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Patent US4260700 - Underwater curing of epoxy resin and amine-terminated liquid polymer and ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin cures rapidly at ambient temperatures under water while displacing water from substrate surfaces and bonding strongly thereto. The mixture comprises (A) 1 equivalent of at least one non-cycloaliphatic epoxy resin, (B)...http://www.google.com/patents/US4260700?utm_source=gb-gplus-sharePatent US4260700 - Underwater curing of epoxy resin and amine-terminated liquid polymer and product thereofAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4260700 APublication typeGrantApplication numberUS 05/761,562Publication dateApr 7, 1981Filing dateJan 24, 1977Priority dateJan 24, 1977Publication number05761562, 761562, US 4260700 A, US 4260700A, US-A-4260700, US4260700 A, US4260700AInventorsThomas R. Cassutt, James W. Messerly, Ronald L. SenderlingOriginal AssigneeThe B.F. Goodrich CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (11), Non-Patent Citations (1), Referenced by (22), Classifications (9) External Links: USPTO, USPTO Assignment, EspacenetUnderwater curing of epoxy resin and amine-terminated liquid polymer and product thereof
US 4260700 AAbstract
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin cures rapidly at ambient temperatures under water while displacing water from substrate surfaces and bonding strongly thereto. The mixture comprises (A) 1 equivalent of at least one non-cycloaliphatic epoxy resin, (B) from about 0.01 to about 1.5 equivalents 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.
1. 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) 1 equivalent 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 0.01 to about 1.5 equivalents of at least one amine-terminated liquid polymer containing an average from about 1.5 to about 4 amine groups per molecule, said groups being primary, secondary or a mixture thereof, and said polymer having the formula ##STR13## wherein Y is an univalent radical obtained by removing a hydrogen from an amine group of an aliphatic, alicyclic or heterocyclic 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 containing carbon-carbon linkages comprising at least 95% of total polymeric backbone weight, said backbone B 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) 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 ##STR14## said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms, and said R1 being hydrogen, an alkyl radical containing 1 to 18 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical containing 2 to 12 carbon atoms. 2. A process of claim 1 wherein said carboncarbon linkages comprise 100% 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 ##STR15## said R being hydrogen or an alkyl radical containing 1 to 3 carbon atoms and said R1 being hydrogen, an alkyl radical containing 1 to 8 carbon atoms, or an alkoxyalkyl, alkylthioalkyl or cyanoalkyl radical containing 2 to 8 carbon atoms.
5. A process of claim 4 wherein said epoxy resin is selected from the group consisting of (1) alkanediol diglycidyl ethers having the formula ##STR16## wherein X is an alkylene or alkylidene group containing from 1 to 10 carbon atoms, and n is from 0 to 20, (2) diglycidyl ethers of bisphenols, said bisphenols having the formula ##STR17## wherein R5 is a bivalent radical containing from 1 to 8 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 ##STR18## wherein R2 is hydrogen, or an alkyl radical containing from 1 to 4 carbon atoms, (g) vinyl nitriles having the formula ##STR19## wherein R3 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms, (h) divinyls and diacrylates, (i) amides of α,β-olefinically unsaturated carboxylic acids containing 2 to 8 carbon atoms, and (j) allyl alcohol.
This is a continuation-in-part of our co-pending U.S. patent application Ser. No. 749,853, filed Dec. 13, 1976, now abandoned which in turn is a continuation-in-part of our U.S. patent application Ser. No. 618,632, filed Oct. 1, 1975, now abandoned.
Underwater-curing coatings are known in the art (Drisko, Paint and Varnish Production, Vol. 58, p. 31, July, 1968). Such coatings typically comprise 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.
A mixture of an amine-terminated liquid polymer and a non-cycloaliphatic epoxy resin is applied to a surface and cured under water. The mixture comprises (A) 1 equivalent of at least one non-cycloaliphatic epoxy resin, and (B) from about 0.01 to about 1.5 equivalents of at least one amine-terminated liquid polymer having a carbon-carbon backbone.
