CA1167191A - Water-based adhesive systems - Google Patents
Water-based adhesive systemsInfo
- Publication number
- CA1167191A CA1167191A CA000380682A CA380682A CA1167191A CA 1167191 A CA1167191 A CA 1167191A CA 000380682 A CA000380682 A CA 000380682A CA 380682 A CA380682 A CA 380682A CA 1167191 A CA1167191 A CA 1167191A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer latex
- elastomeric copolymer
- alkyl halide
- range
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
- C09J119/02—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THF DISCLOSURE
Halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latexes provide adhesive systems which afford adhesive strengths comparable to commercial solvent-based adhesies in bond natural and synthetic elastomers to rigid and non-rigid substrates. Adhesives prepared from such latexes exhibit excellent preheat tolerance and environ-mental resistance.
Halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latexes provide adhesive systems which afford adhesive strengths comparable to commercial solvent-based adhesies in bond natural and synthetic elastomers to rigid and non-rigid substrates. Adhesives prepared from such latexes exhibit excellent preheat tolerance and environ-mental resistance.
Description
7~
BACKGROUND O~ THE I~VENTION
This invention .relates to water-based organic com-positions. ~ore particularly, the invention relates to water-based organic polymer containing compositions especially suit-able for use as adhesives for bonding natural and synthetic elastomers to rigid and non-rigid substrates.
Historically, the ma~or commercial adhesives which have been utilized to boncl natural and synthetic elastomers to the same or different e]astomers, as well as to non-rigid and other rigid substrates, including metals, wood, ceramics, natural and synthetic organic and inorgani.c fibers, and the like, have been solvent-based, that is, the adhesive ingre-dients, including active components such as film-forming materials and adhesion-improving additives and also non-active components such as fillers and extenders, are dissol-ved or dis.persed in volatile, inert organic solvents suchas toluene, .xylene and trichloroethane. Increasing concern over deleterious effects of solvent emissions to the atmos-phere on the environment and to human safety has led to a concerted effort by industry to develop replacement adhesive systems. Alternatives to the current solvent-borne rubber-metal adhesives which have been proposed include the use of certain exempt solvents as defined by various governmental regulations, high solids adhesives at greater than 70% solids to minimize the amounts of inert solvent used, 100% solids compositions which contain substantially no inert solvents, film adhesives and water-borne adhesives. The water-borne adhesives, that is the adhesive ingredients are soluble in or dispersed into water, are especially attractive since they appear less susceptible to conflict with environmental regulations than adhesives containing any amount of solvent and they appear suited for use with the application equip-ment currently being used with the existing solvent-borne adhesives.
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~ particular problem in the development of water-borne adhesive systems was finding a suitable film-forming polymer or other material which in aqueous media would serve as a counterpart to -the film-forming materials currently being used in solvent-borne adhesives. Generally, the basic formulating materials used to prepare solvent-borne adheslves are not soluble in water. Efforts to prepare satisfactory emulsions from these materials generally failed. A particul-arly promising approach has been the development o emulsion-polymerized copolymers of halogenated conjugated diene andhalogenated vinyl monomers, of which the copolymer of 2,3-dichloro-l, 3-butadiene and alpha-chloroacrylonitrile is representative. From these emulsion copolymers, aqueous adhesive systems have been prepared which provide primary rubber-to-metal adhesion values substantially equivalent to those obtained with state-of-the-art solvent-borne adhesives.
However, these newly~developed aqueous adhesives exhibit less-than desirable attributes with respect to environmental resistance and pre-heat tolerance, that is, the capability of the adhesive to retain i-ts adhesiveness while the adhe-sively-coated substrate is a-t bondiny temperatures during processing before being contacted with the elastomer compo-sition.
In accordance with the present invention, there are provided storage-stable, heat-activatable, one-package, water-based adhesive systems which are especially suitable for bonding natural and synthetic rubbers to rigid and non-rigid substrates, and which provide adhesive strengths com-parable to commercial solvent-based adhesive systems, and which exhibit significantly improved pre-heat tolerance and environmental resistance. According to another aspect oE the invention, there is provided a method for bonding natural and synthetic elastomers to the same or different elastomers and to rigid and non-rigid substrates.
More particularly, the adhesive composi-tions of
BACKGROUND O~ THE I~VENTION
This invention .relates to water-based organic com-positions. ~ore particularly, the invention relates to water-based organic polymer containing compositions especially suit-able for use as adhesives for bonding natural and synthetic elastomers to rigid and non-rigid substrates.
Historically, the ma~or commercial adhesives which have been utilized to boncl natural and synthetic elastomers to the same or different e]astomers, as well as to non-rigid and other rigid substrates, including metals, wood, ceramics, natural and synthetic organic and inorgani.c fibers, and the like, have been solvent-based, that is, the adhesive ingre-dients, including active components such as film-forming materials and adhesion-improving additives and also non-active components such as fillers and extenders, are dissol-ved or dis.persed in volatile, inert organic solvents suchas toluene, .xylene and trichloroethane. Increasing concern over deleterious effects of solvent emissions to the atmos-phere on the environment and to human safety has led to a concerted effort by industry to develop replacement adhesive systems. Alternatives to the current solvent-borne rubber-metal adhesives which have been proposed include the use of certain exempt solvents as defined by various governmental regulations, high solids adhesives at greater than 70% solids to minimize the amounts of inert solvent used, 100% solids compositions which contain substantially no inert solvents, film adhesives and water-borne adhesives. The water-borne adhesives, that is the adhesive ingredients are soluble in or dispersed into water, are especially attractive since they appear less susceptible to conflict with environmental regulations than adhesives containing any amount of solvent and they appear suited for use with the application equip-ment currently being used with the existing solvent-borne adhesives.
~L6~7~99~
~ particular problem in the development of water-borne adhesive systems was finding a suitable film-forming polymer or other material which in aqueous media would serve as a counterpart to -the film-forming materials currently being used in solvent-borne adhesives. Generally, the basic formulating materials used to prepare solvent-borne adheslves are not soluble in water. Efforts to prepare satisfactory emulsions from these materials generally failed. A particul-arly promising approach has been the development o emulsion-polymerized copolymers of halogenated conjugated diene andhalogenated vinyl monomers, of which the copolymer of 2,3-dichloro-l, 3-butadiene and alpha-chloroacrylonitrile is representative. From these emulsion copolymers, aqueous adhesive systems have been prepared which provide primary rubber-to-metal adhesion values substantially equivalent to those obtained with state-of-the-art solvent-borne adhesives.
However, these newly~developed aqueous adhesives exhibit less-than desirable attributes with respect to environmental resistance and pre-heat tolerance, that is, the capability of the adhesive to retain i-ts adhesiveness while the adhe-sively-coated substrate is a-t bondiny temperatures during processing before being contacted with the elastomer compo-sition.
In accordance with the present invention, there are provided storage-stable, heat-activatable, one-package, water-based adhesive systems which are especially suitable for bonding natural and synthetic rubbers to rigid and non-rigid substrates, and which provide adhesive strengths com-parable to commercial solvent-based adhesive systems, and which exhibit significantly improved pre-heat tolerance and environmental resistance. According to another aspect oE the invention, there is provided a method for bonding natural and synthetic elastomers to the same or different elastomers and to rigid and non-rigid substrates.
More particularly, the adhesive composi-tions of
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the present invention comprise a latex of an elastomeric copolymer prepared by emulsion copolymerization in an a~ueous medium in the presence of at least one anionic sur-factant or mixture of at least one anionic surfactant and at least one nonionic surfactant of a mixture of, (a), at least one conjugated diene selected from the group consis-ting of 2-halo-1,3-butadiene and 2,3-dihalo-1,3-butadiene;
and, (b), at least one monoalkenyl aromatic alkyl halide.
Option~lly, and preferably, the adhesive latices of the invention will have dispersed therein from 1 to 200, pre-ferably from 10 to 150 parts by weight, per 100 parts by weight of elastomeric copolymer solids, of at least one aromatic nitroso compound. The adhesive compositions of the invention can also have optionally included therein from 20 to 90 percent by weight of at least one water-soluble or water-dispersible auxiliary film-forming material selected from the group consisting of halogenated rubber, halogenated resins and phenolic resins, said percentage being based on total weight of said elastomeric copolymer solids and said auxiliary film-forming material. J
With respect to the halogenated conjugated diené
monomers, the 2,3-dihalo-1,3-butadienes are currently pre-ferred, with 2,3, dichloro-l, 3-butadiene being the current monomer of choice. The bromine- and iodine-substitu-ted 1,3-butadiene monomers can also be employed to form the elastomeric copolymer latices of the invention. With respect to the comonomer, the term "monoalkenyl aromatic alkyl halide" is intended to include those monomers wherein an alkenyl group is attached directly to an aromatic nucleus containing from 6 to 1~ carbon atoms and at least one halogen-substituted al]cyl group is also attached directly to the aromatic nucleus, the halogen being substituted on the alpha carbon atom. The terms "halo", "halogen", "halo-genated" and "halide" are intended to includ~ chlorine, bromine and iodine substituents, with chlorine being the q3:~
current substituent of choice. More particularly, the mono-alkenyl aromatic alkyl halides have the characteristic formula~
I. ~ CX2 = Cx ~ R) ; and ~- Cx2 = Cx ,~ ;
(R)b (R)b wherein X is hydrogen, chlorinel bromine or iodine, R is an alkyl group having from 1 to 4 carbon atoms in which the alpha carbon atom of said alkyl group, that is, the carbon atom which is attached directly to the aromatic nucleus, is substituted with from 1 to 3 halogen atoms selected from the group consisting of chlorine, bromine or iodine; a is 1 or 2 and b is zero, 1 or 2, with the proviso that at least one b be at least one. Currently, X is hydro-gen, R is one, the halogen groups is one, a is one and b is one. Monoalkenyl aromatic alkyl halides having the formula (I) are the current comonomers of choice. Representative monoalkenyl aromatic alkyl halides include vinyl benzyl chloride (p-chloromethyl-vinylbenzene), p-trichloromethyl-vinylbenzene~ p~ ~-chloroethyl~-vinylbenzene, p-( ~ -chloro-butyl)-vinylbenzene; ~ -chlorovinyl-benzylchloride; o,m-di ( ~ -chloroethyl)-vinylbenzene; 4-chloromethyl-vinylnapthalene, the corresponding bromine and iodine analogsl and the like.
The current monoalkenyl aromatic alkyl halide of choice is vinylbenzyl chloride.
