CA2061021C - Acrylic adhesive composition and organoboron initiator system - Google Patents
Acrylic adhesive composition and organoboron initiator systemInfo
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- CA2061021C CA2061021C CA 2061021 CA2061021A CA2061021C CA 2061021 C CA2061021 C CA 2061021C CA 2061021 CA2061021 CA 2061021 CA 2061021 A CA2061021 A CA 2061021A CA 2061021 C CA2061021 C CA 2061021C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Abstract
A two-part initiator system useful in acrylic adhesive compositions comprising in one-part a stable organoboron amine complex and in the second part an organic acid destabilizer or activator. This initiator is particularly useful in elastomeric acrylic adhesive compositions and provides a fast, room temperature cure with good stability and exhibiting both high tensile strength and high peel strength.
Description
ACRYLIC ADHESIVE COMPOSITION AND
ORGANOBORON INITIATOR SYSTEM
BACKGROUND OF THE INVENTION
This invention relates to a novel organoboron complex initiator system and an acrylic a&esive composition containing this initiator. More particularly this invention involves a two-part initiator system co~ lising in one-part a stable organoboron amine complex and in the second part an organic acid destabilizer oractivator. This initiator system is especially useful in elastomeric acrylic adhesive compositions.
Adhesive compositions including acrylic adhesives such as solutions of elastomeric polymers in soluble polymerizable acrylic or methacrylic monomers are well known in the art. These cc,lllposilions which are especially known for their toughening properties generally include a redox system which comprises a catalyst or initiator, an accelerator and an activator to initiate cure, as well as other additives such as a&esion promoters, chelators, cross-linking agents, thickeners and plasticizers.
Two-part acrylic a&esives where an activator is added as a separate second component are widely used and are known for curing speed as well as toughness. The catalyst or initiator typically used in these adhesives are free-radical initiators of the organic peroxy or hydroperoxy type, perester or peracid type.
Many known adhesive systems, such as the epoxies, require a thermal cure to obtain desirable properties, while others that do not, usually require prolonged cure times. In comparison, the adhesive composition with organoboron amine complex initiator of this invention cures at room temperature and reaches high tensile strength in a short period of time. Additionally, the adhesive composition of this invention has shown exceptional stability on ageing while exl~ lg both hightensile strength and high peel strength.
SUMMARY OF THE INVENTION
This invention involves a novel two-part organoboron amine complex ini~ ing system useful in elastomeric acrylic adhesives compositions to provide better and faster room temperature curing thereof.
The organoboron inhi~ting system of this invention is a two-part system 1 5 COI~ illg:
A) a stabilized organoboron amine complex of the forrnula:
R ~ 3 R~ - B ~ N - H (I) where R, R, and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or )n where R5 and R6are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6, and B) an organic acid activator having the formula:
R - COOH
where R is hydrogen, alkyl or alkenyl of 1 to 8 carbon atoms, or aryl having 6 to 10 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The stabilized organoboron amine complex of the structure (I) which comprises one part of the initiator of this invention is made by combining an organoboron compound with a primary or secondary amine or polyamine containing primary or secondary amines. The organoboron colllpoulld has the formula:
'R2 where R, R, and R2 are alkyl of 1 to 10 carbon atoms or phenyl, perferably alkyl of 1 to 4 carbons. In this formula, the alkyl groups may be straight or branch chained and the phenyl group may contain subsSit~ent~ such as alkyl, alkoxy or halogen.
Illustrative compounds of this type include, e.g., trimethylboron, triethylboron, tri-n-butylboron, tri-sec-butylboron and tri-isobutylboron.
The amine which is used in forming the organoboron amine complex (I) may be any primary or secondary amine or polyamine containing a primary or secondary amine, or ammonia and having the following formula:
N --~4 where R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or ~C~2~ ~ ) R6 or ~CH2~n ~ _ where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atorns, m is 2 to 10, and n is 1 to 6. The alkyl groups in this formula may be straight or branch chained.
Preferably, the R groups noted in the amine will be hydrogen or alkyl of 1 to 4 carbon atoms, m will be 2 to 6 and more preferably 2 to 3 and n will be 1 to 2. Illustrative compounds of this type include, e.g., n-octylamine, 1 ,6-diaminohexane, diethylamine, dibutylamine, diethylene triamine, dipropylene diamine, ammonia, 1,3-propylenediamine and 1 ,2-propylenediamine.
The stabilized amine complex can be prepared by combining a solution of the organoboron with the amine under an inert atmosphere with cooling as needed.
The activator used as the second part or component of the initiator system will be a compound which will destabilize or liberate the free organoboron compound by removing the amine group and thereby allow it to initiate the polymerization process.
S This activator is an organic acid having the formula:
R-COOH
where R is H, alkyl of alkenyl of 1 to 8 and preferably 1 to 4 carbon atoms, or aryl of 6 to 10, preferably 6 to 8 carbon atoms. It is further understood that the alkyl or alkenyl group of this organic acid may be straight or branch chained and the aryl may contain substituents such as alkyl, alkoxy or halogen. Illustrative examples of compounds of this type include: acrylic acid, methacrylic acid, benzoic acid, and p-methoxybenzoic acid.
Generally the initiator system of this invention will comprise the organoboron amine complex and an effective destabilizing amount of the organic acid activator.
More particularly from about 0.1:1 to 200:1 parts by weight of acid to amine complex and preferably from about 1:1 to 24:1 parts by weight of acid to amine complex may be used.
The organoboron initiator of this invention is particularly useful in acrylic adhesive compositions and especially solutions of elastomeric or rubber polymers in compatible polymerizable acrylic monomers.
The polymerizable acrylic monomer may be monofunctional, polyfunctional or a combination thereof.
One class of poly~ i~ble monomers useful in the present compositions correspond to the general formula:
o ~R\ R O
H2C=C--C--O ~ C8 ~ C 1-0 C--C=C~2 R~ R / P n R-wherein R is selected from the group consi~ g of hydrogen methyl, ethyl, _C~2O~ and -C82-o-c-f=cH2;
R' R' is selected from the group consisting of hydrogen, chlorine, methyl and ethyl;
R" is selected from the group consisting of hydrogen, hydroxy, and o - o - C - Cl =CH2;
R' m is an integer equal to at least 1, e.g., from 1 to 8 or higher and preferably from 1 to 4 inclusive;
n is an integer equal to at least 1, e.g., from 1 to 20 or more; and p is one of the following: 0 or 1.