The amine-terminated liquid polymers suitable as component (B) in the compositions of this invention have the formula ##STR1## wherein Y is a univalent radical obtained by removing a hydrogen from an amine group of an aliphatic, alicyclic or heterocyclic 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 95% by weight of total polymeric backbone weight, more preferably about 100% by weight of total polymeric backbone weight. The amine-terminated polymers contain an average from about 1.5 to about 4 primary and/or secondary amine groups per molecule, more preferably from about 1.7 to about 3 primary and/or secondary amine groups per molecule. The amine-terminated polymers may have Brookfield viscosities (measured using a Brookfield RVT viscometer at 27� C.) from about 500 cps to about 2,500,000 cps, more preferably from about 500 cps to about 1,200,000 cps. The amine-terminated liquid polymers may have amine equivalent weights (gram molecular weight per primary and/or secondary amine group, but exclusive of tertiary amine groups) from about 300 to about 4,000, more preferably from about 600 to about 3,000.
Carboxyl-terminated liquid polymers having carbon-carbon backbone linkages may contain polymerized units of at least one vinylidene monomer having at least one terminal CH2 ═< group and selected from the group consisting of (a) monoolefins containing 2 to 14 carbon atoms, more preferably 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-dodecene and the like; (b) dienes containing 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, such as butadiene, isoprene, 2-isopropyl-1,3-butadiene, and the like; (c) vinyl and allyl esters of carboxylic acids containing 2 to 8 carbon atoms such as vinyl acetate, vinyl propionate, allyl acetate, and the like; (d) vinyl and allyl ethers of alkyl radicals containing 1 to 8 atoms such as vinyl methyl ether, allyl methyl ether, and the like; and (e) acrylic acids and acrylates having the formula ##STR2## wherein R is hydrogen or an alkyl radical containing 1 to 3 carbon atoms and R1 is hydrogen or an alkyl radical containing 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 2 to 8 carbon atoms. Examples of suitable acrylates include ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, hexylthioethyl acrylate, β-cyanoethyl acrylate, cyanooctyl acrylate, methyl methacrylate, ethyl methacrylate, octyl methacrylate and the like. 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 are selected from the group consisting of (a) monoolefins containing 2 to 14 carbon atoms, more preferably 2 to 8 carbon atoms; (b) dienes containing 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms; and (e) acrylic acids and acrylates having the formula ##STR3## wherein R is hydrogen or an alkyl radical containing 1 to 3 carbon atoms and R1 is hydrogen or an alkyl radical containing 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. Excellent results were obtained with 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% up to about 50% by weight, 50% by weight, more preferably from 0% up to about 35% by weight, of at least one comonomer selected from the group consisting of (f) vinyl aromatics having the formula ##STR4## wherein R2 is hydrogen, halogen or an alkyl radical containing from 1 to 4 carbon atoms, such as styrene, α-methyl styrene, chlorostyrene, vinyl toluene, and the like; (g) vinyl nitriles having the formula wherein R3 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms, such as acrylonitrile, methacrylonitrile and the like; (h) divinyls and diacrylates such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, and the like; (i) amides of α,β-olefinically unsaturated carboxylic acids containing 2 to 8 carbon atoms such as acrylamide and the like; and (j) allyl alcohol and the like. Liquid polymer compositions comprising polymerized units of a major amount of at least one vinylidene monomer listed in (a) to (e) with a minor amount of at least one comonomer listed in (f) to (j) are within the scope of this invention.
More preferred comonomers may be selected from the group consisting of (f) vinyl aromatics having the formula ##STR5## wherein R2 is selected from the group consisting of hydrogen and alkyl radicals containing 1 to 4 carbon atoms; and (g) vinyl nitriles having the formula ##STR6## wherein R3 is hydrogen or an alkyl radical containing 1 to 3 carbon atoms. Excellent results were obtained using styrene and acrylonitrile.