~6'~1~3~
The elastomeric copolymer latices which are employ~
ed in the present invention are prepared by emulsion poly-merization of the halogenated conjugat.ed diene and monoal-kenyl aromatic alkyl halide comonomers in an aqueous medium in the presence of an lonic or mixed ionic-nonionic surfac-tant system, with ionlc surfactant systems being currentlypreferred. It has been found that the elastomeric copolymer products best suited for use in the practice of this inven-tion contain from 67 to 97, preferably 75 to 97, and, opti~
mally, 93 to 97 percent by weight of halogenated conjugated diene; and,correspondingly. from 3 to 33, preferably 3 -to 25, and, optimally, 3 to 7, percent by weight of monoalkenyl aro-matic alkyl halide. The amounts of each comonomer can, how-ever, extend beyond these limits, but there is no currently known reason to do so.
The emulsion polymerization is carried out in a closed vessel in which the space not occupied by the reaction mixture ls preferably maintained free of oxygen by a blanket of inert gas, such as nitrogen. The induction period of tpe polymerization reaction is extended by the presence of o~ygen and it is desirable to effect the reaction in the substan-tial absence of oxygen. In the broad sense, the emulsion poly-merization is effected by mixing the monomeric ingredients, emulsifying this mixture, and subjecting the emulsion to moderate polymerization conditions until substantially all of the monomer charge has been polymerized. ~owever, for various practical reasons which need not be discussed here, it has been discovered that emulsion polymerization of halo-genated conjugated diene and monoalkenyl aromatic alkyl halide comonomers is more efficiently accomplished by a semi-continuous procedure comprising the addition at a constantrate of anemulsion of halogenated conjugated diene and mono-alkenyl aromatic alkyl halide monomers to a polymerization zone containing an aqueous solution or dispersion of poly-merization initiator. Pol.ymerization conditions are other-wise esentially the same as for conventional batch polymeri-~6'71~
zation p~ocesses and need not be discussed here. The poly-merization reaction is exothermic and the reaction tempera-ture should be maintained below about 75C., preferably below about 60C. Substantially any free radical-generating catalyst or initiator, including the well--known redox catalyst systems, such as ammonium persulfate/sodium metabisulfite, benzoyl peroxide, hydrogen peroxide, di-t-butylperoxide, azo-bis(isobutryonitrile), alkali metal persulfates and alkali rnetal and ammonium perborates can be employed Eor the copoly-merization reaction to assure more rapid onset of the reac-tion and more reproducible results. Followiny the polymeriza-tion, unreacted volatiles can be removed by vacuum treatment at elevated temperatures or steam distillation, with the specific method being a matter of choiceO
Of the prime importance to obtaining latices which provide acceptable adhesion is the choice of surEactant agents. It has been found that it is necessary to employ anionic surfactant agents or mixtures of anionic and non~
ionic surfactant agents, wi-th such mixtures being currently preferred. While cationic surfactants are effective emul~i-fying agents as such, their use in the preparation of the elastomeric copolymer latices of this invention, either alone or i~ combination with either or both anionic and non-ionic agents, is detrimental to adhesive performance. The surfactant systems will be used in a range from 0.01 to 15 weight percent, preferably l to 10 weight percent, based on weight of monomers charged. The use of anionic-nonionic mixed surfactant systems is currently preferred, at a ratio of 1.2-2.1:1, preferably 1.3-2.0:1, anionic; nonionic agent.
Representative anionic agents include carboxylates, such as fatty acid soaps from lauric, stearic and oleic acids, and acyl derivatives of sarosine such as methyl glycine; sul-fates, such as sodium lauryl sulfate (Duponol C*); sulfated natural oils and esters, such as Turkey Red Oil; alkyl aryl polyether sulfates, such as Triton X-301*; alkyl aryl polyether *a trademark ~L~6'7~
sulfonates, such as Tri-ton X-200* and Ultrawet* DS, K, 35K
and 42Ki isopropyl naphthalene sulfonates, such as Aerosol 05, and sulfosuccinates and sulfosuccinamates such as Aerosol* OT, M~, ~R, 102 and 18; phosphate esters, such as short chain fa-tty alcohol parti.al esters of complex phosphates (Victawet*); and orthophosphate esters of polyethoxylated fatty alcohols Gafac*). Representative nonionic agents in~
clude ethoxylated (ethylene oxide derivatives of) mono-and . polyhydricalcohols, such as the Triton octyl- and nonyl-phenol series; ethylene oxide/propylene oxide block copolymers, such as the Pluronic* series; esters, such as glyceryl monostear-ate; products of the dehydration of sorbitol, such as sorbi-tan monosteara-te and polyethylene oxide sorbitan monolaurate (Span* and Tween* series); and amides, such as lauric acid isopropanol amide (Lauridit* LP). Currently preferred is a 1.8:1 mlxture of sodium dodecyldiphenyl ether disulfonate (Dowfax 2Al*) anionic surfactant and nonylphenol polythylene glycol (Triton X-100) nonionic surfactant. The anionic and anionic-nonionic surfactant systems which must be employed in the practice of -this invention are described in more depth in "Emulsions:Theory and Practice", by Paul Becker,~
Chapter 6, Reinhold Publishing Corp., New York, 1965; and in McCutcheon's "Detergents and Emulsifiers, 1972 Annual".
The elastomeric copolymer latices resulting from the emulsion copolymerization of halogenated conjugated dienes and monoalkenyl aromatic alkyl halides in accordance with this invention invariably show a pH in the range of 2-3. While such acidic compositions do provide excellent adhesive performances, it is advisable to adjust the pH to a value in the range of about 4 to 11, pre~erably 6-10 with acid-scavengers or buffers, such as Zinc oxide, dibasic lead phosphate, sodium acetate-acetic acid mixtures and the like, with dibasic lead phosphate being the current compound of choice. Such stabilizers will, of course, be used in an amount sufficient to provide the desired pH level.
*a trademark ~71~3~
The aromatie nitxoso compounds whieh are suitable for use in the practice oE the present invention ean be any aromatie hydroearbon sueh as benzene, naphthalene, anthri--cen-e and biphenyl whieh eontains at least two nitroso groups attached direetly to non-adjaeent ring earbon atoms. More particularly, such nitroso compounds are deseribed as poly-C-nitroso aromatic compounds hav:ing from l -to 3 aromatic nuelei, including fused.aromatie nuclei having from 2 to 6 nitroso groups attached directly to non-adjacent nuclear earbon atoms. The presently preferred poly-C-nitroso mater-ials are the di-nitroso aromatic compounds, especially the di-nitroso benzenes and i-nitroso naphthalenes, sueh as the meta- or paradinitrosobenzenes and the meta- or para-dinitrosonapthalenes~ The nuelear hydrogen atoms of the aromatie nueleus ean be replaeed by alkyl, alkoxy, eyeloalkyl, aryl, aryalkyl, alkaryl, arylamine, arylnitroso, amino, halo-gen, and -the like groups. The presence of sueh substituents on the aromatic nucleus has little effect on the activity of the poly-C-nitroso compounds in the present invention. As far as is currently known, there is no limitation as to the character of the substituents, which can be organic or ih-organie in nature. Thus, where reference is made to poly-C-nitroso "aromatic compound", "benzenes", or "naphthalenes", it will be understood to inelude both substituted and un-substituted nitroso eompounds, unless otherwise speeified.
Partieularly preferred poly-C-nitroso compounds have the formula (R3) Ar - ~N)2;
wherein Ar is seleeted from the group consisting phenylene and naphthalene;
R is a monovalent organic radical selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, arylamine and alkoxy radicals having from l to 20 carbon atoms, amino, or halogen, and is preferably an alkyl group having from l to 8 carbon atoms; and ..~
~7~
is 0, 1, 2, 3, or 4 and is preferably 0.
~ partial non-limitlng listing of suitable poly-C-ni-troso compounds which are suitable for use in the practice of the invention include m-dinitroso-benzene, p-dinitroso-benzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, 2,5-di-nitroso-p-cymene, 2-methyl~ dinitrosobenzene, 2-methyl-5-chloro-1,4-dinitrosobenzene, 2-fluoro-1,4-dini--trosobenzene, 2-metho~y-1,3-dinitroso-benzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzene, and 2-cyclohexyl-1,4-dinitrosobenzene.
Substantially any of the polymeric matexials which have been heretofore employed as film formers or film-form-ing adjuncts in adhesive formulations are suitable for use in the practice of the present invention as auxiliary film-forming materials. Such film-forming materials include, with-out limitation, thermosetting condensation polymers, such as thermosetting phenolic resins, thermosetting epoxy resins, thermosetting polyester resins, thermosetting triazine resins, and the like; polymers and copolymers of polyethylenical~y unsaturated materials such as poly(vinylbutyral); poly(v,inyl formal); poly-(vinyl acetate); chlorinated poly(vinyl chloride); copolymers of vinyl acetate and vinyl chloride;
chlorinated copolymers of vinyl acetate and vinyl chloride;
polymers of acrylic acid; copolymers of acrylic acid and conjugated dienes, such as 1,3-butadiene; 2-chloro-1,3-butadiene; 2,3-dichloro-1,3-butadiene; and the like, and including after halogenated products thereoE; polymers of methacrylic acid; copolymers of methacrylic acid and con-jugated dienes; co-polymers of vinylpyridine and conjugated dienes, and including polyvalent reaction products thereof;
cellulosic materials such as cellulose acetate butyrate; and - the like. Particularly preferred film-forming materials are halogen-containîng rubbers, including without limitation, - chlorinated natural rubber; polychloroprene; chlorinated polychloroprene; chlorinated polybutadiene; chlorinated -~
polyethylene; chlorinated ethylene/
:
~, _ g _ 19~
propylene copolymexs; chlorina~ed ethylene/propylene/non-conjugated diene terpolymers; chlorinated copolymers of butadiene and st~vrene; chlorosulfonated polyethylene; bro-minated poly(2,3-dichloro-1,3-butadiene); mixtures of such halogen-containin~ rubbers with hydrohalogenated rubbersor hypohalogenated rubbers; mi~-tures of two or more such halogen-containing rubbers and the like. Other suitable polymeric film-forming adjuncts include cellulosic esters such as cellu-lose acetate butyrate; natural rubber; butyl rubber; e-thylene/
propylene copolymer (EP~) rubber; ethylene/propylene/diene terpolymer (EPDM) rubber; polymers and copolymers of diene having from ~ to 12 carbon atorns, such as polybutadiene, and including also copolymers of such dienes of one or more different monomers copolyrnerizable therewith, such as S~R
and butadiene/acrylonitrile rubber. As indicated halogenated polymeric materials, and particularly chlorinated and bromi-nated rubbers, are preferred auxiliary film-forming materials.