Monomers useful in this invention and which come within the above general formula include, for example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol ~iim~th~crylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trim~th~crylate, and other polyther diacrylates and dimethacrylates .
The above class of monomers is in essence described in U.S. Pat. No.
3,043,820 issued July 10, 1962 (to R. H. Krieble).
A second class of polymerizable monomers useful in the present compositions correspond to the general formula:
R R
H2C=C cl=cH2 I-O ( R -O~ Cl-R -ICl ( O-R t O-ICl O O O O
wherein R leplesell~ hydrogen, chlorine, methyl or ethyl; R' le~l~s~n~ alkylene with 2-6 carbon atoms; and, R" lepresell~ (CH2)m in which m is an integer of from 0 to 8, or ~ H H C=C
\ / CH3 C=C or C=C , and n represents an integer of from 1 to 4.
Typical monomers of this class include, for example, dimethacrylate of bis(ethylene glycol) adipate, dimethacrylate of bis(ethylene glycol) maleate, S dimethacrylate of bis(diethylene glycol) phthalate, flimPth~crylate of bis(tetraethylene glycol) phthalate, dimethacrylate of bis(tetraethylene glycol) sebacate, dimethacrylates of bis(tetraethylene glycol) maleate, and the diacrylates and chloroacrylates corresponding to said dimethacrylates, and the like.
The above class of monomers is in essence describes in U.S Pat. No. 3,457,212 issued July 22, 1969 (Sumitomo Chemical Company, L,td.).
Also useful herein are monomers which are isocyanate-hydroxyacrylate or isocyante-aminoacrylate reaction products which may be characterized as acrylateterminated polyurethanes and polyureides or polyureas. These monomers correspondto the general formula:
- o D
A-X-C-NH n B
wherein X is selected from the group consisting of -O- and R
- N -, and R is a member selected from the group consisting of hydrogen and lower alkyl of 1 to 7 carbon atoms; A lepl~se~ the organic residue of an active hydrogen containing acrylic ester wherein the active hydrogen has been removed, the ester being hydroxy or amino ~ub~liluled on the alkyl portion thereof and the methyl, ethyl and chlorine homologs thereof; n is an integer from 1 to 6 inclusive; and B is a mono- or polyvalent organic radical selected from the group consisting of alkyl, alkylene, alkenyl, cycloalkyl, cycloalkylene, aryl, aralkyl, alkaryl, poly(oxyalkylene), poly(carboalkoxyalkylene), and heterocyclic radicals both substituted and unsubstituted.
Typical monomers of this class include the reaction product of mono- or polyisocyanate, for example, toluene diisocyanate, with an acrylate ester containing a hydroxy or amino group in the non-acrylate portion thereof, for example, hydroxyethyl methacrylate.
The above class of monomers is in essence described in U.S. Pat. No.
ORGANOBORON INITIATOR SYSTEM
BACKGROUND OF THE INVENTION
This invention relates to a novel organoboron complex initiator system and an acrylic a&esive composition containing this initiator. More particularly this invention involves a two-part initiator system co~ lising in one-part a stable organoboron amine complex and in the second part an organic acid destabilizer oractivator. This initiator system is especially useful in elastomeric acrylic adhesive compositions.
Adhesive compositions including acrylic adhesives such as solutions of elastomeric polymers in soluble polymerizable acrylic or methacrylic monomers are well known in the art. These cc,lllposilions which are especially known for their toughening properties generally include a redox system which comprises a catalyst or initiator, an accelerator and an activator to initiate cure, as well as other additives such as a&esion promoters, chelators, cross-linking agents, thickeners and plasticizers.
Two-part acrylic a&esives where an activator is added as a separate second component are widely used and are known for curing speed as well as toughness. The catalyst or initiator typically used in these adhesives are free-radical initiators of the organic peroxy or hydroperoxy type, perester or peracid type.
Many known adhesive systems, such as the epoxies, require a thermal cure to obtain desirable properties, while others that do not, usually require prolonged cure times. In comparison, the adhesive composition with organoboron amine complex initiator of this invention cures at room temperature and reaches high tensile strength in a short period of time. Additionally, the adhesive composition of this invention has shown exceptional stability on ageing while exl~ lg both hightensile strength and high peel strength.
SUMMARY OF THE INVENTION
This invention involves a novel two-part organoboron amine complex ini~ ing system useful in elastomeric acrylic adhesives compositions to provide better and faster room temperature curing thereof.
The organoboron inhi~ting system of this invention is a two-part system 1 5 COI~ illg:
A) a stabilized organoboron amine complex of the forrnula:
R ~ 3 R~ - B ~ N - H (I) where R, R, and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or )n where R5 and R6are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6, and B) an organic acid activator having the formula:
R - COOH
where R is hydrogen, alkyl or alkenyl of 1 to 8 carbon atoms, or aryl having 6 to 10 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The stabilized organoboron amine complex of the structure (I) which comprises one part of the initiator of this invention is made by combining an organoboron compound with a primary or secondary amine or polyamine containing primary or secondary amines. The organoboron colllpoulld has the formula:
'R2 where R, R, and R2 are alkyl of 1 to 10 carbon atoms or phenyl, perferably alkyl of 1 to 4 carbons. In this formula, the alkyl groups may be straight or branch chained and the phenyl group may contain subsSit~ent~ such as alkyl, alkoxy or halogen.
Illustrative compounds of this type include, e.g., trimethylboron, triethylboron, tri-n-butylboron, tri-sec-butylboron and tri-isobutylboron.
The amine which is used in forming the organoboron amine complex (I) may be any primary or secondary amine or polyamine containing a primary or secondary amine, or ammonia and having the following formula:
N --~4 where R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or ~C~2~ ~ ) R6 or ~CH2~n ~ _ where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atorns, m is 2 to 10, and n is 1 to 6. The alkyl groups in this formula may be straight or branch chained.
Preferably, the R groups noted in the amine will be hydrogen or alkyl of 1 to 4 carbon atoms, m will be 2 to 6 and more preferably 2 to 3 and n will be 1 to 2. Illustrative compounds of this type include, e.g., n-octylamine, 1 ,6-diaminohexane, diethylamine, dibutylamine, diethylene triamine, dipropylene diamine, ammonia, 1,3-propylenediamine and 1 ,2-propylenediamine.
The stabilized amine complex can be prepared by combining a solution of the organoboron with the amine under an inert atmosphere with cooling as needed.
The activator used as the second part or component of the initiator system will be a compound which will destabilize or liberate the free organoboron compound by removing the amine group and thereby allow it to initiate the polymerization process.