The 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. For example, a carboxyl-terminated polymer and an aliphatic monohydric alcohol can be reacted under reflux in the presence of a small amount of an acid catalyst. Suitable acid catalysts include organic acids such as monoesters and diesters of orthophosphoric acid, alkarylsulfonic acids such as p-toluenesulfonic 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 esterification reaction contain from 1 to about 12 carbon atoms, more preferably from 1 to 6 carbon atoms, and have boiling points below about 150� C., more preferably below about 100� C. Primary aliphatic monohydric alcohols are preferred. Examples of suitable aliphatic monohydric alcohols include alkanols containing from 1 to 6 carbon atoms, such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and the like. Other suitable aliphatic monohydric alcohols include 2-methoxyethanol, 2-ethoxyethanol and the like. Excellent results may be obtained using ethanol, 1-propanol or 1-butanol. Excellent results may also be obtained using methanolic or ethanolic diazomethane.
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 cycloaliphatic ethers containing from 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as tetrahydrofuran, diethylether and the like; and esters containing from 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, ethyl propionate and the like. Also suitable as solvents and more preferred are aromatic compounds having the formula ##STR7## wherein R4 is hydrogen, or an alkyl radical containing 1 to 3 carbon atoms, and at least two R4 's are hydrogen. More preferably R4 is hydrogen, or an alkyl radical containing 1 to 2 carbon atoms, and at least three R4 's are hydrogen. Suitable aromatic solvents include benzene, toluene, o-, m- and p-xylene, o-, m- and p-diethylbenzene, cumene, mesitylene and the like.
No catalyst is required, and many types of mixing apparatus can be used in the amine termination reaction. For example, 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 80� C. to about 200� C., until more than 90% of carboxyl, ester or acid chloride groups have reacted with the amines, i.e., until the amidation reaction is more than 90% complete. Reaction time is typically about 1 to 120 hours. By-products may be removed by evaporation or the like as they are formed (e.g., water from the carboxylamine reaction, HCl from the acid chloride-amine reaction, and alcohol from the ester-amine reaction). The amine-terminated liquid polymer may be purified by vacuum distillation or by washing with a solvent such as a benzenemethanol mixture in order to remove the unreacted amine, followed by drying the polymer. The structure of amide formed during preparation of the amine-terminated liquid polymers can be determined by infrared spectroscopy. Amine value can be analyzed quantitatively following the procedure described by Siggia, Quantitative Organic Analysis via Functional Groups, N.Y., Wiley and Sons, Inc., 1963, pp. 452-456, using a toluene/isopropanol solvent mixture instead of Siggia's ethylene glycol/isopropanol mixture.
UNDERWATER CURING OF NON-CYCLOALIPHATIC EPOXY RESINS AND AMINE-TERMINATED LIQUID POLYMERS
The compositions used in the process of this invention comprise (A) 1 equivalent of at least one noncycloaliphatic epoxy resin described hereinafter and (B) from about 0.01 to about 1.5 equivalents of at least one amine-terminated liquid polymer described heretofore. 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 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 epoxy equivalent weights (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 esters of polycarboxylic acids, epoxidized polyolefins, and glycidyl ether resins, with glycidyl ether resins being preferred. Examples of suitable polyglycidyl esters of polycarboxylic acids include the diglycidyl ester of linoleic dimer acid, the triglycidyl ester of linoleic trimer acid, and the like. Suitable glycidyl ether resins include polyallyl glycidyl ether; the diglycidyl ether of chlorendic diol; the diglycidyl ether of dioxanediol; the diglycidyl ether of endomethylene cyclohexanediol; epoxy novolac resins; alkanediol diglycidyl ethers, alkanetriol triglycidyl ethers; and the like.
Other more preferred glycidyl ether resins include alkanetriol triglycidyl ethers wherein the alkane group contains from 2 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as glyceryl triglycidyl ether, the triglycidyl ether of trimethylolpropane and the like. Another more preferred class of glycidyl ether resins is the diglycidyl ethers of bisphenols, the bisphenols having the formula ##STR9## wherein R5 is a bivalent 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 preferably an alkylene or alkylidene group containing 1 to 6 carbon atoms. Examples of suitable bisphenols include methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, bisphenol amine, and the like. Excellent results were obtained using isopropylidene bisphenol (bisphenol A). Examples of suitable diglycidyl ethers of bisphenols include diglycidyl ethers of isopropylidene bisphenol having the formula ##STR10## wherein n is from about 0 to about 20, more preferably from about 0 to about 2.
