition of Example 3 cured slowly and both adhesion and flexibility were ~ery poor.
Exam~es 4 - 8 Under~ater curing compositions in each of the following examples were prepared following -the general mixing and sample preparation procedure described hereto-_ 28 -~L~9~
fore. Testing was done after 72 hours exposure to water at 25 C. Test results are summarized in Table II.
TABLE II
Example 4 5 6 7 8 Reci~
Epon 828, Wt. Parts 100 100 100 - -Epi-Rez 510, Wt. Parts - - - 100 ~TBN, Wto Parts 500 Sys-tem X, Part 1, Wt.Parts - - - - 30 10 System X, Part 2, Wt.Parts - - - - 40 Versamid 115, Wt.Parts - 100 ~ lQ0 ~ersamid 140, Wt.Parts ~ - 100 TiO2,Wt.Parts 250 50 75 5 Test Data -Cure time, Hours ~3 ~24 ~ ~24 ~2l~
Average ~dhesion, lbs/in. 8-9 7-8 5-6 7-8 3_L~
Maximum Adheslon, lbs/in. 12 8.5 6.5 9.5 5 ~lexibili-ty Very Fair Poor Fair Very Good Poor The sample in example 4 cured rapidly and demonstrated superior peel adhesion strength and flexi-bility. In contrast, the prior art compositions o~
examples 5-8 cured more slowly, demonstrated lower peel adhesion strengths and had only very poor to fair flexi bilities.
Compositions described heretofore, comprising at least one non-cycloaliphatic epoxy resin and at least one amine-terminated liquid polymer having a carbon-carbon backbone, cure rapidly and have excellent adhesive strength, with flexibility improving with increasing amount of amine-terminated liquid polymer. The compositions cure underwater in the process of this inven-tion and are useful as underwater repair putties, adhesives, coatings and the like for ship hulls, sonar domes, wooden or concrete piers, and the like.
Claims (18)
1. A process comprising applying an under-water-curing composition to a dry or wet surface or a surface submerged in water, and thereafter curing the composition on said wet or submerged surface, said com-position comprising (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin containing at least an average of about 1.7 epoxy groups per molecule, said resin having an epoxy equivalent weight from about 70 to about 6,000, and (B) from about 1 to about 2,000 parts by weight of at least one amine-terminated liquid polymer containing an average from about 1.7 to about 3 amine groups per molecule, said groups being primary, secondary or a mixture thereof, and said polymer having the formula Y-? ? B ? ?-Y
wherein Y is a univalent radical obtained by removing hydro-gen from an amine group of an aliphatic, alicyclic, hetero-cyclic or aromatic amine containing from 2 to 20 carbon atoms and at least two amine groups, at least two of said amine groups being primary, secondary or a mixture thereof, and B is a polymeric backbone comprising carbon-carbon linkages and-containing polymerized units of at least one vinylidene monomer having at least one terminal CH2=C<
group, said monomer being selected from the group consist-ing of (a) monoolefins containing 2 to 14 carbon atoms, (b) dienes containing 4 to 10 carbon atoms, (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms, (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms, and said R1 being a member selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms, alkoxyalkyl of 2 to 12 carbon atoms, alkylthioalkyl of 2 to 12 carbon atoms and cyanoalkyl of 2 to 12 carbon atoms.
wherein Y is a univalent radical obtained by removing hydro-gen from an amine group of an aliphatic, alicyclic, hetero-cyclic or aromatic amine containing from 2 to 20 carbon atoms and at least two amine groups, at least two of said amine groups being primary, secondary or a mixture thereof, and B is a polymeric backbone comprising carbon-carbon linkages and-containing polymerized units of at least one vinylidene monomer having at least one terminal CH2=C<
group, said monomer being selected from the group consist-ing of (a) monoolefins containing 2 to 14 carbon atoms, (b) dienes containing 4 to 10 carbon atoms, (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms, (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms, and said R1 being a member selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms, alkoxyalkyl of 2 to 12 carbon atoms, alkylthioalkyl of 2 to 12 carbon atoms and cyanoalkyl of 2 to 12 carbon atoms.
2. A process of claim 1, wherein said carbon-carbon linkages comprises at least 90% by weight of total polymeric backbone weight, and said monomer is selected from the group consisting of (a) monoolefins containing 2 to 8 carbon atoms, (b) dienes containing 4 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms and said R1 being a member selected from the group consisting of hydrogen, alkyl of 1 to 8 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, alkylthioalkyl of 2 to 8 carbon atoms and cyanoalkyl of 2 to 8 carbon atoms.