The relative ratios of elastomeric copolymer to auxiliary film-forming materials, when employed, is generally in the range from 10 to 90, percent by weight of elastomeric cop~ly-mer with a corresponding 90 to 10, preferably 80 to 10, per-cent by weight of auxiliary film-forming material.
The adhesive compositions of the present invention may also utilize fillers, extenders and coloring agents such as carbon black, as well as various metallic oxides, etc.
These fillers are inert from the standpoint of affecting the adhesive properties of the compositionO
Generally, the solids content of the adhesive com-position may range from as low as 5% to as high as about 60%
solids.
A salient feature of the aqueous adhesive composi-tions of this invention is good shelf life, that is, can stability. Wh~reas conventional aqueous adhesives have rela-tively short (l day - 2 weeks) shelf life, the invention com-positions have a shelf life in excess of two months. Another ~L16~7~
merito~ious featu~e is that the invention compositions do not exhibit a decline in bonding ability when coa-ted on a substrate and stored in air ove~ a period o~ time. Neither does the bond between rubber and substrate (with the adhe-sive a-t the interface) deteriora-te upon prolonged e~posure to air.
The method of bonding na-tural and synthetic rubbers to rigid and non~rigid substrates using the curable adhesive composition of this invention ge:nerally comprises the steps of (1) makiny or preparing the a:bove described aqueous adhe-sive composition; (2) coating the substrate with a thin layer of the composition; (3) drying the adhesive coating such as by air drying or heating in an oven at slightly elevated temperatures; (4) contacting the adhesive coated substrate with a vulcanizable rubber composition; and (5) curing the adhesive concurrently with vulcanization of the rubber.
The adhesive compositions of the present invention are prepared by conventional emulsification techniques which do not require further elucidation herein.
The following examples are provided to illustrate the invention. All parts and percentages which relate to composition are by weight unless otherwise indicated. In these examples, rubber adhesion is tested according to ASTM D-429, method B, modified to 40 C. Adhesion values are reported in kilonewtons per linear meter, kN/m. Mode of failure is reported conventionally as R, CM, CP or the like, with a numerical value indicating percent. Boiling water resistance is tested by immersing test samples in boiling water for two hours. Failure is determined by peeling rubber from metal with pliers immediately after removal from water.
This test is more severe than standard tests in which the sample is cooled to ambient temperature before peeling.
When the adhesiye being tested is employed with a primer (2-coat adhesive systems), the metal parts are coated with ~;'7~
the prime~, allowed to dry, c~ated with adhesive and again allowed to dry beEore being bonded to the elastomer stock.
Otherw~se, the unprimed ~etal par-ts are coated with adhe-sive and allowed ko dry before being bonded to the elas-tomer stock. The pre-heat tolerance test is effected by maintaining the adhesively-coated part at vulcanization tem-peratures, prior to contacting the adhesive with the rubher composition being bonded, for a period of time corresponding to actual commer~lal practice. Standard adhesion tests are then made of the adhesively-bonded assemblies.
EXAMPLE I
__ __ Preparation of halogenated conjugated diene-mono-alkenyl aromatic alkyl halide copolymer latex A first reaction zone is charged with 288 g distilled water, 27 g sodium dodecyldiphenyl ether disulfonate anionic surfactant, 15 g ethoxylated octyl phenol anionic surfactant, 0.9g sodium bicarbonate and 1.8 g sodium metabisulfite, and purged with nitrogen. To the reaction is added a charge of 515 g 2,3-dichloro-1,3-butadiene (halogenated conjugated diene) and 16 g vinyl benzyl chloride (monoalkenyl aromatic alkyl halide). The contents of the reaction zone are cooled to below 40 C and vigorously stirred to a preemulsion. A
Second reaction zone is charged with 72 g distilled water and 1 8 g ammonium persulfate, purged with nitrogen, and its contents ar~ heated to a temperature of 40-45 C. The pre-emulsion from the first reaction zone is added to the con-tents of the second reaction zone at a constant rate over the course of 90 minutes, while maintaining the reaction temperature in the range of 40-45 C. After completing the addition of preemulsion, the reaction mixture is allowed to polymerize for an additional 60 minutes at 40-45 C. The resulting copolymer latex has a 95:5 halogenated conjugated diene:monoalkenyl aromatic alkyl halide composition. The pH
of the latex is adjusted ta 6.8 with dibasic lead phosphate.
The latex has a total solids content (TSC) of 43%.
,.~
~ ~ 12 -~67~3~
Preparation o~ 2_3-dich oro-but / cr~lonl-trile copolymer latex A reaction zone is charged with 6.9 g disodium dodecyldiphenyl ether disulfonate anionic surfactant, 4.6 g ethoxylated octylphenol nonionic surEactant and 172 g dis-tilled water. The reac-tion zone is purged with nitrogen and 129 g 2,3-dichloro-1,3 butadiene and 42 g ~-chloroacryloni-trile are added. The resulting mixture is emulsified with vigorous stirring. To this emulsion are addedO.5 gammonium persulfate and 0.5 g sodium dithionite. The reac-tion exo therms to 45 C. After the lnitial exotherm, the contents of the reaction zone are hea-ted at 55 C for 75 minutes.
There is then added, at a constan-t rate over the course of 5 hours, separately but simultaneously, (1), an emulsion consisting of 74 g disodium dodecyldiphenyl ether disulfonate anionic surfactant, 49.1 g ethoxylated octylphenol nonionic surfactant, 1420 g 2,3-dichloro-1,3-butadiene and 465 g~-chloroacrylonitrile in lB28 g distilled wateri and, (2), an aqueous activator solution containing 8 g sodium pyrophos-phate, 4 g ammonium persulfate and 4 g sodium metabisulfitein 334 g distilled water. During the addition of the comono-mer emulsion and the activator solution, the reaction temper-ture is maintained in the range of 55-60 C. After the addi-tions are comple~ed, the copolymerization reaction is allowed to continue for 90 minutes at a temperature of 55 C. There is then added to the reaction zone at a constant rate over the course of 45 minutes 100 g 2,3-dichloro-1,3-butadiene emulsified in 90 g distilled water containing 3.75 g diso-dium dodecyldiphenyl ether disulfonate anionic surfac-tant and 2.5 g ethoxylated octylphenol nonionic surfactant. Simu-ltaneously, and also at a constant xate, a solution consis-ting of 0.6 g sodiu~ pyrophosphate, 0.3 g ammonium persulfate and 0.3 g sodium metab~sulfite in 25 g distilled water is added to the copolymerization reaction zone. After the addi-tions are complete, the copolymerization reaction mixture ~L~,,.6~ 3~L
is heated an additional 90 mirlutes at 55 C. The`resulting copolymer latex has a 3O25;1 2,3-dichloro-1,3-bu-tadiene: ~ -chloroacrylonitrile composit~on.
EX~MPLE I~
llalogenated con~ugated diene-monoalkenyl aromatic alkyl halide copolymer latex, halogenated conjugated diene homopolymer latex and monoalkenyl aromatic alkyl halide homo-polymer latex are employed to prepare the following adhesive compositions, with all amounts being stated in parts by weight on a dry weight basis:
Adhesive: A B C_ D
Halogenated conjugated 100 100 0 0 diene-monoalkenyl aro-matic alkyl halide co-polymer latexa Halogenated conjugated 0 0 95 95 dieneb Homopolymer latexd Monalkenyl aromatic alkyl 0 0 5 5 halideC Homopolymer latexd Dinitrosobenzene 0 36 0 36 Water~ in an amount to provide a total solids content o~,40~.
a = Copolymer latex of Example I
b = 2,3-dichloro-1,3-butadiene c = Vinyl benzyl chloride 5 d = Homopolymer latex prepared by conventional batch poly-merization process.
The adhesive compositions are employed to bond sol-vent-wiped, grit-blasted, cold-rolled steel to sulfur-vul-canizable natural rubber and poly-(styrene-butadiene) rubber compositions. The steel parts are coated with solvent-based, heat-xeactive phenolic resin primer prior to application of the adhesive. The natural rubber assemblies are cured at 153 C for 15 minutes and tested for boiling water resistance.
The synthetlc rubber assemblies are cured at 153 C ~or 30 m;`nutes, at no preheat and with 10 minutes prehea~, and
the present invention comprise a latex of an elastomeric copolymer prepared by emulsion copolymerization in an a~ueous medium in the presence of at least one anionic sur-factant or mixture of at least one anionic surfactant and at least one nonionic surfactant of a mixture of, (a), at least one conjugated diene selected from the group consis-ting of 2-halo-1,3-butadiene and 2,3-dihalo-1,3-butadiene;
and, (b), at least one monoalkenyl aromatic alkyl halide.
Option~lly, and preferably, the adhesive latices of the invention will have dispersed therein from 1 to 200, pre-ferably from 10 to 150 parts by weight, per 100 parts by weight of elastomeric copolymer solids, of at least one aromatic nitroso compound. The adhesive compositions of the invention can also have optionally included therein from 20 to 90 percent by weight of at least one water-soluble or water-dispersible auxiliary film-forming material selected from the group consisting of halogenated rubber, halogenated resins and phenolic resins, said percentage being based on total weight of said elastomeric copolymer solids and said auxiliary film-forming material. J
With respect to the halogenated conjugated diené
monomers, the 2,3-dihalo-1,3-butadienes are currently pre-ferred, with 2,3, dichloro-l, 3-butadiene being the current monomer of choice. The bromine- and iodine-substitu-ted 1,3-butadiene monomers can also be employed to form the elastomeric copolymer latices of the invention. With respect to the comonomer, the term "monoalkenyl aromatic alkyl halide" is intended to include those monomers wherein an alkenyl group is attached directly to an aromatic nucleus containing from 6 to 1~ carbon atoms and at least one halogen-substituted al]cyl group is also attached directly to the aromatic nucleus, the halogen being substituted on the alpha carbon atom. The terms "halo", "halogen", "halo-genated" and "halide" are intended to includ~ chlorine, bromine and iodine substituents, with chlorine being the q3:~
current substituent of choice. More particularly, the mono-alkenyl aromatic alkyl halides have the characteristic formula~
I. ~ CX2 = Cx ~ R) ; and ~- Cx2 = Cx ,~ ;
(R)b (R)b wherein X is hydrogen, chlorinel bromine or iodine, R is an alkyl group having from 1 to 4 carbon atoms in which the alpha carbon atom of said alkyl group, that is, the carbon atom which is attached directly to the aromatic nucleus, is substituted with from 1 to 3 halogen atoms selected from the group consisting of chlorine, bromine or iodine; a is 1 or 2 and b is zero, 1 or 2, with the proviso that at least one b be at least one. Currently, X is hydro-gen, R is one, the halogen groups is one, a is one and b is one. Monoalkenyl aromatic alkyl halides having the formula (I) are the current comonomers of choice. Representative monoalkenyl aromatic alkyl halides include vinyl benzyl chloride (p-chloromethyl-vinylbenzene), p-trichloromethyl-vinylbenzene~ p~ ~-chloroethyl~-vinylbenzene, p-( ~ -chloro-butyl)-vinylbenzene; ~ -chlorovinyl-benzylchloride; o,m-di ( ~ -chloroethyl)-vinylbenzene; 4-chloromethyl-vinylnapthalene, the corresponding bromine and iodine analogsl and the like.