Also suitable as chain extenders and/or cross-linkers and more preferred in this invention are dihydric aromatic compounds containing from 6 to 24 carbon atoms, more preferably from 6 to 18 carbon atoms. Suitable dihydric aromatic compounds include catechol, resorcinol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and, even more preferably, bisphenols having the formula ##STR11## 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 bisphenol, isopropylidene bisphenol, butylidene bisphenol, octylidene bisphenol, bisphenol sulfide, bisphenol sulfone, bisphenol ether, bisphenol amine, and the like. Excellent results were obtained using isopropylidene bisphenol (bisphenol A).
The epoxy resin compositions usable in the process of this invention comprise (A) 1 equivalent of at least one non-cycloaliphatic epoxy resin described heretofore, (B) from about 0.01 to about 1.5 equivalents, more preferably from about 0.05 to about 1.2 equivalents, 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 compositions after mixing typically is from about 2 hours to about 4 hours. Heating the mixture up to about 100� C. may be helpful to obtain dissolution and uniform dispersion of the materials, but such heating causes the compositions to cure much more rapidly.
Adhesive and coating thicknesses of the underwater-curing compositions described heretofore may vary widely but are typically from about 0.001 inch to about 0.25 inch and more, preferably from about 0.005 inch to about 0.1 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 like. The compositions may cure at temperatures from about 28� F. to about 100� F. and more, with cure time decreasing as temperature increases. Underwater cure time generally may range from about 1 hour to about 20 hours, more typically from about 3 hours to 12 hours.
In each example 1-14 a 2-liter, 4-necked glass flask was cleaned thoroughly with soap and water, rinsed first with water and then with acetone, and flushed with nitrogen until dry. The flask was equipped with an air stirrer, thermocouple, nitrogen inlet tube, and Dean-Stark water trap with water condenser. A carboxyl-terminated liquid polymer and N-(2-aminoethyl)piperazine were charged to the flask with stirring, and the reaction mixture was heated to about 120� C. to 130� C. using an oil bath. The flask was purged continuously with nitrogen during reaction. After final EphrCOOH of the reaction mixture was reduced to less than 10% of the initial EphrCOOH, the gas inlet tube was replaced by a stopper, and the water condenser was connected to a vacuum pump. A vacuum (about 1 to 2 mm hg) was drawn on the flask and maintained for about 2 hours in order to remove some excess N-(2-aminoethyl)piperazine and other volatiles. Brookfield viscosity in each example was measured at 27� C. using a Brookfield RVT viscometer and #4 spindle. Data is set forth in Table I.
TABLE I__________________________________________________________________________Carboxyl-terminated Liquid Polymer                    Acrylo-   N-(2-aminoethyl)piperazine                                             Amine-Terminated                                             Liquid Ex.(grams) Wt.     EphrCOOH+           Viscosity(cps.)Brookfield                     (Wt. %)nitrile                          (Wt. %)Styrene                               (grams) Wt.                                    ##STR12##                                              Viscosity(cps.)Polymer-                                             Brookfield__________________________________________________________________________ 1  1000.4    0.044   43,000 @ 27� C.                     0    0    85.2                                   1.5          244,000 @ 27�                                             C. 2  1000 0.044   44,200 @ 27� C.                     0    0    170.3                                   3.0          76,500 @ 27�                                             C. 3  1000 0.047   65,400 @ 24� C.                     0    0    121.3                                   2.0           290,000                                             @ 24� C. 4  1000 0.047   65,600 @ 22� C.                     0    0    181.4                                   3.0           194,000                                             @ 22� C. 5  8250 0.043   61,200 @ 22� C.                     0    0   1373 3.0          187,200 @ 22�                                             C. 6  1000 0.053   75,000 @ 