3. A process of claim 2, wherein said epoxy resin has an epoxy equivalent weight from about 70 to about 2,000.
4. A process of claim 3, wherein said epoxy resin is a glycidyl ether resin.
5. A process of claim 4, wherein said epoxy resin is selected from the group consisting of (1) alkanediol diglycidyl ethers having the formula wherein X is an alkylene or alkylidene group containing from 1 to 10 carbon atoms, and n is from 1 to 25, (2) di- and polyglycidyl ethers of bisphenols, said bisphenols having the formula wherein R5 is a bivalent radical containing from 1 to 8 carbon atoms of at least one atom selected from the group consisting of C, O, S and N, and (3) alkanetriol triglycidyl ethers wherein the alkane group contains from 2 to 10 carbon atoms.
6. A process of claim 5, wherein said vinylidene monomer contains copolymerized therewith from 0% up to about 50% by weight of at least one comonomer selected from the group consisting of (f) vinyl aromatics having the formula wherein R2 is a member selected from the group consisting of hydrogen, halogen and alkyl of 1 to 4 carbon atoms, (g) vinyl nitriles having the formula wherein R3 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms, (h) vinyl halides, (i) divinyls and di-acrylates, (j) amides of .alpha.,.beta.-olefinically unsaturated carboxy-lic acids containing 2 to 8 carbon atoms, and (k) allyl alcohol.
7. A process of claim 6 wherein said amine groups have different reactivities, and said comonomer is selected from the group consisting of (f) said vinyl aromatics and (g) said vinyl nitriles.
8. A process of claim 7 wherein said epoxy resin is a diglycidyl ether of isopropylidene bisphenol, said amine is at least one N-(aminoalkyl)piperazine, the aminoalkyl group of said amine contains from 1 to 12 carbon atoms, said vinylidene monomer is at least one of said dienes, and said comonomer is at least one of said vinyl nitriles.
9. A process of claim 8 wherein said diene is butadiene, said vinyl nitrile is acrylonitrile, and said amine is N-(2-aminoethyl)piperazine.
10. A product of a process comprising applying an underwater-curing composition to a dry or wet surface or a surface submerged in water, and thereafter curing the composition on said wet or submerged surface, said composition comprising (A) 100 parts by weight of at least one non-cycloaliphatic epoxy resin containing at least an average of about 1.7 epoxy groups per molecule, said resin having an epoxy equivalent weight from about 70 to about 6,000, and (B) from about 1 to about 2,000 parts by weight of at least one amine-terminated liquid polymer con-taining an average from about 1.7 to about 3 amine groups per molecule, said groups being primary, secondary or a mixture thereof, and said polymer having the formula Y-? ? B ? ?-Y
wherein Y is a univalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing from 2 to 20 carbon atoms and at least two amine groups, at least two of said amine groups being primary, secondary or a mixture thereof, and B is a polymeric backbone comprising carbon-carbon linkages and containing polymerized units of at least one vinylidene monomer having at least one terminal CH2=C< group, said monomer being selected from the group consisting of (a) mono-olefins containing 2 to 14 carbon atoms, (b) dienes contain-ing 4 to 10 carbon atoms, (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms, (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms, and said R1 being a member selected from the group consisting of alkyl of 1 to 18 carbon atoms, alkoxy-alkyl of 2 to 12 carbon atoms, alkylthioalkyl of 2 to 12 carbon atoms, and cyanoalkyl radical of 2 to 12 carbon atoms.
wherein Y is a univalent radical obtained by removing hydrogen from an amine group of an aliphatic, alicyclic, heterocyclic or aromatic amine containing from 2 to 20 carbon atoms and at least two amine groups, at least two of said amine groups being primary, secondary or a mixture thereof, and B is a polymeric backbone comprising carbon-carbon linkages and containing polymerized units of at least one vinylidene monomer having at least one terminal CH2=C< group, said monomer being selected from the group consisting of (a) mono-olefins containing 2 to 14 carbon atoms, (b) dienes contain-ing 4 to 10 carbon atoms, (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms, (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms, and said R1 being a member selected from the group consisting of alkyl of 1 to 18 carbon atoms, alkoxy-alkyl of 2 to 12 carbon atoms, alkylthioalkyl of 2 to 12 carbon atoms, and cyanoalkyl radical of 2 to 12 carbon atoms.