The current monoalkenyl aromatic alkyl halide of choice is vinylbenzyl chloride.
~6'~1~3~
The elastomeric copolymer latices which are employ~
ed in the present invention are prepared by emulsion poly-merization of the halogenated conjugat.ed diene and monoal-kenyl aromatic alkyl halide comonomers in an aqueous medium in the presence of an lonic or mixed ionic-nonionic surfac-tant system, with ionlc surfactant systems being currentlypreferred. It has been found that the elastomeric copolymer products best suited for use in the practice of this inven-tion contain from 67 to 97, preferably 75 to 97, and, opti~
mally, 93 to 97 percent by weight of halogenated conjugated diene; and,correspondingly. from 3 to 33, preferably 3 -to 25, and, optimally, 3 to 7, percent by weight of monoalkenyl aro-matic alkyl halide. The amounts of each comonomer can, how-ever, extend beyond these limits, but there is no currently known reason to do so.
The emulsion polymerization is carried out in a closed vessel in which the space not occupied by the reaction mixture ls preferably maintained free of oxygen by a blanket of inert gas, such as nitrogen. The induction period of tpe polymerization reaction is extended by the presence of o~ygen and it is desirable to effect the reaction in the substan-tial absence of oxygen. In the broad sense, the emulsion poly-merization is effected by mixing the monomeric ingredients, emulsifying this mixture, and subjecting the emulsion to moderate polymerization conditions until substantially all of the monomer charge has been polymerized. ~owever, for various practical reasons which need not be discussed here, it has been discovered that emulsion polymerization of halo-genated conjugated diene and monoalkenyl aromatic alkyl halide comonomers is more efficiently accomplished by a semi-continuous procedure comprising the addition at a constantrate of anemulsion of halogenated conjugated diene and mono-alkenyl aromatic alkyl halide monomers to a polymerization zone containing an aqueous solution or dispersion of poly-merization initiator. Pol.ymerization conditions are other-wise esentially the same as for conventional batch polymeri-~6'71~
zation p~ocesses and need not be discussed here. The poly-merization reaction is exothermic and the reaction tempera-ture should be maintained below about 75C., preferably below about 60C. Substantially any free radical-generating catalyst or initiator, including the well--known redox catalyst systems, such as ammonium persulfate/sodium metabisulfite, benzoyl peroxide, hydrogen peroxide, di-t-butylperoxide, azo-bis(isobutryonitrile), alkali metal persulfates and alkali rnetal and ammonium perborates can be employed Eor the copoly-merization reaction to assure more rapid onset of the reac-tion and more reproducible results. Followiny the polymeriza-tion, unreacted volatiles can be removed by vacuum treatment at elevated temperatures or steam distillation, with the specific method being a matter of choiceO
Of the prime importance to obtaining latices which provide acceptable adhesion is the choice of surEactant agents. It has been found that it is necessary to employ anionic surfactant agents or mixtures of anionic and non~
ionic surfactant agents, wi-th such mixtures being currently preferred. While cationic surfactants are effective emul~i-fying agents as such, their use in the preparation of the elastomeric copolymer latices of this invention, either alone or i~ combination with either or both anionic and non-ionic agents, is detrimental to adhesive performance. The surfactant systems will be used in a range from 0.01 to 15 weight percent, preferably l to 10 weight percent, based on weight of monomers charged. The use of anionic-nonionic mixed surfactant systems is currently preferred, at a ratio of 1.2-2.1:1, preferably 1.3-2.0:1, anionic; nonionic agent.
Representative anionic agents include carboxylates, such as fatty acid soaps from lauric, stearic and oleic acids, and acyl derivatives of sarosine such as methyl glycine; sul-fates, such as sodium lauryl sulfate (Duponol C*); sulfated natural oils and esters, such as Turkey Red Oil; alkyl aryl polyether sulfates, such as Triton X-301*; alkyl aryl polyether *a trademark ~L~6'7~
sulfonates, such as Tri-ton X-200* and Ultrawet* DS, K, 35K
and 42Ki isopropyl naphthalene sulfonates, such as Aerosol 05, and sulfosuccinates and sulfosuccinamates such as Aerosol* OT, M~, ~R, 102 and 18; phosphate esters, such as short chain fa-tty alcohol parti.al esters of complex phosphates (Victawet*); and orthophosphate esters of polyethoxylated fatty alcohols Gafac*). Representative nonionic agents in~
clude ethoxylated (ethylene oxide derivatives of) mono-and . polyhydricalcohols, such as the Triton octyl- and nonyl-phenol series; ethylene oxide/propylene oxide block copolymers, such as the Pluronic* series; esters, such as glyceryl monostear-ate; products of the dehydration of sorbitol, such as sorbi-tan monosteara-te and polyethylene oxide sorbitan monolaurate (Span* and Tween* series); and amides, such as lauric acid isopropanol amide (Lauridit* LP). Currently preferred is a 1.8:1 mlxture of sodium dodecyldiphenyl ether disulfonate (Dowfax 2Al*) anionic surfactant and nonylphenol polythylene glycol (Triton X-100) nonionic surfactant. The anionic and anionic-nonionic surfactant systems which must be employed in the practice of -this invention are described in more depth in "Emulsions:Theory and Practice", by Paul Becker,~
Chapter 6, Reinhold Publishing Corp., New York, 1965; and in McCutcheon's "Detergents and Emulsifiers, 1972 Annual".
The elastomeric copolymer latices resulting from the emulsion copolymerization of halogenated conjugated dienes and monoalkenyl aromatic alkyl halides in accordance with this invention invariably show a pH in the range of 2-3. While such acidic compositions do provide excellent adhesive performances, it is advisable to adjust the pH to a value in the range of about 4 to 11, pre~erably 6-10 with acid-scavengers or buffers, such as Zinc oxide, dibasic lead phosphate, sodium acetate-acetic acid mixtures and the like, with dibasic lead phosphate being the current compound of choice. Such stabilizers will, of course, be used in an amount sufficient to provide the desired pH level.
*a trademark ~71~3~
The aromatie nitxoso compounds whieh are suitable for use in the practice oE the present invention ean be any aromatie hydroearbon sueh as benzene, naphthalene, anthri--cen-e and biphenyl whieh eontains at least two nitroso groups attached direetly to non-adjaeent ring earbon atoms. More particularly, such nitroso compounds are deseribed as poly-C-nitroso aromatic compounds hav:ing from l -to 3 aromatic nuelei, including fused.aromatie nuclei having from 2 to 6 nitroso groups attached directly to non-adjacent nuclear earbon atoms. The presently preferred poly-C-nitroso mater-ials are the di-nitroso aromatic compounds, especially the di-nitroso benzenes and i-nitroso naphthalenes, sueh as the meta- or paradinitrosobenzenes and the meta- or para-dinitrosonapthalenes~ The nuelear hydrogen atoms of the aromatie nueleus ean be replaeed by alkyl, alkoxy, eyeloalkyl, aryl, aryalkyl, alkaryl, arylamine, arylnitroso, amino, halo-gen, and -the like groups. The presence of sueh substituents on the aromatic nucleus has little effect on the activity of the poly-C-nitroso compounds in the present invention. As far as is currently known, there is no limitation as to the character of the substituents, which can be organic or ih-organie in nature. Thus, where reference is made to poly-C-nitroso "aromatic compound", "benzenes", or "naphthalenes", it will be understood to inelude both substituted and un-substituted nitroso eompounds, unless otherwise speeified.
Partieularly preferred poly-C-nitroso compounds have the formula (R3) Ar - ~N)2;
wherein Ar is seleeted from the group consisting phenylene and naphthalene;
R is a monovalent organic radical selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, arylamine and alkoxy radicals having from l to 20 carbon atoms, amino, or halogen, and is preferably an alkyl group having from l to 8 carbon atoms; and ..~
~7~
is 0, 1, 2, 3, or 4 and is preferably 0.
~ partial non-limitlng listing of suitable poly-C-ni-troso compounds which are suitable for use in the practice of the invention include m-dinitroso-benzene, p-dinitroso-benzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, 2,5-di-nitroso-p-cymene, 2-methyl~ dinitrosobenzene, 2-methyl-5-chloro-1,4-dinitrosobenzene, 2-fluoro-1,4-dini--trosobenzene, 2-metho~y-1,3-dinitroso-benzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzene, and 2-cyclohexyl-1,4-dinitrosobenzene.