23� C.                     9.9  0    205.1                                   3.0          89,000 @ 23�                                             C. 7   940 0.053   75,000 @ 22� C.                     9.9  0    192.8                                   3.0          130,000 @ 22�                                             C. 8  1001.4    0.054   191,000 @ 23� C.                    18.1  0    209.3                                   3.0          320,000 @ 23�                                             C. 9  1000 0.052   177,000 @ 23� C.                    18.2  0    201.2                                   3.0          187,000 @ 23�                                             C.10  1001.1    0.056 1,320,000 @ 22� C.                    26.5  0    108.5                                   1.5       &gt;2,000,000 @ 22�                                             C.11  1003 0.056 1,320,000 @ 22� C.                    26.5  0    217.4                                   3.0        1,008,000 @ 32�                                             C.12  1200 0.056 1,320,000 @ 22� C.                    26.5  0    260 3.0          870,000 @ 22�                                             C.13++    1005 0.068   244,400 @ 22� C.                    17.5  0    132.2                                   1.5          802,000 @ 22�                                             C.14  1000 0.05    850,000 @ 21� C.                     0   20    181.9                                   2.8       &gt;2,000,000 @ 21�                                             C.__________________________________________________________________________ +Carboxyl equivalent weight per hundred weight parts of carboxylterminate liquid polymer. ++Carboxyl-terminated terpolymer of butadiene, acrylonitrile and acrylic acid +++AEP/CTP Ratio = desired ratio of moles of N(2-aminoethyl) piperazine (AEP) to equivalents of carboxylterminated liquid polymer (CTP).
A number of amine-terminated liquid polymers like those in Table I were analyzed by potentiometric titration according to the modified Siggia procedure described heretofore. EphrAMINE may be defined as primary and/or seconday amine equivalent weight (exclusive of tertiary amine content) per hundred weight parts of amine-terminated liquid polymer. The EphrAMINE ranged from about 0.04 to about 0.2 depending upon residual N-(2-aminoethyl)piperazine content. The infrared spectra and potentiometric titration data, as well as nuclear magnetic resonance spectra, indicated that carboxyl groups of carboxyl-terminated liquid polymers reacted mainly with the primary amine group of N-(2-aminoethyl)piperazine to produce amine-terminated liquid polymers having mainly free secondary amine groups.
Example 15 demonstrates again the preparation of an amine-terminated liquid polymer from N-(2-aminoethyl)piperazine and a carboxyl-terminated butadieneacrylonitrile liquid polymer. The carboxyl-terminated liquid polymer was prepared according to the method of U.S. Pat. No. 3,285,949 and was found to have a Brookfield viscosity at 27� C. of 106,000 cps., an EphrCOOH of 0.052, a carboxyl equivalent weight of 1923, and an acrylonitrile content of 16.0 wt.%. The amount of N-(2-aminoethyl)-piperazine required to react with a given amount of the carboxyl-terminated liquid polymer was calculated using the formula described for examples 1-14.
Example 16 demonstrates preparation of an amine-terminated liquid polymer from N-methyl-1,3-propanediamine and a carboxyl-terminated butadiene-acrylonitrile liquid polymer. The carboxyl-terminated liquid polymer was prepared according to the method of U.S. Pat. No. 3,285,949 and was found to have a Brookfield viscosity at 27� C. of 128,000 cps., an EphrCOOH of 0.056, a carboxyl equivalent weight of 1786, and an acrylonitrile content of 16.1 wt.%. The amount of N-methyl-1,3-propanediamine required to react with a given amount of the carboxyl-terminated liquid polymer was calculated using the formula described for examples 1-14, with N-methyl-1,3-propanediamine substituted for N-(2-aminoethyl)piperazine.
1000 grams (0.56 equivalent) of the carboxyl-terminated liquid polymer and 99 grams (1.12 moles) of N-methyl-1,3-propanediamine were charged to the flask with stirring, and the reaction mixture was heated to about 130� C. using an oil bath. The flask was purged continuously with nitrogen during reaction. Reaction was continued for 51 hours at 130� C. and 54 hours at 150� C., for a total reaction time of 105 hours.