S This activator is an organic acid having the formula:
R-COOH
where R is H, alkyl of alkenyl of 1 to 8 and preferably 1 to 4 carbon atoms, or aryl of 6 to 10, preferably 6 to 8 carbon atoms. It is further understood that the alkyl or alkenyl group of this organic acid may be straight or branch chained and the aryl may contain substituents such as alkyl, alkoxy or halogen. Illustrative examples of compounds of this type include: acrylic acid, methacrylic acid, benzoic acid, and p-methoxybenzoic acid.
Generally the initiator system of this invention will comprise the organoboron amine complex and an effective destabilizing amount of the organic acid activator.
More particularly from about 0.1:1 to 200:1 parts by weight of acid to amine complex and preferably from about 1:1 to 24:1 parts by weight of acid to amine complex may be used.
The organoboron initiator of this invention is particularly useful in acrylic adhesive compositions and especially solutions of elastomeric or rubber polymers in compatible polymerizable acrylic monomers.
The polymerizable acrylic monomer may be monofunctional, polyfunctional or a combination thereof.
One class of poly~ i~ble monomers useful in the present compositions correspond to the general formula:
o ~R\ R O
H2C=C--C--O ~ C8 ~ C 1-0 C--C=C~2 R~ R / P n R-wherein R is selected from the group consi~ g of hydrogen methyl, ethyl, _C~2O~ and -C82-o-c-f=cH2;
R' R' is selected from the group consisting of hydrogen, chlorine, methyl and ethyl;
R" is selected from the group consisting of hydrogen, hydroxy, and o - o - C - Cl =CH2;
R' m is an integer equal to at least 1, e.g., from 1 to 8 or higher and preferably from 1 to 4 inclusive;
n is an integer equal to at least 1, e.g., from 1 to 20 or more; and p is one of the following: 0 or 1.
Monomers useful in this invention and which come within the above general formula include, for example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol ~iim~th~crylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trim~th~crylate, and other polyther diacrylates and dimethacrylates .
The above class of monomers is in essence described in U.S. Pat. No.
3,043,820 issued July 10, 1962 (to R. H. Krieble).
A second class of polymerizable monomers useful in the present compositions correspond to the general formula:
R R
H2C=C cl=cH2 I-O ( R -O~ Cl-R -ICl ( O-R t O-ICl O O O O
wherein R leplesell~ hydrogen, chlorine, methyl or ethyl; R' le~l~s~n~ alkylene with 2-6 carbon atoms; and, R" lepresell~ (CH2)m in which m is an integer of from 0 to 8, or ~ H H C=C
\ / CH3 C=C or C=C , and n represents an integer of from 1 to 4.
Typical monomers of this class include, for example, dimethacrylate of bis(ethylene glycol) adipate, dimethacrylate of bis(ethylene glycol) maleate, S dimethacrylate of bis(diethylene glycol) phthalate, flimPth~crylate of bis(tetraethylene glycol) phthalate, dimethacrylate of bis(tetraethylene glycol) sebacate, dimethacrylates of bis(tetraethylene glycol) maleate, and the diacrylates and chloroacrylates corresponding to said dimethacrylates, and the like.
The above class of monomers is in essence describes in U.S Pat. No. 3,457,212 issued July 22, 1969 (Sumitomo Chemical Company, L,td.).
Also useful herein are monomers which are isocyanate-hydroxyacrylate or isocyante-aminoacrylate reaction products which may be characterized as acrylateterminated polyurethanes and polyureides or polyureas. These monomers correspondto the general formula:
- o D
A-X-C-NH n B
wherein X is selected from the group consisting of -O- and R
- N -, and R is a member selected from the group consisting of hydrogen and lower alkyl of 1 to 7 carbon atoms; A lepl~se~ the organic residue of an active hydrogen containing acrylic ester wherein the active hydrogen has been removed, the ester being hydroxy or amino ~ub~liluled on the alkyl portion thereof and the methyl, ethyl and chlorine homologs thereof; n is an integer from 1 to 6 inclusive; and B is a mono- or polyvalent organic radical selected from the group consisting of alkyl, alkylene, alkenyl, cycloalkyl, cycloalkylene, aryl, aralkyl, alkaryl, poly(oxyalkylene), poly(carboalkoxyalkylene), and heterocyclic radicals both substituted and unsubstituted.
Typical monomers of this class include the reaction product of mono- or polyisocyanate, for example, toluene diisocyanate, with an acrylate ester containing a hydroxy or amino group in the non-acrylate portion thereof, for example, hydroxyethyl methacrylate.
The above class of monomers is in essence described in U.S. Pat. No.
3,425,988 issued February 4, 1969 (Loctite Corporation).
Another class of monomers useful in the present application are the mono- and polyacrylate and methacrylate esters of bisphenol type compounds. These monomersmay be described by formula:
CHz-C - C-(o-C-C8z~nO ~ I ~ ~ O-(C8z ~C O~C C CHz where R' is methyl, ethyl, carboxyalkyl or hydrogen; R2 is hydrogen, methyl or ethyl;
R3 is hydrogen, methyl or hydroxyl; R4 is hydrogen, chlorine, methyl or ethyl; and n is an integer having a value of 0 to 8.
Representative monomers of the above-described class include: ~limPth~crylate and diacrylate esters of 4,4'-bis-hydroxyethoxy-bisphenol A; tlimf~th~cyylate and diacrylate esters of bisphenol A; etc. These monomers are es~e.nti~lly described in Japanese Patent Publication No. 70-15640 (to Toho Chemical Manuf. Ltd.).
In addition to the monomers already described, other useful monomers are monofuntional acrylate and methacrylate esters and the sl~bstitllt~d derivatives thereof such as hydroxy, amide, cyano, chloro, and silane derivitives. Such monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isoboronyl methacrylate, hydroxyethyl methacrylate, hydro~yl,lupyl acrylate, hydro~ylJIu~,yl methacrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decylmethacrylate, dodecyl methacrylate, cyclohexyl methacrylate, tert-butyl methacrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N-tert-butyl acrylamide, N-tert-octyl acrylamide, N-butoxyacrylamide, g~mm~ methacrylo~y~ro~yl trimethoxysilane, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate, tetrahydrofurfuryl methacrylate, tetrahydlorulrulyl chloroacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.
The monomers useful herein are seen to be polymerizable monomers having one or more acrylic or substituted acrylic groups as a common, unifying characteristic, and for convenience may be generically termed acrylic monomers.