Substantially any of the polymeric matexials which have been heretofore employed as film formers or film-form-ing adjuncts in adhesive formulations are suitable for use in the practice of the present invention as auxiliary film-forming materials. Such film-forming materials include, with-out limitation, thermosetting condensation polymers, such as thermosetting phenolic resins, thermosetting epoxy resins, thermosetting polyester resins, thermosetting triazine resins, and the like; polymers and copolymers of polyethylenical~y unsaturated materials such as poly(vinylbutyral); poly(v,inyl formal); poly-(vinyl acetate); chlorinated poly(vinyl chloride); copolymers of vinyl acetate and vinyl chloride;
chlorinated copolymers of vinyl acetate and vinyl chloride;
polymers of acrylic acid; copolymers of acrylic acid and conjugated dienes, such as 1,3-butadiene; 2-chloro-1,3-butadiene; 2,3-dichloro-1,3-butadiene; and the like, and including after halogenated products thereoE; polymers of methacrylic acid; copolymers of methacrylic acid and con-jugated dienes; co-polymers of vinylpyridine and conjugated dienes, and including polyvalent reaction products thereof;
cellulosic materials such as cellulose acetate butyrate; and - the like. Particularly preferred film-forming materials are halogen-containîng rubbers, including without limitation, - chlorinated natural rubber; polychloroprene; chlorinated polychloroprene; chlorinated polybutadiene; chlorinated -~
polyethylene; chlorinated ethylene/
:
~, _ g _ 19~
propylene copolymexs; chlorina~ed ethylene/propylene/non-conjugated diene terpolymers; chlorinated copolymers of butadiene and st~vrene; chlorosulfonated polyethylene; bro-minated poly(2,3-dichloro-1,3-butadiene); mixtures of such halogen-containin~ rubbers with hydrohalogenated rubbersor hypohalogenated rubbers; mi~-tures of two or more such halogen-containing rubbers and the like. Other suitable polymeric film-forming adjuncts include cellulosic esters such as cellu-lose acetate butyrate; natural rubber; butyl rubber; e-thylene/
propylene copolymer (EP~) rubber; ethylene/propylene/diene terpolymer (EPDM) rubber; polymers and copolymers of diene having from ~ to 12 carbon atorns, such as polybutadiene, and including also copolymers of such dienes of one or more different monomers copolyrnerizable therewith, such as S~R
and butadiene/acrylonitrile rubber. As indicated halogenated polymeric materials, and particularly chlorinated and bromi-nated rubbers, are preferred auxiliary film-forming materials.
The relative ratios of elastomeric copolymer to auxiliary film-forming materials, when employed, is generally in the range from 10 to 90, percent by weight of elastomeric cop~ly-mer with a corresponding 90 to 10, preferably 80 to 10, per-cent by weight of auxiliary film-forming material.
The adhesive compositions of the present invention may also utilize fillers, extenders and coloring agents such as carbon black, as well as various metallic oxides, etc.
These fillers are inert from the standpoint of affecting the adhesive properties of the compositionO
Generally, the solids content of the adhesive com-position may range from as low as 5% to as high as about 60%
solids.
A salient feature of the aqueous adhesive composi-tions of this invention is good shelf life, that is, can stability. Wh~reas conventional aqueous adhesives have rela-tively short (l day - 2 weeks) shelf life, the invention com-positions have a shelf life in excess of two months. Another ~L16~7~
merito~ious featu~e is that the invention compositions do not exhibit a decline in bonding ability when coa-ted on a substrate and stored in air ove~ a period o~ time. Neither does the bond between rubber and substrate (with the adhe-sive a-t the interface) deteriora-te upon prolonged e~posure to air.
The method of bonding na-tural and synthetic rubbers to rigid and non~rigid substrates using the curable adhesive composition of this invention ge:nerally comprises the steps of (1) makiny or preparing the a:bove described aqueous adhe-sive composition; (2) coating the substrate with a thin layer of the composition; (3) drying the adhesive coating such as by air drying or heating in an oven at slightly elevated temperatures; (4) contacting the adhesive coated substrate with a vulcanizable rubber composition; and (5) curing the adhesive concurrently with vulcanization of the rubber.
The adhesive compositions of the present invention are prepared by conventional emulsification techniques which do not require further elucidation herein.
The following examples are provided to illustrate the invention. All parts and percentages which relate to composition are by weight unless otherwise indicated. In these examples, rubber adhesion is tested according to ASTM D-429, method B, modified to 40 C. Adhesion values are reported in kilonewtons per linear meter, kN/m. Mode of failure is reported conventionally as R, CM, CP or the like, with a numerical value indicating percent. Boiling water resistance is tested by immersing test samples in boiling water for two hours. Failure is determined by peeling rubber from metal with pliers immediately after removal from water.
This test is more severe than standard tests in which the sample is cooled to ambient temperature before peeling.
When the adhesiye being tested is employed with a primer (2-coat adhesive systems), the metal parts are coated with ~;'7~
the prime~, allowed to dry, c~ated with adhesive and again allowed to dry beEore being bonded to the elastomer stock.
Otherw~se, the unprimed ~etal par-ts are coated with adhe-sive and allowed ko dry before being bonded to the elas-tomer stock. The pre-heat tolerance test is effected by maintaining the adhesively-coated part at vulcanization tem-peratures, prior to contacting the adhesive with the rubher composition being bonded, for a period of time corresponding to actual commer~lal practice. Standard adhesion tests are then made of the adhesively-bonded assemblies.
EXAMPLE I
__ __ Preparation of halogenated conjugated diene-mono-alkenyl aromatic alkyl halide copolymer latex A first reaction zone is charged with 288 g distilled water, 27 g sodium dodecyldiphenyl ether disulfonate anionic surfactant, 15 g ethoxylated octyl phenol anionic surfactant, 0.9g sodium bicarbonate and 1.8 g sodium metabisulfite, and purged with nitrogen. To the reaction is added a charge of 515 g 2,3-dichloro-1,3-butadiene (halogenated conjugated diene) and 16 g vinyl benzyl chloride (monoalkenyl aromatic alkyl halide). The contents of the reaction zone are cooled to below 40 C and vigorously stirred to a preemulsion. A
Second reaction zone is charged with 72 g distilled water and 1 8 g ammonium persulfate, purged with nitrogen, and its contents ar~ heated to a temperature of 40-45 C. The pre-emulsion from the first reaction zone is added to the con-tents of the second reaction zone at a constant rate over the course of 90 minutes, while maintaining the reaction temperature in the range of 40-45 C. After completing the addition of preemulsion, the reaction mixture is allowed to polymerize for an additional 60 minutes at 40-45 C. The resulting copolymer latex has a 95:5 halogenated conjugated diene:monoalkenyl aromatic alkyl halide composition. The pH
of the latex is adjusted ta 6.8 with dibasic lead phosphate.
The latex has a total solids content (TSC) of 43%.
,.~
~ ~ 12 -~67~3~
Preparation o~ 2_3-dich oro-but / cr~lonl-trile copolymer latex A reaction zone is charged with 6.9 g disodium dodecyldiphenyl ether disulfonate anionic surfactant, 4.6 g ethoxylated octylphenol nonionic surEactant and 172 g dis-tilled water. The reac-tion zone is purged with nitrogen and 129 g 2,3-dichloro-1,3 butadiene and 42 g ~-chloroacryloni-trile are added. The resulting mixture is emulsified with vigorous stirring. To this emulsion are addedO.5 gammonium persulfate and 0.5 g sodium dithionite. The reac-tion exo therms to 45 C. After the lnitial exotherm, the contents of the reaction zone are hea-ted at 55 C for 75 minutes.
There is then added, at a constan-t rate over the course of 5 hours, separately but simultaneously, (1), an emulsion consisting of 74 g disodium dodecyldiphenyl ether disulfonate anionic surfactant, 49.1 g ethoxylated octylphenol nonionic surfactant, 1420 g 2,3-dichloro-1,3-butadiene and 465 g~-chloroacrylonitrile in lB28 g distilled wateri and, (2), an aqueous activator solution containing 8 g sodium pyrophos-phate, 4 g ammonium persulfate and 4 g sodium metabisulfitein 334 g distilled water. During the addition of the comono-mer emulsion and the activator solution, the reaction temper-ture is maintained in the range of 55-60 C. After the addi-tions are comple~ed, the copolymerization reaction is allowed to continue for 90 minutes at a temperature of 55 C. There is then added to the reaction zone at a constant rate over the course of 45 minutes 100 g 2,3-dichloro-1,3-butadiene emulsified in 90 g distilled water containing 3.75 g diso-dium dodecyldiphenyl ether disulfonate anionic surfac-tant and 2.5 g ethoxylated octylphenol nonionic surfactant. Simu-ltaneously, and also at a constant xate, a solution consis-ting of 0.6 g sodiu~ pyrophosphate, 0.3 g ammonium persulfate and 0.3 g sodium metab~sulfite in 25 g distilled water is added to the copolymerization reaction zone. After the addi-tions are complete, the copolymerization reaction mixture ~L~,,.6~ 3~L
is heated an additional 90 mirlutes at 55 C. The`resulting copolymer latex has a 3O25;1 2,3-dichloro-1,3-bu-tadiene: ~ -chloroacrylonitrile composit~on.
EX~MPLE I~
llalogenated con~ugated diene-monoalkenyl aromatic alkyl halide copolymer latex, halogenated conjugated diene homopolymer latex and monoalkenyl aromatic alkyl halide homo-polymer latex are employed to prepare the following adhesive compositions, with all amounts being stated in parts by weight on a dry weight basis:
Adhesive: A B C_ D
Halogenated conjugated 100 100 0 0 diene-monoalkenyl aro-matic alkyl halide co-polymer latexa Halogenated conjugated 0 0 95 95 dieneb Homopolymer latexd Monalkenyl aromatic alkyl 0 0 5 5 halideC Homopolymer latexd Dinitrosobenzene 0 36 0 36 Water~ in an amount to provide a total solids content o~,40~.
a = Copolymer latex of Example I
b = 2,3-dichloro-1,3-butadiene c = Vinyl benzyl chloride 5 d = Homopolymer latex prepared by conventional batch poly-merization process.
The adhesive compositions are employed to bond sol-vent-wiped, grit-blasted, cold-rolled steel to sulfur-vul-canizable natural rubber and poly-(styrene-butadiene) rubber compositions. The steel parts are coated with solvent-based, heat-xeactive phenolic resin primer prior to application of the adhesive. The natural rubber assemblies are cured at 153 C for 15 minutes and tested for boiling water resistance.
The synthetlc rubber assemblies are cured at 153 C ~or 30 m;`nutes, at no preheat and with 10 minutes prehea~, and
3~
tested ~o~ peel adhesion according to ~STM D-420,~Method B, modi~ied to 45 C. The results a~e reported in the following tahle:
~dhesx~e Failure Mode g 100 R
Peel adhesion and pre heat tolerance, zero and 10 minutes, synthetic (SBR) rubber.
Pre-heat @ Adhesion Failure Adhesive 53C, Min. kN/m Mode A 0 14.7 7 R
A 10 19.4 5 R
B 0 31.0 100 R
B 10 26.3 88 R
C 0 6.8 100 RC
D 0 24.7 93 R
D 10 10.5 30 R
EXAMPLE III
The latexes of Example 1 are employed to prepare the following adhesives, with all amounts being stated in parts by weight on a dry weight basis:
Adhesive E F G H_ I
Halogenated conjugated 85 63.75 42.5 21.25 0 diene-monoalkenyl armo-matic alkyl halide co-polymer la-tex 2,3-dichloro-1,3- 0 21.25 42.5 63.75 85 butadiene- ~-chloro-acrylonitrile copoly~er latex Dinitrosobenzene 15 15 15 15 15 % TSC in water 43 43 43 43 43 The adhesive compositions are employed to bond ~l - 14a -.. . . .. . ..