An amine-terminated liquid polymer was produced having a Brookfield viscosity at 27� C. of 1,000,000 cps. The liquid polymer was found by potentiometric titration to have undergone 100% conversion and to have an EphrAMINE of 0.0745, a residual N-methyl-1,3-propanediamine content of 0.823 wt.% and an amine equivalent weight of 1340. After vacuum drying, the liquid polymer was found to have an EphrAMINE equivalent weight of 1776. An infrared spectrum was obtained having broad amide carbonyl bands at 1640-1675 cm-1, indicating that primary as well as secondary amine groups of N-methyl-1,3-propanediamine reacted with carboxyl groups of the carboxyl-terminated liquid polymer to produce an amine-terminated liquid polymer.
Example 17 demonstrates preparation of an amine-terminated liquid polymer from 4,4'-trimethylenedipiperidine and a carboxyl-terminated butadiene-acrylonitrile liquid polymer. The carboxyl-terminated liquid polymer was prepared according to the method of U.S. Pat. No. 3,285,949 and was found to have a Brookfield viscosity at 27� C. of 128,000 cps., an EphrCOOH of 0.056, a carboxyl equivalent weight of 1786, and an acrylonitrile content of 16.1 wt. %. The amount of 4,4'-trimethylenedipiperidine required to react with a given amount of the carboxyl-terminated liquid polymer was calculated using the formula described for examples 1-14, with 4,4'-trimethylenedipiperidine substituted for N-(2-aminoethyl)piperazine.
1000 grams (0.56 equivalent) of the carboxyl-terminated liquid polymer and 236 grams (1.12 moles) of 4,4'-trimethylenedipiperidine were charged to the flask with stirring, and the reaction mixture was heated to about 130� C. using an oil bath. The flask was purged continuously with nitrogen during reaction. Reaction was continued for 5 hours at 130� C., 19 hours at 140� C., 4 hours at 150� C., 3 hours at 180� C., 16 hours at 150� C., and 8 hours at 180� C., for a total of 55 hours.
An amine-terminated liquid polymer was produced having a Brookfield viscosity at 27� C. of 445,000 cps. The liquid polymer was found by potentiometric titration to have undergone 100% conversion and to have an EphrAMINE of 0.1245, a residual 4,4'-trimethylenedipiperidine content of 8.55 wt. % and an amine equivalent weight of 803. After vacuum drying, the liquid polymer was found to have an EphrAMINE of 0.0473 and an amine equivalent weight of 2114. An infrared spectrum was obtained having an amide carbonyl band at 1648 cm-1, indicating that secondary amine groups of 4,4'-trimethylenedipiperidine reacted with carboxyl groups of the carboxyl-terminated liquid polymer to produce an amine-terminated liquid polymer.
Example 18 demonstrates preparation of an amine-terminated liquid polymer from 4-(aminomethyl) piperidine and a carboxyl-terminated butadiene-acrylonitrile liquid polymer. The carboxyl-terminated liquid polymer was prepared according to the method of U.S. Pat. No. 3,285,949 and was found to have a Brookfield viscosity at 27� C. of 128,000 cps., an EphrCOOH of 0.056, a carboxyl equivalent weight of 1786, and an acrylonitrile content of 16.1 wt. %. The amount of 4-(aminomethyl)piperidine required to react with a given amount of the carboxyl-terminated liquid polymer was calculated using the formula described for examples 1-14, with 4-(aminomethyl)piperidine substituted for N-(2-aminoethyl)piperazine.
1000 grams (0.56 equivalent) of the carboxyl-terminated liquid polymer and 128 grams (1.12 moles) of 4-(aminomethyl)piperidine were charged to the flask with stirring, and the reaction mixture was heated to about 130� C. using an oil bath. The flask was purged continuously with nitrogen during reaction. Reaction was continued for 7 hours at 130� C. and 41 hours at 150� C., for a total of 48 hours.
An amine-terminated liquid polymer was produced having a Brookfield viscosity at 27� C. of 1,000,000 cps. The liquid polymer was found by potentiometric titration to have undergone 99.9% conversion and to have an EphrAMINE OF 0.1182, a residual 4-(aminomethyl)piperidine content of 3.69 wt. %, and an amine equivalent weight of 850. After vacuum drying, the liquid polymer was found to have an EphrAMINE of 0.057 and an amine equivalent weight of 1788. An infrared spectrum was obtained having broad amide carbonyl bands at 1640-1675 cm-1, indicating that primary as well as secondary amine groups of 4-(aminomethyl)piperidine reacted with carboxyl groups of the carboxyl-terminated liquid polymer to produce an amine-terminated liquid polymer.
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 mill. Additional filler (if used) was mixed with an amine-terminated liquid polymer on an ink mill. The two mixtures were stirred together 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�200 mm�2.2 mm. 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�200 mm surface of a strip. Application was made by hand or using a putty knife. Compositional thickness on the rubber strip was about 0.25 inch. 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 together in order to eliminate water between them and allowed to cure underwater.
The amine-terminated liquid polymers used in the following examples were prepared readily using a carboxyl-terminated liquid polymer (prepared by the method of U.S. Pat. No. 3,285,949) and N-(2-aminoethyl)-piperazine in the amine-termination reaction. The amine-terminated liquid polymers, identified as ATBN, were amine-terminated poly(butadiene/acrylonitrile) copolymers having an acrylonitrile content of about 9.5% by weight of polymer, a viscosity at 27� C. of about 90,000 cps. and a molecular weight of about 3,600.
The non-cycloaliphatic epoxy resin most frequently used was a liquid diglycidyl ether of bisphenol 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 25� C. of about 100 to 170 cps., this resin being sold under the trademark "Epon 812" by Shell Chemical Company. Yet another non-cycloaliphatic 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 25� C. of about 10,000 to 16,000 cps. The latter material is sold under the trademark "Epi-Rez 510" by Celanese Corp.
Peel adhesion strength was tested using the procedure in ASTM D-903. Flexibility was evaluated by bending up to 360� and by stretching by hand.
Underwater-curing compositions in each of the following examples were prepared following the general mixing and sample preparation procedure described heretofore. Testing was done after about 48 hours exposure to water at 23� C. Test results are summarized in Table II.
Underwater curing compositions in each of the following examples were prepared following the general mixing and sample preparation procedure described heretofore. Testing was done after 72 hours exposure to water at 25� C. Test results are summarized in Table III.
TABLE III______________________________________Example       22      23      24   25     26______________________________________RecipeEpon 828, Wt. Parts         100     100     100  --     --(Equivalents) (0.53)  (0.53)  (0.53)Epi-Rez 510, Wt. Parts         --      --      --   100    --(Equivalents)                      (0.53)ATBN, Wt. Parts         500     --      --   --     --(Equivalents) (0.26)System X, Part 1,         --      --      --   --     30Wt. PartsSystem X, Part 2, Wt.         --      --      --   --     40PartsVersamid 115, Wt. parts         --      100     --   100    --(Equivalents)         (0.42)       (0.42)Versamid 140, Wt. Parts       100(Equivalents) --      --      (0.68)                              --     --TiO2, Wt. Parts         250     50      75   50     --Test DataCure time, Hours         &#732;3                 &#732;24                         &#732;7                              &#732;24                                     &#732;24Average Adhesion,         8-9     7-8     5-6  7-8    3-4lbs./in.Maximum Adhesion,         12      8.5     6.5  9.5    5lbs./in.Flexibility   Very    Fair    Poor Fair   Very         Good                        Poor______________________________________