The elastomer or rubber polymers may be any of the typically available syntheticrubbers that are soluble in the monomer such as those based on polyisoprenes, polybutadienes, polyolefins, polyurethane, polyesters, etc. Examples of elastomeric materials include homopolymers such as polybutadiene, polyisoprene and polyisobutylene; diene type copolymers such as butadiene/styrene copolymer, butadiene/acrylonitrile copolymer, butadiene/methyl methacrylate copolymer and butadiene/alkyl acrylate copolymer; ethylene/vinyl acetate copolymers; ethylene/alkyl acrylate copolymers (1-8 carbons in the alkyl group), rubbery polyalkyl acrylates or copolymers thereof; polyulclhane; chlorinated polyethylenes; and EPDM
(ethylene/propylene/diene terpolymers).
The elastomers of these structures may contain a functional group at one or bothends or within a particular segment or repeating unit of the copolymer. Among the suitable functional groups are vinyl, epoxy, carboxyalkyl, and mercapto groups. Other functional groups may be employed as deemed useful as determined by routine experimentation.
One preferred group of elastomers are the block copolymers. Several such block copolymers are m~mlf~rtllred by Shell Chemical Company under the tradename Kraton*
and by Firestone under the tradename Stereon*. In particular, Stereon 840A, a poly(styrene-b-but~ çn~-b-styrene) block copolymer, has been found to be especially useful in the instant adhesive composition. Other plefelled block copolymers of this type are available under the tradename Solprene* 416, m~mlf~rhlred by Phillips Petroleum Co.
The monomer solution containing the elastomer or rubbery polymer is commonly prepared by dissolving the elastomer in the monomer, which may be in the form of a syrup. In some cases, the monomer solution may be prepared by extracting a rubbery polymer from a latex of the rubbery polymer in water, as used for suspension polymerization, and then dissolving in the monomer.
The amount of the acrylic monomer to be used in this invention may vary somewhat depending on the specific properties desired but generally about 10 to 90% by weight of the composition and preferably about 15 to 80% by weight is used.
Adjustment within these ranges are easily made within the skill of the art. The elastomer is generally present in amounts of about 5 to 80% by weight and preferably about 20 to 60% by weight of the composition.
3 5 *trade-mark The second part of the initiator which contains the acid activator, preferably may also contain a peroxy or hydlopeloxy component having the formula:
R-OOH
where R is hydrogen, alkyl of 1 to 10 preferably 4 to 10 carbon atoms or aryl or alkaryl of 6 to 14, preferably 6 to 10 carbon atoms. Illustrative compounds of this type are t-butyl hydroperoxide and cumene hydroperoxide. Typically these hydroperoxy compounds which aid in the initiation of polymerization are used in the initiator system in amounts of about 0.2:1 to 100:1 and preferably from about 0.4:1 to 20:1 parts by weight of hydroperoxy to amine complex.
The organoboron amine complex used in an adhesive composition in accordance with this invention generally comprises from about 0.1 to S % by weight of the total composition and preferably from about 0.5 to 2.5 % and the organic acid activator '~
comprises from about 0.5 to 20%, preferably from about 1 to 12% by weight of the total composition. When a hydroperoxy compound is used in the a&esive composition, it generally co~ ises from about 0.2 to 10% by weight of the total composition and preferably from about 0.5 to 2%.
Other additives useful in elastomeric acrylic adhesives of this type, such as adhesion promoters, chelators, cross-linking agents, inhibitors, activators such as N,N-dimethyltoluidine as well as thickeners, plasticizers and diluents may also be used in the adhesive compositions of this invention.
The organoboron initiator system as described above comprises a two component system. When used in the acrylic rubber compositions of this invention generally the two parts are mixed in equal quantities of the monomer-polymer solution, but this may vary at the discretion of the user. That is, the stabilized organoboron compound is added to a solution of the elastomer or rubber polymer dissolved in the polymerizable acrylic monomer and the organo acid activator and optional hydroperoxy compound are added as a second part which also may be in a solution of the rubber polymer in acrylic monomer.
Adhesive compositions of this invention are particularly useful in structural and semi-structural applications such as speaker magnets, metal-metal bonding (automotive) glass-metal bonding, glass-glass bonding, circuit board component bonding, selected CA 0206l02l l998-06-l9 plastic to metal, glass, wood, etc. and electric motor m~nPt~.
In the following examples, which are merely illustrative of the embodiments of this invention, all parts and percentages are given by weight and all lelllpel~lules are in degrees Celsius unless otherwise noted.
EXAMPLE I
Preparation of Or~anoboron Amine Complexes Into a 3-neck flask cont~inin~ a stirrer, condenser, thermometer and a nitrogen purge, 11.1 g (0.15 m, 50% excess) of 1,3-propylene diamine was added and the nitrogen purge continued while 100 ml of 1 molar solution (0. lm) of tributylboron in tetrahydrofuran was further added. A mild exotherm developed and the temperature was kept below about 40~C by cooling as necessary. When the addition was complete, the mixture was stirred for about 0.5 hour and transferred to a bottle previously flushed with nitrogen. This amine complex is i~1entifi~d below as initiator XII as well as other amine complexes prepared in a similar manner using the amines and amounts indicated.
AMINE AMOUNT lNl~lATOR NO.
ethylene diamine 6.0 g (O.lOm) ethylene dlamine 9.O g (0.15 m) II
ethylene dlamine 12.0 g (0.20 m~ III
1,2-propylene diamine 11.1 g (0.15 m) IV
n-octylamine 19.4 g (0.15 m) V
1,6-diaminohexane 17.4 g (O.lS m) VI
diethylenetriamine 10.3 g (O.lO m) VII
1,3-propylene diamine~ . 7.4 g (O.lO m) VIII
Another class of monomers useful in the present application are the mono- and polyacrylate and methacrylate esters of bisphenol type compounds. These monomersmay be described by formula:
CHz-C - C-(o-C-C8z~nO ~ I ~ ~ O-(C8z ~C O~C C CHz where R' is methyl, ethyl, carboxyalkyl or hydrogen; R2 is hydrogen, methyl or ethyl;
R3 is hydrogen, methyl or hydroxyl; R4 is hydrogen, chlorine, methyl or ethyl; and n is an integer having a value of 0 to 8.
Representative monomers of the above-described class include: ~limPth~crylate and diacrylate esters of 4,4'-bis-hydroxyethoxy-bisphenol A; tlimf~th~cyylate and diacrylate esters of bisphenol A; etc. These monomers are es~e.nti~lly described in Japanese Patent Publication No. 70-15640 (to Toho Chemical Manuf. Ltd.).
In addition to the monomers already described, other useful monomers are monofuntional acrylate and methacrylate esters and the sl~bstitllt~d derivatives thereof such as hydroxy, amide, cyano, chloro, and silane derivitives. Such monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isoboronyl methacrylate, hydroxyethyl methacrylate, hydro~yl,lupyl acrylate, hydro~ylJIu~,yl methacrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decylmethacrylate, dodecyl methacrylate, cyclohexyl methacrylate, tert-butyl methacrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N-tert-butyl acrylamide, N-tert-octyl acrylamide, N-butoxyacrylamide, g~mm~ methacrylo~y~ro~yl trimethoxysilane, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate, tetrahydrofurfuryl methacrylate, tetrahydlorulrulyl chloroacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.
The monomers useful herein are seen to be polymerizable monomers having one or more acrylic or substituted acrylic groups as a common, unifying characteristic, and for convenience may be generically termed acrylic monomers.
The elastomer or rubber polymers may be any of the typically available syntheticrubbers that are soluble in the monomer such as those based on polyisoprenes, polybutadienes, polyolefins, polyurethane, polyesters, etc. Examples of elastomeric materials include homopolymers such as polybutadiene, polyisoprene and polyisobutylene; diene type copolymers such as butadiene/styrene copolymer, butadiene/acrylonitrile copolymer, butadiene/methyl methacrylate copolymer and butadiene/alkyl acrylate copolymer; ethylene/vinyl acetate copolymers; ethylene/alkyl acrylate copolymers (1-8 carbons in the alkyl group), rubbery polyalkyl acrylates or copolymers thereof; polyulclhane; chlorinated polyethylenes; and EPDM
(ethylene/propylene/diene terpolymers).
The elastomers of these structures may contain a functional group at one or bothends or within a particular segment or repeating unit of the copolymer. Among the suitable functional groups are vinyl, epoxy, carboxyalkyl, and mercapto groups. Other functional groups may be employed as deemed useful as determined by routine experimentation.
One preferred group of elastomers are the block copolymers. Several such block copolymers are m~mlf~rtllred by Shell Chemical Company under the tradename Kraton*
and by Firestone under the tradename Stereon*. In particular, Stereon 840A, a poly(styrene-b-but~ çn~-b-styrene) block copolymer, has been found to be especially useful in the instant adhesive composition. Other plefelled block copolymers of this type are available under the tradename Solprene* 416, m~mlf~rhlred by Phillips Petroleum Co.
The monomer solution containing the elastomer or rubbery polymer is commonly prepared by dissolving the elastomer in the monomer, which may be in the form of a syrup. In some cases, the monomer solution may be prepared by extracting a rubbery polymer from a latex of the rubbery polymer in water, as used for suspension polymerization, and then dissolving in the monomer.
The amount of the acrylic monomer to be used in this invention may vary somewhat depending on the specific properties desired but generally about 10 to 90% by weight of the composition and preferably about 15 to 80% by weight is used.
Adjustment within these ranges are easily made within the skill of the art. The elastomer is generally present in amounts of about 5 to 80% by weight and preferably about 20 to 60% by weight of the composition.
3 5 *trade-mark The second part of the initiator which contains the acid activator, preferably may also contain a peroxy or hydlopeloxy component having the formula:
R-OOH
where R is hydrogen, alkyl of 1 to 10 preferably 4 to 10 carbon atoms or aryl or alkaryl of 6 to 14, preferably 6 to 10 carbon atoms. Illustrative compounds of this type are t-butyl hydroperoxide and cumene hydroperoxide. Typically these hydroperoxy compounds which aid in the initiation of polymerization are used in the initiator system in amounts of about 0.2:1 to 100:1 and preferably from about 0.4:1 to 20:1 parts by weight of hydroperoxy to amine complex.
The organoboron amine complex used in an adhesive composition in accordance with this invention generally comprises from about 0.1 to S % by weight of the total composition and preferably from about 0.5 to 2.5 % and the organic acid activator '~
comprises from about 0.5 to 20%, preferably from about 1 to 12% by weight of the total composition. When a hydroperoxy compound is used in the a&esive composition, it generally co~ ises from about 0.2 to 10% by weight of the total composition and preferably from about 0.5 to 2%.
Other additives useful in elastomeric acrylic adhesives of this type, such as adhesion promoters, chelators, cross-linking agents, inhibitors, activators such as N,N-dimethyltoluidine as well as thickeners, plasticizers and diluents may also be used in the adhesive compositions of this invention.
The organoboron initiator system as described above comprises a two component system. When used in the acrylic rubber compositions of this invention generally the two parts are mixed in equal quantities of the monomer-polymer solution, but this may vary at the discretion of the user. That is, the stabilized organoboron compound is added to a solution of the elastomer or rubber polymer dissolved in the polymerizable acrylic monomer and the organo acid activator and optional hydroperoxy compound are added as a second part which also may be in a solution of the rubber polymer in acrylic monomer.
Adhesive compositions of this invention are particularly useful in structural and semi-structural applications such as speaker magnets, metal-metal bonding (automotive) glass-metal bonding, glass-glass bonding, circuit board component bonding, selected CA 0206l02l l998-06-l9 plastic to metal, glass, wood, etc. and electric motor m~nPt~.
In the following examples, which are merely illustrative of the embodiments of this invention, all parts and percentages are given by weight and all lelllpel~lules are in degrees Celsius unless otherwise noted.
EXAMPLE I
Preparation of Or~anoboron Amine Complexes Into a 3-neck flask cont~inin~ a stirrer, condenser, thermometer and a nitrogen purge, 11.1 g (0.15 m, 50% excess) of 1,3-propylene diamine was added and the nitrogen purge continued while 100 ml of 1 molar solution (0. lm) of tributylboron in tetrahydrofuran was further added. A mild exotherm developed and the temperature was kept below about 40~C by cooling as necessary. When the addition was complete, the mixture was stirred for about 0.5 hour and transferred to a bottle previously flushed with nitrogen. This amine complex is i~1entifi~d below as initiator XII as well as other amine complexes prepared in a similar manner using the amines and amounts indicated.