~ ~' solvent-wiped, grit blasted, cold-~olled steel to sulfur-vulcanizable natural rubbex compositions. The steel parts are coated with solvent-based, heat-reactive phenolic resin primer prior to application o~ the adhesive. The assemblies are cured at 153 C for 15 minutes and tested for boiling water resistance. The results are reported in the followiny table:
Boiling water resistance, 2 hrs. immersion @ 100 C.
AdhesiveFailure Mode EXAMPLE IV
Halogenated conjugated diene-monoalkenyl aromat.ic aklyl halide copolymer latexes having monoalkenyl aromatic alkyl halide contents of 5, 11, 15 and 22 percent by weight, respectively are prepared from 2,3-dichloro-1,3-butadiene and vinyl benzyl chloride following the procedure of Example I. Each of the latexes are employed to prepare adhesive çom-positions according to the following formulas, with all amounts being reported in parts by weight on a dry weight basis.
Formula A B
Copolymer latex 100 100 Partially hydrogenated10.5 0 terphenyl plasticizer Zinc oxide 5.5 5.5 Dinitrosobenzene 20.0 20.0 Calcium carbonate 20.0 0 Carbon black 20.0 0 % TSC in water 41.8 410 8 The several adhesive compositions are employed to bond solyent-wiped~ grit-blasted, cold-rolled steel to - 14b -. _, . ,,_ , . ., . , . . . . .. , ... . . ,, .. , , . . .. _, . ... ... ~ . . .... .... .. .
~lG~
sulfur-vulcanizable natural rubber and poly(butadiene-styxene) xubber compositions. The steel parts are coated with either solvent-based heat-reactlve phenolic resin pri-mer or wa-ter-based novolak phenol.ic resin primer cornpositions prior to application oE the adhesive compositions. The natural rubber assemblies are cured at 153 C for 15 minutes, at no preheat and at preheat of 153 C Eor 6 minutes. The synthetic rubber assemblies are cured at 153 C fox 30 minutes at the same preheat conditions. Peel adhesion tests oE both natural and synthetic rubber compositions are eEfected according to ASTM D-429, Method B. modiEied to 45 C. The natural rubber assemblies are tested ~or boiling water resis-tance by immer-sion ~or two hours at 100 C. Test results are reported in the following table:
Boiling Water Resistance, Natural Rubber, Preheat: None Vinyl senzyl Chloride, Failure PrimerFormula Wt ~ Mode Solvent A 5 99 R
Solvent A 11 88 R
Solvent A 15 67 R
Solvent A 22 52 R ' Solvent B 5 99 R
Solvent B 11 94 R
Solvent B 15 59 R
Solvent B 22 98 R
~1 14c -Vinyl Benz~l Chloricle, ~rin:ler Formula Wt. ,~i Failure Mode Aqueous A 5 30 R
Aqueous A 11 47 R
Aqueous A . 15 33 R
Aqueous A 22 37 R
Aqueous B 5 40 R
Aqueous B 11 28 R
Aqueous B 15 35 R
Aqueous B 22 32 R
10 Peel Adhesion, Mo and 6 Minute Preheat~ Natural and Synthetic Rubber Preheat: None Vin~l Benzyl Chloride, Peel Adhesion PrimerElastorner Forrnula Wt. % kN/M Failure Mode SolventNatural A 5 8.6100 TR
SolventNatural A 11 6.57 VTR
SolventNatural A 15 ' 8.2100 TR
SolventNatural A 22 7.5100 VTR
Aqueous Natural A 5 9.350 VTR
Aqueous Natural A 11 8.699 TR
Aqueous Natural A 15 6.530 VTR
AqueousNatural A 22 6.538 VTR
SolventSynthetic A 5 25.7 78 R
Sol~Tent Synthetic A 11 26.9 99 R
SolventSynthetic A 15 20.6 23 R
SolventSynthetic A 22 21.4 24 R
AqueousS~mthetic A 5 16.8 41 R
AqueousSynthetic A 11 23.8 32 R
AqueousSynthetic A 15 19.7 42 R
AqueousSynthetic ,A 22 18.9 14 R
., Vin~l Benzyl Chloride, Peel Adnesion . ~imer Elastomer Formula.~,Vt. '~o kM/rnF~ilure I~/Iode Solvent Matural B 5 8. 4 77 TR
Solvent Natural B 11 7.0 73 VTR
Solvent Natural B 15 8. ô100 VTR
Solvent Natural B 22 7.2 77 ~TR
Aqueous Natural B 5 ~. 1 95 VTR
Aqueous Natural B 11 8.7 99 TR
Aqueous Natural B 15 7. 4 47 VTR
Aqueous Natural B 22 7. 0 23 VTR
Solvent Synthetic B 5 28. 1, SB 100 R
Solvent Synthetic B 11 28. 5 97 R
Solvent Synthetic B 15 27. 8, SB 100 R
Solvent Synthetic B 22 23. 6, SB 95 R
Aqueous Synthetic B 5 20. 6 34 R
Aqueous Synthetic B 11 19. 3 32 R
Aqueous Synthetic B 15 23.2 59 R
Aqueous Synthetic B 22 24.0, SB 60 R
Preheat: 6 Minutes at 153 C
- Vinyl Benzyl C'hloride, Peel Adhesion Primer Elastomer FormulaWt. % kN/mFailure Mode Solvent Natural A 5 6.7 100 RC
Solvent Natural A 11 5.0 100 RC
Solvent Natural A 15 4. 8 100 RC
Solvent Natural A 22 PBH 100 RC
Aqueous Natural A 5 3. 8 22 RC
Aqueous Natural A 11 4. 6 40 RC
Aqueous Natural A 15 4. 6 63 RC
Aqueous Natural A 22 4. 6 90 RC
. ~ Solvent Synthetic A 5 10. 5 100 RC
Solvent Synthetic A 11 12.7 100 RC
Solvent Synthetic A 15 9.8 100 RC
Solvent Synthetic A 22 11. 5 100 RC
. . ~
~i7J;9~
_r2hea~: 8 ~IIinutes at 153 C
Vinyl Benzyl Chlorid~, Peel Adhesion Primer Elastomer Formula~Nt. a'O __ kIii/mailur~ ~rode Aqueous Synthetic A 5 9. 3 13 RC
Aqueous Synthetic A 11 ~. 6 37 RC
Aqueous Synthetic A 13 9.1 42 RC
Aqueous Synthetic A 22 8. 9 20 RC
Solvent Natural B 5 7. 9 23 TR
Solvent Natural B 11 5.1 100 RC
Solvent Natural B 15 3. 9 100 RC
Solvent Natural B 22 PBH 100 RC
Aqueous Natural B 5 6. 2 5 VTR
Aqueous Natural B 11 7. 4 17 VTR
Aqueous Natural B 15 5.3 83 RC
Aqueous Natural B 22 5. 0 98 RC
Solvent Synthetic B 5 28. 0 98 R
Solvent Synthetic B 11 28.8 97 R
Solvent Synthetic B 15 2~. 5, SB 93 R
Solvent Synthetic B 22 24. 9 83 R
Aqueous Synthetic B 5 10.1 13 RC
Aqueous Synthetic B 11 15. 4 31 R
Aqueous Synthetic B 15 13. 2 43 R
Aqueous Synthetic B 22 15.4 5 R
EXAMPLE V
The halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex of Example I is employed to prepare the following adhesives, with amounts being reported in parts by weight on a dry weight basis:
Adhesive V-A V-B V-C
Copolymer latex 100 100 100 Dibasic lead phosphate 20 20 20 Dinitrosobenzene 20 50 100 % TSC in water 41.841. 8 41.8 ..
~G7~"3~L
The adhesive compositions are employed to bond solvent-wiped, grit-blastedr cold-rolled stcel to sulfur-vulcanlzable natural and pol~-(butadiene-styrene) s~nthetic rubber compositions. The steel par-ts are coated with an a~ueous primer comprising non-heat-reactive phenolic resin and resin curative ~rior to appl:ication of the adhesives.
The adhesively-coated parts are subjected to preheat bake at times of 9, 12, and 15 minutes at 153 C before being con-tacted with the vulcanizable rubber compositions. The natllral 10rubber assemblIes are cured at 153 C fox 15 minutes, with the synthetic rubber assemblies being cured at 153 C for 30 minutes. The assemblies are tested according to ASTM D~
429, Method B.modified to 45C: The results are reported in the following table:
15_eheat esistance, Natural Rubber Preheat Peel Adhesion AdhesiveMinutes kN/mFailure Mode .....
V-A 9 9.4100 R
V-A 12 8.763 VTR
V-A 15 7.730 VTR
V-B 9 9.1100 R
V-B 12 8.998 R
V-B 15 8.2100 R
V-C 9 9.4100 R
V-C 12 8.980 R
V-C 15 9.1100 R
Preheat Resistance, Poly(Butadiene-St~rene) Rubber Preheat Peel Adhesion AhesiveMinutes kN/mFailure Mode V-A 9 21.475 R
V-A 12 10.,6100 RC
V-A 15 9.1100 RC
V-B ~ 24.9, SB100 R
V-B 12 22.6 96 R
.
~6~
Prehea-t Resist~nce, Poly(Butadiene-Styrenë) Rubber P~eheat Peel Adhesion ~dhesi~eMinutes kN~mFailure Mode V-B 15 24,589 R
V-C 9 24.0,SB100 R
V-C 12 21.4,SB95 R
V-C 15 24.0,SB100 R
EXAMPLE ~I
~ halogenated conjugated diene-monoalkenyl aroma-tic alkyl halide copolymer latex having a monoalkenyl aroma-tic aklyl halide content of 22 weight percent is prepared from 2,3-dichloro-1,3-butadiene and vinyl ben~yl chloride following the procedure of Example I. The latex is used to prepare the following adhesive, with all amounts being re-ported in parts by weight on a dry weight basis:Copolymer latex 100Dinitrosobenzene 18 TSC in water 43 The adhesive composition is employed to bond sol-vent-wiped, grit-blasted, cold-rolled steel to a variety,of sulfur-vulcanizable natural and synthetic rubber compositions.
The steel parts are coated with a solvent-based heat-reactive phenolic resin primer prior to application oE the adhesive.
The assemblies are cured at conventional conditions of the time, temperature and pressure for each elastomer stock.
After cure, the assemblies are tested for primary adhesion only according to the method of ASTM D-429, Method B, modi-fied to 45C.- The results are reported below.
Peel Adhesion Elastomer Type kN/mFailure Mode Natural 8.4 100 R
Neoprene 20.1 100 R
Ethylene-propylene-diene 17.3 92 R
terpolymer Poly(styrene-~utadiene) 26.4 98 R
Butyl 15.4 85 R
~, _ 19 _ ... . .... ....
tested ~o~ peel adhesion according to ~STM D-420,~Method B, modi~ied to 45 C. The results a~e reported in the following tahle:
~dhesx~e Failure Mode g 100 R
Peel adhesion and pre heat tolerance, zero and 10 minutes, synthetic (SBR) rubber.
Pre-heat @ Adhesion Failure Adhesive 53C, Min. kN/m Mode A 0 14.7 7 R
A 10 19.4 5 R
B 0 31.0 100 R
B 10 26.3 88 R
C 0 6.8 100 RC
D 0 24.7 93 R
D 10 10.5 30 R
EXAMPLE III
The latexes of Example 1 are employed to prepare the following adhesives, with all amounts being stated in parts by weight on a dry weight basis:
Adhesive E F G H_ I
Halogenated conjugated 85 63.75 42.5 21.25 0 diene-monoalkenyl armo-matic alkyl halide co-polymer la-tex 2,3-dichloro-1,3- 0 21.25 42.5 63.75 85 butadiene- ~-chloro-acrylonitrile copoly~er latex Dinitrosobenzene 15 15 15 15 15 % TSC in water 43 43 43 43 43 The adhesive compositions are employed to bond ~l - 14a -.. . . .. . ..
~ ~' solvent-wiped, grit blasted, cold-~olled steel to sulfur-vulcanizable natural rubbex compositions. The steel parts are coated with solvent-based, heat-reactive phenolic resin primer prior to application o~ the adhesive. The assemblies are cured at 153 C for 15 minutes and tested for boiling water resistance. The results are reported in the followiny table:
Boiling water resistance, 2 hrs. immersion @ 100 C.
AdhesiveFailure Mode EXAMPLE IV
Halogenated conjugated diene-monoalkenyl aromat.ic aklyl halide copolymer latexes having monoalkenyl aromatic alkyl halide contents of 5, 11, 15 and 22 percent by weight, respectively are prepared from 2,3-dichloro-1,3-butadiene and vinyl benzyl chloride following the procedure of Example I. Each of the latexes are employed to prepare adhesive çom-positions according to the following formulas, with all amounts being reported in parts by weight on a dry weight basis.
Formula A B
Copolymer latex 100 100 Partially hydrogenated10.5 0 terphenyl plasticizer Zinc oxide 5.5 5.5 Dinitrosobenzene 20.0 20.0 Calcium carbonate 20.0 0 Carbon black 20.0 0 % TSC in water 41.8 410 8 The several adhesive compositions are employed to bond solyent-wiped~ grit-blasted, cold-rolled steel to - 14b -. _, . ,,_ , . ., . , . . . . .. , ... . . ,, .. , , . . .. _, . ... ... ~ . . .... .... .. .
~lG~
sulfur-vulcanizable natural rubber and poly(butadiene-styxene) xubber compositions. The steel parts are coated with either solvent-based heat-reactlve phenolic resin pri-mer or wa-ter-based novolak phenol.ic resin primer cornpositions prior to application oE the adhesive compositions. The natural rubber assemblies are cured at 153 C for 15 minutes, at no preheat and at preheat of 153 C Eor 6 minutes. The synthetic rubber assemblies are cured at 153 C fox 30 minutes at the same preheat conditions. Peel adhesion tests oE both natural and synthetic rubber compositions are eEfected according to ASTM D-429, Method B. modiEied to 45 C. The natural rubber assemblies are tested ~or boiling water resis-tance by immer-sion ~or two hours at 100 C. Test results are reported in the following table:
Boiling Water Resistance, Natural Rubber, Preheat: None Vinyl senzyl Chloride, Failure PrimerFormula Wt ~ Mode Solvent A 5 99 R
Solvent A 11 88 R
Solvent A 15 67 R
Solvent A 22 52 R ' Solvent B 5 99 R
Solvent B 11 94 R
Solvent B 15 59 R
Solvent B 22 98 R
~1 14c -Vinyl Benz~l Chloricle, ~rin:ler Formula Wt. ,~i Failure Mode Aqueous A 5 30 R
Aqueous A 11 47 R
Aqueous A . 15 33 R
Aqueous A 22 37 R
Aqueous B 5 40 R
Aqueous B 11 28 R
Aqueous B 15 35 R
Aqueous B 22 32 R
10 Peel Adhesion, Mo and 6 Minute Preheat~ Natural and Synthetic Rubber Preheat: None Vin~l Benzyl Chloride, Peel Adhesion PrimerElastorner Forrnula Wt. % kN/M Failure Mode SolventNatural A 5 8.6100 TR
SolventNatural A 11 6.57 VTR
SolventNatural A 15 ' 8.2100 TR
SolventNatural A 22 7.5100 VTR
Aqueous Natural A 5 9.350 VTR
Aqueous Natural A 11 8.699 TR
Aqueous Natural A 15 6.530 VTR
AqueousNatural A 22 6.538 VTR
SolventSynthetic A 5 25.7 78 R
Sol~Tent Synthetic A 11 26.9 99 R
SolventSynthetic A 15 20.6 23 R
SolventSynthetic A 22 21.4 24 R
AqueousS~mthetic A 5 16.8 41 R
AqueousSynthetic A 11 23.8 32 R
AqueousSynthetic A 15 19.7 42 R
AqueousSynthetic ,A 22 18.9 14 R
., Vin~l Benzyl Chloride, Peel Adnesion . ~imer Elastomer Formula.~,Vt. '~o kM/rnF~ilure I~/Iode Solvent Matural B 5 8. 4 77 TR
Solvent Natural B 11 7.0 73 VTR
Solvent Natural B 15 8. ô100 VTR
Solvent Natural B 22 7.2 77 ~TR
Aqueous Natural B 5 ~. 1 95 VTR
Aqueous Natural B 11 8.7 99 TR
Aqueous Natural B 15 7. 4 47 VTR
Aqueous Natural B 22 7. 0 23 VTR
Solvent Synthetic B 5 28. 1, SB 100 R
Solvent Synthetic B 11 28. 5 97 R
Solvent Synthetic B 15 27. 8, SB 100 R
Solvent Synthetic B 22 23. 6, SB 95 R
Aqueous Synthetic B 5 20. 6 34 R
Aqueous Synthetic B 11 19. 3 32 R
Aqueous Synthetic B 15 23.2 59 R
Aqueous Synthetic B 22 24.0, SB 60 R
Preheat: 6 Minutes at 153 C
- Vinyl Benzyl C'hloride, Peel Adhesion Primer Elastomer FormulaWt. % kN/mFailure Mode Solvent Natural A 5 6.7 100 RC
Solvent Natural A 11 5.0 100 RC
Solvent Natural A 15 4. 8 100 RC
Solvent Natural A 22 PBH 100 RC
Aqueous Natural A 5 3. 8 22 RC
Aqueous Natural A 11 4. 6 40 RC
Aqueous Natural A 15 4. 6 63 RC
Aqueous Natural A 22 4. 6 90 RC
. ~ Solvent Synthetic A 5 10. 5 100 RC
Solvent Synthetic A 11 12.7 100 RC
Solvent Synthetic A 15 9.8 100 RC
Solvent Synthetic A 22 11. 5 100 RC
. . ~
~i7J;9~
_r2hea~: 8 ~IIinutes at 153 C
Vinyl Benzyl Chlorid~, Peel Adhesion Primer Elastomer Formula~Nt. a'O __ kIii/mailur~ ~rode Aqueous Synthetic A 5 9. 3 13 RC
Aqueous Synthetic A 11 ~. 6 37 RC
Aqueous Synthetic A 13 9.1 42 RC
Aqueous Synthetic A 22 8. 9 20 RC
Solvent Natural B 5 7. 9 23 TR
Solvent Natural B 11 5.1 100 RC
Solvent Natural B 15 3. 9 100 RC
Solvent Natural B 22 PBH 100 RC
Aqueous Natural B 5 6. 2 5 VTR
Aqueous Natural B 11 7. 4 17 VTR
Aqueous Natural B 15 5.3 83 RC
Aqueous Natural B 22 5. 0 98 RC
Solvent Synthetic B 5 28. 0 98 R
Solvent Synthetic B 11 28.8 97 R
Solvent Synthetic B 15 2~. 5, SB 93 R
Solvent Synthetic B 22 24. 9 83 R
Aqueous Synthetic B 5 10.1 13 RC
Aqueous Synthetic B 11 15. 4 31 R
Aqueous Synthetic B 15 13. 2 43 R
Aqueous Synthetic B 22 15.4 5 R
EXAMPLE V
The halogenated conjugated diene-monoalkenyl aromatic alkyl halide copolymer latex of Example I is employed to prepare the following adhesives, with amounts being reported in parts by weight on a dry weight basis:
Adhesive V-A V-B V-C
Copolymer latex 100 100 100 Dibasic lead phosphate 20 20 20 Dinitrosobenzene 20 50 100 % TSC in water 41.841. 8 41.8 ..
~G7~"3~L
The adhesive compositions are employed to bond solvent-wiped, grit-blastedr cold-rolled stcel to sulfur-vulcanlzable natural and pol~-(butadiene-styrene) s~nthetic rubber compositions. The steel par-ts are coated with an a~ueous primer comprising non-heat-reactive phenolic resin and resin curative ~rior to appl:ication of the adhesives.
The adhesively-coated parts are subjected to preheat bake at times of 9, 12, and 15 minutes at 153 C before being con-tacted with the vulcanizable rubber compositions. The natllral 10rubber assemblIes are cured at 153 C fox 15 minutes, with the synthetic rubber assemblies being cured at 153 C for 30 minutes. The assemblies are tested according to ASTM D~
429, Method B.modified to 45C: The results are reported in the following table:
15_eheat esistance, Natural Rubber Preheat Peel Adhesion AdhesiveMinutes kN/mFailure Mode .....
V-A 9 9.4100 R
V-A 12 8.763 VTR
V-A 15 7.730 VTR
V-B 9 9.1100 R
V-B 12 8.998 R
V-B 15 8.2100 R
V-C 9 9.4100 R
V-C 12 8.980 R
V-C 15 9.1100 R
Preheat Resistance, Poly(Butadiene-St~rene) Rubber Preheat Peel Adhesion AhesiveMinutes kN/mFailure Mode V-A 9 21.475 R
V-A 12 10.,6100 RC
V-A 15 9.1100 RC
V-B ~ 24.9, SB100 R
V-B 12 22.6 96 R
.
~6~
Prehea-t Resist~nce, Poly(Butadiene-Styrenë) Rubber P~eheat Peel Adhesion ~dhesi~eMinutes kN~mFailure Mode V-B 15 24,589 R
V-C 9 24.0,SB100 R
V-C 12 21.4,SB95 R
V-C 15 24.0,SB100 R
EXAMPLE ~I
~ halogenated conjugated diene-monoalkenyl aroma-tic alkyl halide copolymer latex having a monoalkenyl aroma-tic aklyl halide content of 22 weight percent is prepared from 2,3-dichloro-1,3-butadiene and vinyl ben~yl chloride following the procedure of Example I. The latex is used to prepare the following adhesive, with all amounts being re-ported in parts by weight on a dry weight basis:Copolymer latex 100Dinitrosobenzene 18 TSC in water 43 The adhesive composition is employed to bond sol-vent-wiped, grit-blasted, cold-rolled steel to a variety,of sulfur-vulcanizable natural and synthetic rubber compositions.
The steel parts are coated with a solvent-based heat-reactive phenolic resin primer prior to application oE the adhesive.
The assemblies are cured at conventional conditions of the time, temperature and pressure for each elastomer stock.
After cure, the assemblies are tested for primary adhesion only according to the method of ASTM D-429, Method B, modi-fied to 45C.- The results are reported below.
Peel Adhesion Elastomer Type kN/mFailure Mode Natural 8.4 100 R
Neoprene 20.1 100 R
Ethylene-propylene-diene 17.3 92 R
terpolymer Poly(styrene-~utadiene) 26.4 98 R
Butyl 15.4 85 R
~, _ 19 _ ... . .... ....
Claims (27)
1. An elastomeric copolymer latex composition con-sisting essentially of a) on a dry weight basis, 100 parts by weight of elastomer latex consisting essentially of at least one emul-sion-polymerized copolymer of, (1) at least one halogenated conjugated diene and, (ii), at least one monoalkenyl aroma-tic alkyl halide; and b) on a dry weight basis, from 0.01 to 15 percent by weight of a surfactant system selected from the group con-sisting of anionic surfactant agents and a mixture of at least one anionic surfactant agent and at least one nonionic surfactant agent; the amount of said surfactant system being based on combined weight of said halogenated conjugated diene and said monoalkenyl aromatic alkyl halide comonomers, said copolymer having a monoalkenyl aromatic alkyl halide content in the range from 3 to 33 percent by weight, said copolymer latex having a total solids content in the range from 5 to 70 percent.
2. An elastomeric copolymer latex composition according to claim 1 wherein said monalkenyl aromatic alkyl halide monomers have the characteristic formula and wherein X is hydrogen, chlorine, bromine or iodine; R is an alkyl group having from 1 to 4 carbon atoms, and the carbon atom of said alkyl group which is attached directly to the aromatic nucleus being substituted with from 1 to 3 halogen atoms selected from the group consisting of chlorine, bromine or iodine; a is 1 or 2; b is 0, 1, or 2; and at least one b is at least 1.
3. An elastomeric copolymer latex according to claim 1 wherein said halogenated conjugated diene comprises 2,3-dichloro-l,3-butadiene.
4. An elastomeric copolymer latex according to claim 1 wherein said monoalkenyl aromatic halide comprises vinyl benzyl chloride.
5. An elastomeric copolymer latex according to claim 3 wherein said monoalkenyl aromatic alkyl halide comprises vinyl benzyl chloride.
6. An elastomeric copolymer latex according to claim 2 wherein said halogenated conjugated diene comprises 2,3-dichloro-1,3-butadiene.
7. An elastomeric copolymer latex according to claim 2 wherein said monoalkenyl aromatic alkyl halide com-prises vinyl benzyl chloride.
8. An elastomeric copolymer latex according to claim 1 having a pH in the range from 4 to 11.
9. An elastomeric copolymer latex according to claim 2 having a pH in the range from 4 to 11.
10. An elastomeric copolymer latex according to claim 5 having a pH in the range from 4 to 11.
11. An elastomeric copolymer latex according to claim 2 having a monoalkenyl aromatic alkyl halide content in the range from 3 to 25 percent by weight.
12. An elastomeric copolymer latex according to claim 5 having a monoalkenyl aromatic alkyl halide content in the range from 3 to 7 percent by weight.
13. A copolymer latex composition according to claim 1 having dispersed therein at least one part by weight, per 100 parts of copolymer solids, of at least one aromatic nitroso compound.
14. A copolymer latex composition according to claim 13 wherein the amount of said aromatic nitroso com-pound is in the range from 1 to 200 parts by weight.
15. A copolymer latex composition according to claim 14 wherein said monoalkenyl aromatic alkyl halide monomers have the characteristic formulae and wherein X is hydrogen, chlorine, bromine or iodine; R is an alkyl group having from 1 to 4 carbon atoms, the carbon atom of said alkyl group which is attached directly to the aromatic nucleus being substituted with from 1 to 3 halogen atoms selected from the group consisting of chlorine, bromine or iodine; a is 1 or 2; b is 0, 1, or 2; and at least one b, is at least 1.
16. An elastomeric copolymer latex composition accor-ding to claim 15 wherein said halogenated conjugated diene comprises 2,3-dichloro-1,3-butadiene.
17. An elastomeric copolymer latex composition according to claim 15 wherein said monoalkenyl aromatic alkyl halide comprises vinyl benzyl chloride.
13. An elastomeric copolymer latex according to claim 16 wherein said monoalkenyl aromatic alkyl halide comprises vinyl benzyl chloride.
19. An elastomeric copolymer latex according to claim 14 having a pH in the range from 4 to 11.
20. An elastomeric copolymer latex according to claim 15 having a pH in the range from 4 to 11.
21. An elastomeric copolymer latex according to claim 15 having a monoalkenyl aromatic halide content in the range from 3 to 25 percent by weight.
22. An elastomeric copolymer latex according to claim 21 having a pH in the range from 4 to 11.
23. An elastomeric copolymer latex according to claim 22 wherein said halogenated conjugated diene comprises 2,3-dichloro-1,3-butadiene.
24. An elastomeric copolymer latex according to claim 22 wherein said monoalkenyl aromatic alkyl halide comprises vinyl benzyl chloride.
25. An elastomeric copolymer latex according to claim 23 wherein said monoalkenyl aromatic alkyl halide com-prises vinyl benzyl chloride.
26. An elastomeric copolymer latex according to claim 18 having a monoalkenyl aromatic alkyl halide content in the range from 3 to 7 percent by weight.
27. An elastomeric copolymer latex according to claim 26 having a pH in the range from 4 to 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16375280A | 1980-06-27 | 1980-06-27 | |
| US163,752 | 1980-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1167191A true CA1167191A (en) | 1984-05-08 |
Family
ID=22591413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380682A Expired CA1167191A (en) | 1980-06-27 | 1981-06-26 | Water-based adhesive systems |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5794029A (en) |
| AU (1) | AU545027B2 (en) |
| CA (1) | CA1167191A (en) |
| DE (1) | DE3125286A1 (en) |
| FR (1) | FR2485557B1 (en) |
| GB (1) | GB2078238B (en) |
| IT (1) | IT1171344B (en) |
| SE (1) | SE8104000L (en) |
| ZA (1) | ZA814165B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4569961A (en) * | 1984-01-12 | 1986-02-11 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane lacquers containing nitroso-aromatics |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483962A (en) * | 1983-07-22 | 1984-11-20 | Lord Corporation | Aqueous adhesive systems |
| DE3400851A1 (en) * | 1984-01-12 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | AQUEOUS VOLCANIZATION ADHESIVE |
| ES2227510T3 (en) * | 1991-05-31 | 2005-04-01 | Lord Corporation | LATEX STABLE POLYMERS OF BUTADIEN. |
| CN103221469B (en) | 2010-07-09 | 2015-09-30 | 阿尔法克勒比施托夫股份公司 | Tackiness agent containing buffer system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2581920A (en) * | 1947-03-21 | 1952-01-08 | Firestone Tire & Rubber Co | Rubber to metal adhesive comprising dichlorobutadiene resin and a chlorinated elastomer and use thereof |
| US2914512A (en) * | 1956-08-27 | 1959-11-24 | Minnesota Mining & Mfg | Copolymer of a conjugated diene and bis-(tri-fluoromethyl) styrene and process for preparing a composition containing same |
| BE566327A (en) * | 1958-04-01 | 1958-10-01 | Lord Mfg Co | Adhesive composition, process of bonding rubber to metal using this composition and composite structures so produced |
-
1981
- 1981-06-19 ZA ZA814165A patent/ZA814165B/en unknown
- 1981-06-23 GB GB8119291A patent/GB2078238B/en not_active Expired
- 1981-06-26 FR FR8112625A patent/FR2485557B1/en not_active Expired
- 1981-06-26 SE SE8104000A patent/SE8104000L/en not_active Application Discontinuation
- 1981-06-26 CA CA000380682A patent/CA1167191A/en not_active Expired
- 1981-06-26 DE DE3125286A patent/DE3125286A1/en not_active Withdrawn
- 1981-06-26 AU AU72304/81A patent/AU545027B2/en not_active Ceased
- 1981-06-27 JP JP56100396A patent/JPS5794029A/en active Granted
- 1981-06-29 IT IT48787/81A patent/IT1171344B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4569961A (en) * | 1984-01-12 | 1986-02-11 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane lacquers containing nitroso-aromatics |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2078238B (en) | 1984-04-18 |
| IT8148787A0 (en) | 1981-06-29 |
| GB2078238A (en) | 1982-01-06 |
| FR2485557B1 (en) | 1985-08-16 |
| JPS625457B2 (en) | 1987-02-05 |
| DE3125286A1 (en) | 1982-04-15 |
| ZA814165B (en) | 1982-07-28 |
| SE8104000L (en) | 1981-12-28 |
| IT1171344B (en) | 1987-06-10 |
| JPS5794029A (en) | 1982-06-11 |
| FR2485557A1 (en) | 1981-12-31 |
| AU545027B2 (en) | 1985-06-27 |
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