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3159499 *Sep 21, 1961Dec 1, 1964Shell Oil CoTreating water-wetted surfaces with corrosion-resistant coating materialUS3673275 *Mar 5, 1970Jun 27, 1972Du PontAcrylic polymers containing epoxy radicalsUS3707583 *Jun 4, 1971Dec 26, 1972Minnesota Mining & MfgAdhesiveUS3823107 *Mar 9, 1972Jul 9, 1974Shell Oil CoEpoxy resin curing agent compositions,their preparation and useUS3894112 *Feb 23, 1974Jul 8, 1975Minnesota Mining & MfgBonding film containing polytetramethyleneoxide elastomeric segments and polyepoxideUS3919142 *Dec 21, 1973Nov 11, 1975Kao CorpLiquid polyamide epoxy resin hardenerUS3926903 *Sep 30, 1974Dec 16, 1975United Technologies CorpCurable crack-resistant epoxy resinUS3926904 *Sep 30, 1974Dec 16, 1975United Technologies CorpCurable crack-resistant epoxy resinUS4018847 *Oct 1, 1975Apr 19, 1977The B. F. Goodrich CompanyFlexible coating compositionsUS4025578 *May 9, 1975May 24, 1977The B. F. Goodrich CompanyElastomeric liquid polymer vulcanizates from epoxy resin, liquid carboxy terminated polymer, dihydric phenol, and an amineDE1815632A1 *Dec 19, 1968Jul 17, 1969Goodrich Co B FHaftkleber* Cited by examinerNon-Patent CitationsReference1 *R. S. Drake et al., Rubber World, Oct. 1968, pp. 51-56.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4447579 *Apr 20, 1982May 8, 1984Cemedine Co., Ltd.Epoxy resin adhesive compositionsUS4463134 *Dec 22, 1981Jul 31, 1984Sumitomo Chemical Company, LimitedModified epoxy resin compositionUS4482667 *Mar 5, 1984Nov 13, 1984The Dow Chemical CompanyModified polyalkylenepolyaminesUS4519843 *Aug 8, 1984May 28, 1985The Dow Chemical CompanyModified polyalkylenepolyaminesUS4535147 *Jul 9, 1984Aug 13, 1985The B. F. Goodrich CompanyPhosphazene modified amine terminated polymers and methodUS4543406 *Oct 15, 1984Sep 24, 1985Nippon Paint Co., Ltd.Cathode-depositing electrodeposition coating compositionUS4749748 *Feb 10, 1986Jun 7, 1988Ube Industries, Ltd.Epoxy resin adhesive compositionUS4769420 *Nov 25, 1986Sep 6, 1988Basf Lacke + Farben AktiengesellschaftBinder which is rendered water-dilutable by protonation with an acid, from carboxyl terminated butadiene/acrylonitrile copolymersUS4988461 *Mar 22, 1990Jan 29, 1991The Bfgoodrich CompanyCompositions of water-dispersed amine-containing polymersUS5080968 *Feb 20, 1990Jan 14, 1992The B. F. Goodrich CompanyComposites of vinyl resins and elastomer-coated fibersUS5089165 *Oct 15, 1990Feb 18, 1992The Bfgoodrich CompanyCompositions of water-dispersed diprimary amine terminated polymersUS5247009 *Mar 13, 1989Sep 21, 1993Nippon Zeon Co., Ltd.Rubber composition containing rubbery polymer and modified liquid polymerUS5320871 *Jun 5, 1992Jun 14, 1994Springborn Laboratories, Inc.Underwater coating for submerged substratesUS5403390 *Mar 11, 1994Apr 4, 1995Spera; Richard J.Cuprous sulfide marine antifoulant paintUS5457165 *Aug 12, 1992Oct 10, 1995Hughes Aircraft CompanyEncapsulant of amine-cured epoxy resin blendsUS5925579 *May 23, 1996Jul 20, 1999Hexcel CorporationReinforcement of structures in high moisture environmentsUS6363681Nov 23, 1999Apr 2, 2002Hexcel CorporationNon-toxic reinforcement of structures in high moisture environmentsUS6555228Feb 2, 2001Apr 29, 2003Dennis A. GuritzaBio-supportive medium, and methods of making and using the sameUS6613435Oct 26, 2000Sep 2, 2003Dennis A. GuritzaBio-supportive matrices, methods of making and using the sameDE10000957A1 *Jan 12, 2000Aug 2, 2001Jordan Paul EltechBastelvergussmasseWO1985001935A1 *Oct 29, 1984May 9, 1985The Dow Chemical CompanyA modified alkylenediamine or polyakylenepolyamine composition and aqueous hydraulic cement slurry employing the compositionWO1987002686A1 *Oct 29, 1986May 7, 1987The Dow Chemical CompanyProcess for manufacture of epoxy resin compositions* Cited by examinerClassifications U.S. Classification525/113, 523/400, 523/177International ClassificationC08L63/00, C08G59/18Cooperative ClassificationC08L63/00, C08G59/18European ClassificationC08L63/00, C08G59/18RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services