AMINE AMOUNT lNl~lATOR NO.
ethylene diamine 6.0 g (O.lOm) ethylene dlamine 9.O g (0.15 m) II
ethylene dlamine 12.0 g (0.20 m~ III
1,2-propylene diamine 11.1 g (0.15 m) IV
n-octylamine 19.4 g (0.15 m) V
1,6-diaminohexane 17.4 g (O.lS m) VI
diethylenetriamine 10.3 g (O.lO m) VII
1,3-propylene diamine~ . 7.4 g (O.lO m) VIII
4-aminomethylpyridine 10.8 g (O.lO m~ IX
3-aminomethylpyridine 10.8 g (O.lO m) X
diethylamine lO 9S g (O.lS m) XI
1,3-propylene diamine 11.1 g (O lS m) XII
1 molar solution of triethylboron in tetrahydrofuran used CA 02061021 1998-06-l9 EXAMPLE II
Preparation of Adhesive Composition An adhesive formulation was prepared consisting of two parts that were mixed just prior to use. The first part contained the monomer-polymer syrup and the stabilized organoboron amine complex initiator from Example I. The second part contained a similar monomer-polymer syrup and an acid activator or reagent that destabilized the organoboron amine complex liberating the free organoboron. When mixed with the first part polymerization was initi~tefl The two adhesive composition parts were:
Part I
Stereon 840A (styrene-butadiene block copolymer) 30 parts Isobornyl methacrylate 70 parts Organoboron amine initiator No. 12l 4 parts Part II
Stereon 840A 30 parts Isobornyl methacrylate 61 parts Methacrylic acid 5 parts Cumene hydroperoxide (CHP) 4 parts Approximately equal portions of Parts I and II were mixed and applied to steel plates and allowed to cure. Tensile shear strength measurement on the adhesive bond was made according to the ASTM standard method D1002-72(1973) and found to be 2000 pSi.
Additional adhesive formulations were prepared in a similar manner using the components as identified below along with the resulting tensile strength determined is described above for the formed adhesive bond.
1 molar solution in tetrahydrofuran RUBBER (%) INITIATOR ~ ACID1 % CHP2 BOND T~NSILE
(~) STR~NGT~ PSI
Stereon 840a (20) XII (O S) 10 0.1 1875 Stereon 840a (253 VIII (O S) 1 1 1550 ~raton 1107 (20)3 II (O.S) 10 1 1850 Kraton 1107 (20~ II (0.25) 10 1 1350 ~raton 1107 (20) II (l.G) 10 1 2100 Hycar 4051 (10)4 IV (0.5) 10 1 - 1200 ~raton 1122 (25)5 VI (0 5) 1 1 1500 stereon 840~ (20) I (O.S) 0.5 1.7 lS00 al~o contain~ 13~ octyl acrylate Stereon 840A (30) ¦ VIII (0.5) ¦ 10 ¦ 1 ¦ 2700 monomer wa~ tetrahydrofur~uryl methacrylate 1. methacrylic acid 2. cumene hydroperoxide 3. styrene-isoprene 4. polyacrylic rubber polymer 5. styrene-isoprene EXAMPLE III
Similar adhesives formulations were prepared as in Example II using an amine complex of 1,3 propylene diamine and triethyl boron as the initiator (initiator No. Vm).
The formulations contained two-parts as in Example II that were mixed just prior to use and had the following compositions:
3 5 * trade-mark .
S Part I
Sample No. In;tiator Rubber1 MonomerA Monomer B MonomerC
3A-I 2 parts 25 pans 60 parts 15 pans (iBOMA) (OMA) 3B-I 2 pans 2~ pans 60 parts 15 pans (iBOMA) (OMA) 3~I 2 pans 25 pans 60 parts 15 pans (IBOMA) (ODA) 3D-I 2 pans 25 pans 60 parns 15 pans (IBOMA) (I iDDA) 3E-I . 2 pans 25 pans 60 pans 15 pans (iBOMA) (HDDMA) 3F-I 2 pans 30 parts -- -- 70 parts (THf ~MA) 3G-I 2 pans 30 pans -- -- 70 parts - (THFMA) 3H-I 2 parls 30 pans -- -- 70 pans (THFMA) 3I-I 2 pans 30 pans -- -- 70 pans - (THFMA) 3J-I 2 parts 30 parts 55 pans -- 15 pans (IBOMA) (HPMA) , Part II
Sample NQ Rubber1 MonomerA Monomer B Acld CHP
3A-ll 25 parts 50 pans 15 pans 10 parts (T:HFMA) (OMA) (MAA) 3~-ll . 25 parts 50 par~s 15 parts 10 parts (IBOMA) (OMA) (MM) 3~ll 2~ pans 50 pans 15 pans 10 parts (THFMA) (ODA) (MM) 3D~I 25 parts 50 parts 15 pans 10 parts ~ ( rHFMA) (HDDA) (MAA) 3E-Il 25 parts 50 pans 15 parts 10 parts l S (THFMA) (HDDMA) (MM) 3F-ll 30 pans 60 pans -- 10 pans 0.12,5 pans (THFMA) (MM) 3G-Il 30 pans 60 pans -- 10 par~s 0.250 pans (THFMA) (MM) 3H-Il 30 pans 60 pans -- 10 pans 0.5 pans THFMA) (MM) 31-ll 30 parts 60 par~s -- 10 pans 1 pan (THFMA) (MM) 3J-II 30 pans 55 parts 15 pans 1 part (THFMA) (HPMA) (MM) Stereon 840A
IBOMA -isobornyl methacrylate OMA -2-ethylhexyl methacrylate ODA -n-octylacrylate/n-decylacrylate mixture HDDA -1,6-hexanediol diacrylate HDDMA -1,6-hexanediol dimethacrylate THFMA -tetrahydrofurfryl methacrylate HPMA -2-hydroxypropyl methacrylate MAA -methacrylate acid CHP -cumene hydroperoxide Approxim~1ely equal portions of Parts I and II were applied to steel plates and allowed to cure at room temperature. The bonds were evaluated for tensile shear strength using ASTM standard method DlO02-72 (1973) in pounds/inch2 (psi) and for T-peel using ASTM standard method Dl876-72 in pounds/linear inch (pli). These results are shown below (where, eg., 3AI +3AII).
Adhesi~e Sample No. Tensile Shear (pai) ~-Peel (pli) 3E 2900 ~ 5
3-aminomethylpyridine 10.8 g (O.lO m) X
diethylamine lO 9S g (O.lS m) XI
1,3-propylene diamine 11.1 g (O lS m) XII
1 molar solution of triethylboron in tetrahydrofuran used CA 02061021 1998-06-l9 EXAMPLE II
Preparation of Adhesive Composition An adhesive formulation was prepared consisting of two parts that were mixed just prior to use. The first part contained the monomer-polymer syrup and the stabilized organoboron amine complex initiator from Example I. The second part contained a similar monomer-polymer syrup and an acid activator or reagent that destabilized the organoboron amine complex liberating the free organoboron. When mixed with the first part polymerization was initi~tefl The two adhesive composition parts were:
Part I
Stereon 840A (styrene-butadiene block copolymer) 30 parts Isobornyl methacrylate 70 parts Organoboron amine initiator No. 12l 4 parts Part II
Stereon 840A 30 parts Isobornyl methacrylate 61 parts Methacrylic acid 5 parts Cumene hydroperoxide (CHP) 4 parts Approximately equal portions of Parts I and II were mixed and applied to steel plates and allowed to cure. Tensile shear strength measurement on the adhesive bond was made according to the ASTM standard method D1002-72(1973) and found to be 2000 pSi.
Additional adhesive formulations were prepared in a similar manner using the components as identified below along with the resulting tensile strength determined is described above for the formed adhesive bond.
1 molar solution in tetrahydrofuran RUBBER (%) INITIATOR ~ ACID1 % CHP2 BOND T~NSILE
(~) STR~NGT~ PSI
Stereon 840a (20) XII (O S) 10 0.1 1875 Stereon 840a (253 VIII (O S) 1 1 1550 ~raton 1107 (20)3 II (O.S) 10 1 1850 Kraton 1107 (20~ II (0.25) 10 1 1350 ~raton 1107 (20) II (l.G) 10 1 2100 Hycar 4051 (10)4 IV (0.5) 10 1 - 1200 ~raton 1122 (25)5 VI (0 5) 1 1 1500 stereon 840~ (20) I (O.S) 0.5 1.7 lS00 al~o contain~ 13~ octyl acrylate Stereon 840A (30) ¦ VIII (0.5) ¦ 10 ¦ 1 ¦ 2700 monomer wa~ tetrahydrofur~uryl methacrylate 1. methacrylic acid 2. cumene hydroperoxide 3. styrene-isoprene 4. polyacrylic rubber polymer 5. styrene-isoprene EXAMPLE III
Similar adhesives formulations were prepared as in Example II using an amine complex of 1,3 propylene diamine and triethyl boron as the initiator (initiator No. Vm).
The formulations contained two-parts as in Example II that were mixed just prior to use and had the following compositions:
3 5 * trade-mark .
S Part I
Sample No. In;tiator Rubber1 MonomerA Monomer B MonomerC
3A-I 2 parts 25 pans 60 parts 15 pans (iBOMA) (OMA) 3B-I 2 pans 2~ pans 60 parts 15 pans (iBOMA) (OMA) 3~I 2 pans 25 pans 60 parts 15 pans (IBOMA) (ODA) 3D-I 2 pans 25 pans 60 parns 15 pans (IBOMA) (I iDDA) 3E-I . 2 pans 25 pans 60 pans 15 pans (iBOMA) (HDDMA) 3F-I 2 pans 30 parts -- -- 70 parts (THf ~MA) 3G-I 2 pans 30 pans -- -- 70 parts - (THFMA) 3H-I 2 parls 30 pans -- -- 70 pans (THFMA) 3I-I 2 pans 30 pans -- -- 70 pans - (THFMA) 3J-I 2 parts 30 parts 55 pans -- 15 pans (IBOMA) (HPMA) , Part II
Sample NQ Rubber1 MonomerA Monomer B Acld CHP
3A-ll 25 parts 50 pans 15 pans 10 parts (T:HFMA) (OMA) (MAA) 3~-ll . 25 parts 50 par~s 15 parts 10 parts (IBOMA) (OMA) (MM) 3~ll 2~ pans 50 pans 15 pans 10 parts (THFMA) (ODA) (MM) 3D~I 25 parts 50 parts 15 pans 10 parts ~ ( rHFMA) (HDDA) (MAA) 3E-Il 25 parts 50 pans 15 parts 10 parts l S (THFMA) (HDDMA) (MM) 3F-ll 30 pans 60 pans -- 10 pans 0.12,5 pans (THFMA) (MM) 3G-Il 30 pans 60 pans -- 10 par~s 0.250 pans (THFMA) (MM) 3H-Il 30 pans 60 pans -- 10 pans 0.5 pans THFMA) (MM) 31-ll 30 parts 60 par~s -- 10 pans 1 pan (THFMA) (MM) 3J-II 30 pans 55 parts 15 pans 1 part (THFMA) (HPMA) (MM) Stereon 840A
IBOMA -isobornyl methacrylate OMA -2-ethylhexyl methacrylate ODA -n-octylacrylate/n-decylacrylate mixture HDDA -1,6-hexanediol diacrylate HDDMA -1,6-hexanediol dimethacrylate THFMA -tetrahydrofurfryl methacrylate HPMA -2-hydroxypropyl methacrylate MAA -methacrylate acid CHP -cumene hydroperoxide Approxim~1ely equal portions of Parts I and II were applied to steel plates and allowed to cure at room temperature. The bonds were evaluated for tensile shear strength using ASTM standard method DlO02-72 (1973) in pounds/inch2 (psi) and for T-peel using ASTM standard method Dl876-72 in pounds/linear inch (pli). These results are shown below (where, eg., 3AI +3AII).
Adhesi~e Sample No. Tensile Shear (pai) ~-Peel (pli) 3E 2900 ~ 5
Claims (14)
1. A curable two-part adhesive composition wherein one-part comprises a polymerizable acrylic monomer and an effective amount of a stable organoboron amine complex initiator of the formula:
where R, R1 and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or or where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6; and the second part contains an effective destabilizing amount of an organic acid activator having the formula:
R - COOH
where R is H, alkyl or alkenyl of 1 to 8 carbons or aryl of 6 to 14 carbon atoms.
where R, R1 and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or or where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6; and the second part contains an effective destabilizing amount of an organic acid activator having the formula:
R - COOH
where R is H, alkyl or alkenyl of 1 to 8 carbons or aryl of 6 to 14 carbon atoms.
2. The composition of Claim 1 wherein in th organoboron amine complex R, R1 and R2 are alkyl of 1 to 4 carbons, R3, R4 and R5 are hydrogen or alkyl of 1 to 4 carbons, R6 is hydrogen, m is 2 to 6 and n is 1 to 2 and in the organic acid activator the R group is an alkyl or alkenyl group of 1 to 4 carbons or an aryl of 6 to 8 carbons.
3. The composition of Claims 1 to 2 wherein from about 0.1:1 to 200:1 parts byweight of acid to amine complex are used.
4. The adhesive composition of Claim 3 wherein the first part of the compositioncontaining the acrylic monomer further comprises a rubber polymer and wherein the second part of the initiator system also contain a hydroperoxy compound.
5. The adhesive composition of Claim 4 wherein the second part containing an organic acid activator further comprises a polymerizable acrylic monomer with a rubber polymer dissolved therein.
6. The composition of Claim 5 wherein from about 0.1 to 5 % by weight of the organoboron amine complex and from about 0.5 to 20% by weight of the organic acid activator based on the total weight of the composition are used.
7. The composition of Claims 4 or 5 wherein the second part further contains a hydroperoxy compound having the formula R-OOH, where R is hydrogen, alkyl of 1 to 10 carbon atoms or aryl or alkaryl of 6 to 14 carbon atoms wherein from about 10 to 90% by weight of the acrylic monomer and from about 5 to 80% by weight of the rubber polymer based on the total weight of the composition are used.
8. The composition of Claim 7 wherein the acrylic monomer is an alkyl acrylate or methacrylate and the rubber polymer is a polymer, copolymer or block copolymer of polybutadiene, polyisoprene, polyisobutylene, butadiene/styrene, butadiene/acrylonitrile and butadiene/alkyl acrylate.
9. A two-part initiator system for use in acrylic adhesive compositions comprising:
(A) a stable organoboron amine complex of the formula:
where R, R1 and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or or where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6, and B) an effective destabilizing amount of an organic acid activator having the formula:
R-COOH
where R is H, alkyl or alkenyl of 1 to 8 carbon atoms or aryl of 6 to 10 carbon atoms.
(A) a stable organoboron amine complex of the formula:
where R, R1 and R2 are alkyl of 1 to 10 carbon atoms or phenyl, R3 and R4 are hydrogen or alkyl of 1 to 10 carbon atoms, or or where R5 and R6 are hydrogen or alkyl of 1 to 10 carbon atoms, m is 2 to 10 and n is 1 to 6, and B) an effective destabilizing amount of an organic acid activator having the formula:
R-COOH
where R is H, alkyl or alkenyl of 1 to 8 carbon atoms or aryl of 6 to 10 carbon atoms.
10. The composition of Claim 9 wherein in the organoboron amine complex, R, R1 and R2 are alkyl of 1 to 4 carbons, R3, R4 and R5 are hydrogen or alkyl of 1 to 4 carbon atoms, R6 is hydrogen, m is 2 to 6 and n is 1 to 2 and wherein the R group of the organic acid of part B is an alkyl or alkenyl group of 1 to 4 carbons or an aryl of 6 to 8 carbons.
11. The composition of Claims 9 or 10 wherein from about 0.1:1 to 200:1 parts by weight acid to amine complex are used.
12. The composition of Claim 11 wherein the second part B) also contains a hydroperoxy compound.
13. The composition of Claim 12 wherein the hydroperoxy compound has the formula R-OOH, where R is hydrogen, alkyl of 1 to 10 carbon atoms or aryl or alkaryl of 6 to 14 carbon and wherein the complex is a combination of tributyl boron andethylene diamine or propylene diamine.
14. A method of bonding facing surfaces which comprises interposing between saidsurfaces the curable adhesive composition of Claim 1 or 5, placing the surfaces in an abutting relationship and permitting the adhesive to cure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US692,766 | 1991-04-29 | ||
| US07/692,766 US5106928A (en) | 1991-04-29 | 1991-04-29 | Acrylic adhesive composition and organoboron initiator system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2061021A1 CA2061021A1 (en) | 1992-10-30 |
| CA2061021C true CA2061021C (en) | 1998-12-22 |
Family
ID=24781936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2061021 Expired - Fee Related CA2061021C (en) | 1991-04-29 | 1992-02-11 | Acrylic adhesive composition and organoboron initiator system |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5106928A (en) |
| EP (1) | EP0511464B1 (en) |
| JP (1) | JPH0772264B2 (en) |
| KR (1) | KR950009549B1 (en) |
| CA (1) | CA2061021C (en) |
| DE (1) | DE69201093T2 (en) |
| ES (1) | ES2067965T3 (en) |
| HK (1) | HK51195A (en) |
| SG (1) | SG28341G (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL270970A (en) * | 1960-11-11 | |||
| US3275611A (en) * | 1960-12-30 | 1966-09-27 | Monsanto Co | Process for polymerizing unsaturated monomers with a catalyst comprising an organoboron compound, a peroxygen compound and an amine |
| DE3041904C2 (en) * | 1980-11-06 | 1984-11-22 | Henkel KGaA, 4000 Düsseldorf | Storage-stable reactive adhesives containing boron compounds |
| DE3143945A1 (en) * | 1981-11-05 | 1983-05-11 | Henkel KGaA, 4000 Düsseldorf | 2-COMPONENT NO-MIX ADHESIVES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| JP2543516B2 (en) * | 1987-03-09 | 1996-10-16 | 三井石油化学工業株式会社 | Dental curable adhesive |
-
1991
- 1991-04-29 US US07/692,766 patent/US5106928A/en not_active Expired - Lifetime
-
1992
- 1992-02-11 CA CA 2061021 patent/CA2061021C/en not_active Expired - Fee Related
- 1992-02-20 ES ES92102863T patent/ES2067965T3/en not_active Expired - Lifetime
- 1992-02-20 DE DE1992601093 patent/DE69201093T2/en not_active Expired - Lifetime
- 1992-02-20 SG SG1995903985A patent/SG28341G/en unknown
- 1992-02-20 EP EP19920102863 patent/EP0511464B1/en not_active Expired - Lifetime
- 1992-02-27 JP JP4111792A patent/JPH0772264B2/en not_active Expired - Fee Related
- 1992-03-04 KR KR1019920003514A patent/KR950009549B1/en not_active IP Right Cessation
-
1995
- 1995-04-06 HK HK51195A patent/HK51195A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0598216A (en) | 1993-04-20 |
| SG28341G (en) | 1995-09-18 |
| EP0511464B1 (en) | 1995-01-04 |
| JPH0772264B2 (en) | 1995-08-02 |
| EP0511464A1 (en) | 1992-11-04 |
| US5106928A (en) | 1992-04-21 |
| KR950009549B1 (en) | 1995-08-24 |
| DE69201093D1 (en) | 1995-02-16 |
| ES2067965T3 (en) | 1995-04-01 |
| DE69201093T2 (en) | 1995-05-11 |
| HK51195A (en) | 1995-04-13 |
| KR920019899A (en) | 1992-11-20 |
| CA2061021A1 (en) | 1992-10-30 |
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