11. A product of a process of claim 10, wherein said carbon-carbon linkages comprise at least 90% by weight of total polymeric backbone weight, and said monomer is selected from the group consisting of (a) monoolefins containing 2 to 8 carbon atoms, (b) dienes containing 4 to 8 carbon atoms, and (e) acrylic acids and acrylates having the formula said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms and said R1 being a member selected from the group consisting of hydrogen, alkyl, of 1 to 8 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, alkylthioalkyl of 2 to 8 carbon atoms and cyanoalkyl of 2 to 8 carbon atoms.
12. A product of a process of claim 11, wherein said epoxy resin has an epoxy equivalent weight from about 70 to about 2,000.
13. A product of a process of claim 12, wherein said epoxy resin is a glycidyl ether resin.
14. A product of a process of claim 13, wherein said epoxy resin is selected from the group consisting of (1) alkanediol diglycidyl ethers having the formula wherein X is an alkylene or alkylidene group containing from 1 to 10 carbon atoms, and n is from 1 to 25 (2) di- and polyglycidyl ethers of bisphenols, said bisphenols having the formula wherein R5 is a bivalent radical containing from 1 to 8 carbon atoms of at least one atom selected from the group consisting of C, O, S and N, and (3) alkanetriol triglycidyl ethers wherein the alkane group contains from 2 to 10 carbon atoms.
15. A product of a process of claim 14 wherein said vinylidene monomer contains copolymerized therewith from 0% up to about 50% by weight of at least one co-monomer selected from the group consisting of (f) vinyl aromatics having the formula wherein R2 is hydrogen, halogen or an alkyl radical containing from 1 to 4 carbon atoms, (g) vinyl nitriles having the formula wherein R3 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms, (h) vinyl halides, (i) divinyls and diacrylates, (j) amides of .alpha.,.beta.-olefinically unsaturated carboxylic acids containing 2 to 8 carbon atoms, and (k) allyl alcohol.
16. A product of a process of claim 15 wherein said amine groups have different reactivities, and said comonomer is selected from the group consisting of (f) said vinyl aromatics and (g) said vinyl nitriles.
17. A product of a process of claim 16 wherein said epoxy resin is a diglycidyl ether of isopropylidene bisphenol, said amine is at least one N-(aminoalkyl) piper-azine, the aminoalkyl group of said amine contains from 1 to 12 carbon atoms, said vinylidene monomer is at least one of said dienes, and said comonomer is at least one of said vinyl nitriles.
18. A product of a process of claim 17 wherein said diene is butadiene, said vinyl nitrile is acrylon-itrile, and said amine is N-(2-aminoethyl) piperazine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61863275A | 1975-10-01 | 1975-10-01 | |
| US618,632 | 1975-10-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091995A true CA1091995A (en) | 1980-12-23 |
Family
ID=24478481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,499A Expired CA1091995A (en) | 1975-10-01 | 1976-09-16 | Underwater curing of epoxy resin and amine-terminated liquid polymer and product thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5936929B2 (en) |
| AU (1) | AU499219B2 (en) |
| CA (1) | CA1091995A (en) |
| DE (1) | DE2643504A1 (en) |
| GB (1) | GB1545807A (en) |
| NL (1) | NL7610824A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57133117A (en) * | 1981-02-10 | 1982-08-17 | Nippon Kokan Kk <Nkk> | Epoxy mastic for molding in form |
| DE3639570A1 (en) * | 1986-11-20 | 1988-06-01 | Basf Lacke & Farben | BY PROTONING WITH ACID WATER-DISCOVERABLE BINDING AGENTS |
-
1976
- 1976-09-16 CA CA261,499A patent/CA1091995A/en not_active Expired
- 1976-09-22 AU AU18000/76A patent/AU499219B2/en not_active Expired
- 1976-09-28 DE DE19762643504 patent/DE2643504A1/en not_active Withdrawn
- 1976-09-30 JP JP11668876A patent/JPS5936929B2/en not_active Expired
- 1976-09-30 NL NL7610824A patent/NL7610824A/en not_active Application Discontinuation
- 1976-10-01 GB GB4076076A patent/GB1545807A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1545807A (en) | 1979-05-16 |
| JPS5249300A (en) | 1977-04-20 |
| NL7610824A (en) | 1977-04-05 |
| DE2643504A1 (en) | 1977-04-14 |
| AU1800076A (en) | 1978-04-06 |
| AU499219B2 (en) | 1979-04-12 |
| JPS5936929B2 (en) | 1984-09-06 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |