CN1095744C - Adhesive composite - Google Patents

Abstract

The present invention relates to a polymerisable acrylic composition which comprises at least one acrylic monomer, an effective quantity of organic borane amine coordination compound with the following formula and an effective quantity of acid for initiating the polymerization of the acrylic monomer, wherein R<1> is an alkyl group containing 1 to 10 carbon atoms; R<2> and R<3> are independently selected from a base group containing phenyl groups and an alkyl group containing 1 to 10 carbon atoms; and R<4> is a base group selected from CH2CH2OH and (CH2)xNH2, wherein the x is an integral number greater than 2, and R<5> is hydrogen or is an alkyl group containing 1 to 10 carbon atoms. The ratio of the nitrogen atoms to the boron atoms of the acid is about 1:1 to 1.5:1. The polymerisable acrylic composition is particularly used for bonding base material with low surface energy.

Description

Bonding compound

The present invention is that international application no is PCT/RU94/00029, and international filing date is that to enter the national applications of China after the stage number be dividing an application of 94195013.1 Chinese patent application to the PCT international application on February 22nd, 1994.

The present invention relates generally to a kind of bonding compound, relate more specifically to a kind of bonding compound that comprises first base material and second base material, particularly comprise adding and be the compound of acrylic adhesive of the polymerization initiator system of base with the organo-borane amine complex.

For a long time always all in the method for seeking a kind of useful, effective bonding low surface energy substrates (as polyethylene, polypropylene and polytetrafluoroethylene (PTFE) (for example TEFLON)).The difficulty that is run into when bonding these materials is well-known.For example referring to the development of D.M.Brewis at rubber and plastics technology, the 1st volume, contained " adhesion problem of polymer surfaces " literary composition in the 1st page (1985).Conventional means is typically by the effect of following two aspects: the surface that (1) improves base material can (can more can closely mate the surface of base material with the surface of adhesive on it, thereby promote that better base material is wetting by adhesive) and/or (2) are got rid of and can be moved to substrate surface and form a weak boundary layer and to bonding additive that has a negative impact and the low-molecular weight polymer component in the adhesive in base material.

As a result, conventional means often uses for example flame treatment of the expensive substrate surface technology of preparing of complexity and valency, corona discharge, and plasma treatment, with the oxidation of ozone or oxidizing acid, and sputter etching.Perhaps, be coated on substrate surface with the material of high surface energy and stamp priming paint.Yet, bonding in order to reach suitable priming paint, must at first use above-mentioned surface preparation technology.As what reported in the disquisition (J.D.Minford, editor, Marcel Dekker, 1991, New York, the 7th volume, 333-435 page or leaf) of bonding and adhesive, all these technology all are well-known.Also habitual usually means known concerning special base material.As a result, they may be useless to the base material of bonding low surface energy usually.

And the complexity of means known and expense make them can't be particularly suitable for retail consumers (for example home repair and the person of doing it yourself etc.) or use to operate among a small circle at present.The problem of worries is that repairing is many by polyethylene, and the daily household article of the cheapness that polypropylene or polystyrene are made is dust basket, wash basket and toy for example.

Therefore, press for very much a kind of simple, wieldy adhesive for a long time, it can easily bonding many base materials, especially the material of low-surface-energy (polyethylene for example, polypropylene and polytetrafluoroethylene (PTFE)), and do not need the complex surfaces preparation, priming etc.

The present invention relates to comprise with the organo-borane amine complex is the bonded composite of adhesive of the polymerization initiator system of base.This adhesive is particularly useful in bonding low surface energy substrates (as polyethylene, polypropylene and polytetrafluoroethylene (PTFE)).

(p.653) Bull.Acad.Sci.USSR, Div.Chem.Sci.1957 have reported that use tributyl monoborane comes polymerizing styrene and methyl methacrylate as catalyst at nineteen fifty-seven G.S.Kolesnikov etc.The tributyl monoborane that adds 2mol% in methyl methacrylate causes polymerisation fast; In 60-90 minute, form transparent solid block.Approximately at the same time, (Journal of Polymer Science such as J.Furakawa, the 26th volume, 113 phases, p.234,1957) reported and found that triethylborane causes some vinyl compounds (as vinyl acetate, vinyl chloride, vinylidene chloride, methacrylate, acrylate and acrylonitrile) polymerisation.After a while, J.Furakawa etc. (Journal of Polymer Science, 28 volumes, 116 phases, 1958) have reported that the vinyl polymerization of triethylborane catalysis reacts and can be quickened significantly by oxygen or oxygen compound (as hydrogen peroxide and metal oxide).Although the existence of significant need aerobic during polymerization reaction take place, the organoborane compounds of type is very easily ignited in air described in known these documents.Therefore, the existence of oxygen is to need and be undesirable simultaneously.

United States Patent (USP) 3 at disclosed E.H.Mottus on the 27th etc. September in 1966,275, disclosed the polymerization olefinic compounds in 611 " with containing organic boron compound, the method for the polymerization catalyst unsaturated monomer of peroxide and amine ", especially the method for alpha-alefinically unsaturated compounds.Good especially is the methacrylate monomers that contains no more than 20 carbon atoms in ester group.Organoboron compound and amine can be added in the reactant mixture dividually or as a complex that generates in advance.A kind of method in back it is reported to have the more tractable advantage of the boron compound of making, and especially is tending towards igniting in air for some and the boron compound that the time can not ignite when cooperation.Described useful especially B catalyst has following general formula: R ₃B, RB (OR) ₂, R ₂B (OR), R ₂BOBR ₂, R ₂BX and R ₂BH, wherein R is an alkyl, is halogen atom for containing 1-10 alkyl and X individual or more a plurality of carbon atoms (being to reach 6 carbon atoms better) preferably.

Described useful amine compounding ingredient has certain basicity, and this is worth preferably about 10 ^-6Or 10 ^-7-5 * 10 ^-10Or 10 ^-10Scope in.Although use pyridine in an embodiment, aniline, toluidines, dimethyl benzylamine and nicotine, that can mention has various amine compounding ingredients.The used amine and the mol ratio of boron compound are about 1: 1, suppose that there is a nitrogen functional group in each boron functional group.It is reported that any peroxide or hydroperoxides are the useful as catalysts component all.

Although Mottus etc. have mentioned methacrylate monomers is carried out polymerization, the polymer of not pointing out gained is as adhesive.Propose the monomer that various acid can be used as polymerization, but do not point out that acid is a kind of component of polymerization system.

In disclosed british patent specification 1 on May 15 nineteen sixty-eight, 113, disclosed use free radical catalyst (as peroxide) in 722 " polymerisable compositions that need oxygen " and triaryl monoborane complex comes the polymeric acrylate monomer, described triaryl monoborane complex has general formula (R ₃) B-Am, wherein R is the aryl that contains 6-12 carbon atom, Am (one of them) is amine such as hexamethylene diamine or monoethanolamine.Come the activated polymerization reaction by heating or adding acid.The composition of gained it is reported and can be used as adhesive.

Chemical abstracts 88532r (73 volumes; 1970) text quoted of " self curing resin of dentistry (Dental Self-curingResin) " and it has reported that in full the tributyl monoborane can make stable in the airly; this is by making it and ammonia or some amine (as aniline; n-butylamine, piperidines, 1; the 2-ethylenediamine) be 1 to cooperate with mol ratio; this digest has also been reported for example isocyanates of available amine acceptor, acid chloride, and sulfonic acid chloride or anhydrous acetic acid carry out reactivation to the tributyl monoborane.As a result, can use complex that the blend of methyl methacrylate and poly-(methyl methacrylate) is carried out polymerization to obtain dental cement.That specifically mentions has the tributyl monoborane-1 that contains respectively as the paratoluensulfonyl chloride of amine acceptor, 2-ethylene diamine complex and a triethylborane-amine complex.

Chemical abstracts 134385q (80 volumes, 1974) " polyolefin or polyvinyl bonding " reported and used 10 parts of methyl methacrylates, 0.2 the bonding polyethylene of mixture of part tributyl monoborane and 10 parts poly-(methyl methacrylates), polypropylene and poly-(vinyl acetate) rod.

The United States Patent (USP) 5 of the M.M.Skoultchi that on April 21st, 1992 announced etc., 106, disclosed a kind of two parts initiator system in 928 " acrylic adhesive composition and the organic boron initiator systems ", it is reported that this system is used for acrylic adhesive composition, especially elastomeric propylene acid adhesive.The first of two parts initiator system is stable organo-borane amine complex; Second portion is the organic acid for activating agent.The organoborane compounds of complex has following general formula:

R wherein, R ₁And R ₂For containing the alkyl or phenyl of 1-10 carbon atom, and the alkyl that contains 1-4 carbon atom is preferably.The amine moiety of complex can be ammonia, primary amine, and secondary amine, or contain the polyamines of primary amine or secondary amine.Useful amine comprises n-octyl amine, 1, and 6-diamino hexane, diethylamine, dibutyl amine, diethylenetriamines, dipropylenediamine, 1,3-trimethylene diamine and 1,2-trimethylene diamine.

The organic acid for activating agent is a kind of by removing the compound that amido removes to stablize or discharge free organoborane compounds, makes its energy initiated polymerization process thus.Comparatively preferably, organic acid has general formula R-COOH, and wherein R is a hydrogen, contains the alkyl or the alkenyl of 1-8 carbon atom (1-4 carbon atom preferably), or contains the aryl of 6-10 carbon atom (6-8 carbon atom preferably).

12 kinds of organoborane amine initator complexs have description in example I.Is in the complex of base at those with diamines or triamine, and nitrogen-atoms is 2 with the ratio of boron atom: 1-4: 1.Is in the complex of base at those with diethylamine and n-octyl amine, and nitrogen-atoms is 1.5: 1 with the ratio of boron atom.

It is reported, adhesive composition is particularly useful in the application of structure and the bonding aspect of half hitch structure, microphone magnet for example, metal-metal bonding, (automobile) glass-metal bonding, glass-glass bonding, circuit board component bonding, selectively plastics and metal, glass, timber etc. and motor magnet bonding.The plastics that those can be bonded will be not described further.

The present invention relates to bonding compound, especially comprise adding and be the compound of acrylic-type adhesive binder of the polymerization initiator system of base with the organo-borane amine complex.This adhesive is useful especially in the base material of bonding low surface energy (for example polyethylene, polypropylene, polytetrafluoroethylene (PTFE) etc.), then uses bonding these base materials of surface preparation technology complicated and that valency is expensive before this.

Polymerisable acrylic type composition comprises, and preferably mainly be made up of following component: at least a acrylic monomers (is alkyl acrylate preferably, as butyl acrylate and/or alkyl methacrylate, as methyl methacrylate), the organic or inorganic acid that is used to cause polymerizable acrylic monomer of the organo-borane amine complex of effective dose and effective dose (acrylic acid for example, methacrylic acid or SnCl ₄).

Useful organo-borane amine complex has following general formula:

Wherein:

R ¹For containing the alkyl of 1-10 (2-5 preferably) carbon atom;

R ²And R ³Be independently selected from the alkyl that contains phenyl groups and contain 1-10 carbon atom, be preferably the alkyl that contains 2-5 carbon atom;

R ⁴For being selected from CH ₂CH ₂OH and (CH ₂) _xNH ₂Group, wherein x is the integer greater than 2, is 2-6 preferably, is 6 better;

R ⁵For hydrogen (better) or contain the alkyl of 1-10 carbon atom; With

Nitrogen-atoms is about 1 with the ratio of boron atom: 1-2: 1, be about 1 better: 1-1.5: 1, be about 1: 1 best.

Molal quantity with acrylic acid groups, part or degree of functionality is a benchmark, and the amount of the organo-borane amine complex that is provided typically is about 0.15-3mol% and (is about 0.2-2.5mol% better; Be about 1-1.5mol% best).Equivalents with amine groups, part or degree of functionality is a benchmark, and the effective dose of acid is about 30-540mol% (being about 230mol% best).

The useful additive that randomly can be included in these compositions is the organo-borane that does not cooperate basically of thickener (for example polymethyl methacrylate) and a small amount of (0.1-7mol% that is about acrylic acid degree of functionality molal quantity), and the latter is useful especially when being base as if the organo-borane amine complex with the monoethanolamine.

In broad terms, the present invention relates to bonding compound, especially using with the organo-borane amine complex is the compound of the acrylic-type adhesive binder that makes of the polymerization initiator system of base.This adhesive is useful especially in the base material of bonding low surface energy (for example polyethylene, polypropylene, polytetrafluoroethylene (PTFE) etc.), then uses bonding these base materials of surface preparation technology complicated and that valency is expensive before this.

Be used for polymerization initiator system of the present invention and comprise, and preferably mainly form by following component: the organo-borane amine complex of effective dose and effective dose in order to discharge the acid of organo-borane with initiated polymerization.Be used for organo-borane amine complex of the present invention and have following general formula:

R wherein ¹Be alkyl and the R that contains 1-10 carbon atom ²And R ³Be independently selected from the alkyl that contains 1-10 carbon atom and contain phenyl groups.More preferably, R ¹, R ²And R ³For containing the alkyl of 1-5 carbon atom, for example methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group and amyl group.Usually, to R1, the short carbon chain lengths of R2 and R3 group is preferably, and reason is that it has improved the aerial stability of complex.Less, not too huge substituting group also is that and bigger, huger group can have a negative impact to bonding preferably." be independently selected from " and be meant R ²And R ³Can be identical or different.R ¹Can with R ²Or R ³Identical or different.R comparatively preferably ¹, R ²And R ³All identical.Found tripropyl, the alkyl borane of triisopropyl and three normal-butyls is useful especially.

The amine component of complex can be monoethanolamine, primary alkyl diamines or secondary alkyl diamine.Therefore, R ⁴Can be and be selected from CH ₂CH ₂OH and (CH ₂) ₆XNH ₂Group, wherein x is the integer greater than 2.R ⁵For hydrogen or contain the alkyl of 1-10 carbon atom.In the better fit thing, R ⁵Be hydrogen (reduce in the organo-borane amine complex and can suppress the sterically hindered of complex formation itself) and R ⁴Be CH ₂CH ₂OH or (CH ₂) ₆XNH ₂, wherein x is the integer of 2-6.And best complex is R wherein ⁴Be CH ₂CH ₂OH (monoethanolamine) or (CH ₂) ₆NH ₂(1, the 6-hexamethylene diamine).

Important and as below be described in more detail, nitrogen-atoms is about 1 with the ratio of boron atom in the complex: 1-2: 1, be about 1 preferably: 1-was about 1: 1-1.5 less than 2: 1 better: 1, be about 1: 1 best.When the ratio of nitrogen-atoms and boron atom surpassed 2: 1, the practicality of complex in polymerization initiator system reduced, and reason is big for the amount all too that obtains the complex that useful molecular weight institute must use in polymerization process.On the other hand, will discharge free organo-borane less than the ratio of 1: 1 nitrogen-atoms and boron atom, material is tending towards igniting.

The effective dose of organo-borane amine complex is even as big as making the easy amount that takes place with the acrylate copolymer that obtains the required enough HMWs of final use of polymerisation.If the amount of organo-borane amine complex is too high, then polymerisation is carried out to such an extent that too fast consequently composition can not mix and use effectively.Useful polymerization rate depends in part on the method for composition to the base material that apply.Like this, the High-Speed Automatic industry polymerization rate of executing material machine (applicator) apply with the machine that manually applies than composition or artificial blended composition fast.

In these parameters, be benchmark in the molal quantity of acrylic acid degree of functionality, the effective dose of organo-borane amine complex is about 0.15-3mol%, is about 0.2-2.5mol% better, is about 1-1.5mol% best.If amine is monoethanolamine, the effective dose of having found complex is greater than 2mol% but less than about 5mol%." acrylic acid degree of functionality " is meant the acrylate moiety or the chemical group of acrylic acid and replacement; In other words, this group has formula and is

Structure, wherein R and R ' are identical or different organic group.

Yet, exemplify as following, comprise a small amount of additionally sometimes further, the organo-borane that does not cooperate is favourable basically.In these examples, be benchmark in the molal quantity of acrylic acid degree of functionality, the effective dose of complex is about 0.3-5mol%, is about 0.5-4mol% better, is about 1-3mol% best.

Advantageously, being used for organo-borane amine complex of the present invention is air-stable." air-stable " is meant when complex at room temperature (about 20 ℃-22 ℃) and at (promptly not under vacuum and inert atmosphere) under other environmental condition when being stored in the container of adding a cover, complex as polymerization initiator can keep fortnight approximately at least, although complex may easily be stored under these conditions several months even reach 1 year or the longer time.Illustrate in greater detail as following, " air-stable " assignment compound do not ignite yet.If the words that complex provides with the form of crystalline material then its air stability can improve.The most stable existence form of complex is a pure white, solid, acicular crystal.Yet even with amorphous solid or viscosity, the form of paste liquid exists, and complex is still useful.After a period of time, best pure white solid acicular crystal also can show as these forms.

The organo-borane amine complex can use known technology easily to prepare.Typically way is, amine (if solid shape) is ground to form tiny powder (preferably in inert atmosphere), mixes (also in inert atmosphere) with organo-borane under slowly stirring.Usually can be observed exothermic phenomenon, therefore advise cooling mixture.Because the high-vapor-pressure of some materials that may use wishes to make reaction temperature to remain on about 70-80 ℃ of low son, but temperature should not remain on to be low to moderate and makes product do sth. in advance the temperature of crystallization.In case material is mixed fully, make the complex cooling to form its crystal.Do not need special storage condition.Although complex being kept at placing dark cold place in the container of adding a cover is preferably.Advantageously, being used for complex of the present invention is prepared need not adding in the presence of the organic solvent of removing subsequently.

Acid is discussed now, and this component makes the organo-borane initiated polymerization by removing amido release organo-borane.Anyly all can use by removing the acid that amido discharges organo-borane.Useful acid comprise Louis silk acid (as SnCl4, TiCl4 etc.) and Bronsted acid (Bronsted acid) for example those to have general formula be R ⁶The acid of-COOH, wherein R ⁶Be hydrogen, alkyl, or contain 1-8, be preferably the alkenyl of 1-4 carbon atom, or contain the aryl that 6-10 is individual, be preferably 6-8 carbon atom.Alkyl and alkenyl can comprise a straight chain or they can have side chain.These groups can be saturated or unsaturated.Aryl can contain as alkyl, the substituting group of alkoxyl or halogen atom and so on.The such acid that is exemplified comprises acrylic acid, methacrylic acid, acetate, benzoic acid and P-methoxybenzoic acid.Other useful Bronsted acid comprises HCl, H2SO4, H3PO4 etc.SnCl4, acrylic acid and methacrylic acid are preferably.

Should use the acid of the effective dose that promotes polymerization.If the acid of using very little, then the speed of polymerisation is too slow, and the monomer of generation polymerization can't suitably improve molecular weight.Yet the amount that reduces acid is helpful to slowing down polymerization rate.On the other hand, if the acid of using is too many, then polymerisation is tending towards carrying out too soon, is having under the situation of adhesive, and it is inappropriate that the material of gained confirms the bonding of low-energy surface.On the other hand, excessive acid can promote bonding with high energy surface.In these parameters, be benchmark in the equivalents of amine degree of functionality in the complex, the amount of used acid is about 30-540mol% preferably, is about 100-350mol% better, is about 150-250mol% best.For methacrylic acid and organo-borane amine complex are based on tripropyl borine and 1, during the 6-hexamethylene diamine, found that the gross weight in composition is a benchmark, the amount of acid is about 0.5-7wt.%, is useful for about 3wt.% better.

The organo-borane amine complex initiator systems is particularly useful for the polypropylene acid monomers, is particularly useful for preparing polymerisable acryloid cement." acrylic monomers " is meant and contains one or more acrylic acid or substitutional crylic acid part, the polymerisable monomer of chemical group or degree of functionality; In other words, this group has general formula and is

Structure, wherein R and R ' are identical or different organic group.Also can use the mixture of acrylic monomers.Polymerisable acrylic monomers can be simple function, multifunctional or their combination.

The most useful monomer is monofunctional acrylate and methacrylate and their substitutive derivative such as hydroxyl, acid amides, cyano group, chlorine and silane derivative.This monomer comprises methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, butyl acrylate, the acrylic acid n-octyl, acrylic acid 2-b hexyl, methacrylic acid 2-b hexyl, decyl-octyl methacrylate, methacrylic acid dodecane ester, cyclohexyl methacrylate, the metering system tert-butyl acrylate, acrylamide, N methacrylamide, DAAM, N tert butyl acrylamide, uncle's N-octyl acrylamide, N-butoxy acrylamide, γ-methacryloxypropyl trimethoxy silane, acrylic acid 2-cyanogen ethyl ester, acrylic acid 3-cyanogen propyl ester, methacrylic acid tetrahydro furfuryl ester, chloroacrylic acid tetrahydro furfuryl ester, glycidyl acrylate, GMA etc.Can use acrylic acid dimethylamino ethyl ester and dimethylaminoethyl acrylate methyl base ammonia ethyl ester.

Good especially is the mixture of alkyl acrylate (for example butyl acrylate) and alkyl methacrylate (for example methyl methacrylate).This polymerisable composition of the present invention mainly comprises, gross weight with composition is a benchmark, the alkyl acrylate of the alkyl methacrylate of about 10-60wt.% (about better 30-40wt.%) and about 10-50wt.% (about better 25-35wt.%).

The polymerisable monomer of another kind of useful type has following general formula: R ⁷Can be and be selected from hydrogen, methyl, ethyl ,-CH ₂OH and

Group.R ⁸Can be and be selected from chlorine, the group of methyl and ethyl, R ⁹Can be and be selected from hydrogen, hydroxyl and

Group.A is the integer more than or equal to 1, is the integer of 1-about 8 better, is the integer of 1-4 best.B is the integer more than or equal to 1, is the integer of 1-about 20 better.C is 0 or 1.

The acrylic monomers that is used for polymerization initiator system comprises ethylene glycol dimethacrylate, glycol diacrylate, polyethyleneglycol diacrylate, tetraethylene glycol dimethacrylate, the diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate and other polyethers diacrylate class and dimethylacrylate class.

Be used for other polymerisable monomer of the present invention and have following general formula:

R ¹⁰Can be hydrogen, chlorine, methyl or ethyl; R ¹¹Can be the alkylidene that contains 2-6 carbon atom; And R ¹²Be (CH ₂) _e(wherein e is the integer of 0-8), or be a kind of in the following radicals:

Neighbour in the phenyl, or any one position of contraposition on substituting group can be arranged.D is the integer of 1-4.

Such typical monomers comprises the dimethylacrylate of two (ethylene glycol) adipate ester, the dimethylacrylate of two (ethylene glycol) maleate, the dimethylacrylate of two (ethylene glycol) phthalic acid ester, the dimethylacrylate of two (tetraethylene glycol) phthalic acid ester, the dimethylacrylate of two (tetraethylene glycol) sebacate, the dimethylacrylate of two (tetraethylene glycol) maleate and corresponding to the diacrylate and the chloropropene acid esters of dimethylacrylate, etc.

Equally also useful monomer is the product of isocyanates-hydroxy acrylate or isocyanates-amino acrylates.These monomers can be called polyurethane and the polyamides urea or the polyureas of acrylate ended.This monomer has following general formula:

Wherein X for be selected from-O-and Group.R ¹³For being selected from hydrogen and the low alkyl group group of (promptly containing 1-7 carbon atom).T is the organic residue that contains the acrylate of reactive hydrogen, and reactive hydrogen has been removed and ester is gone up by hydroxyl or amino the replacement at its moieties (comprising methyl, ethyl and chlorine homologue) therein.F is the integer of 1-6.L is for being selected from alkyl, alkylidene, and alkenyl, cycloalkyl, cycloalkylidene, aryl, aralkyl, alkaryl, poly-(oxyalkylene), one or the multivalence organic group of poly-(carbonyl alkoxyl alkylidene), and heterocyclic group, above-mentioned group all can be substituted and not replace.

Such typical monomers comprises one or PIC (for example toluene di-isocyanate(TDI)) and product at its non-acrylate part hydroxyl or amino acrylate (for example hydroxyethyl methacrylate).

Being used for one type monomer in addition of the present invention is one and polyacrylate and the methacrylate of bisphenol type compound.These monomers can be described as has following structural formula:

R wherein ¹⁴Be methyl, ethyl, carboxyalkyl or hydrogen; R ¹⁵Be hydrogen, methyl or ethyl; R ¹⁶Be hydrogen, methyl or hydroxyl; R ¹⁷Be hydrogen, chlorine, methyl or ethyl; G is the integer of 0-8.

The representative monomers of the above-mentioned type comprises 4,4 '-dimethylacrylate and the diacrylate of two-hydroxyl-oxethyl-bisphenol-A, the dimethylacrylate of bisphenol-A and diacrylate, etc.

Composition can further comprise various optional additives.A kind of useful especially additive is a thickener, the polymethyl methacrylate of low-molecular-weight (promptly being less than or equal to about 1000,000) for example, and its addition can be about 20-40wt.% (percetage by weight) of composition weight.The viscosity that can use thickener to improve composition reaches the various pulpous state denseness of more easily using.

Another kind of useful assistant is a crosslinking agent, and it can be used for improving the solvent resistance of adhesive bond.Typically used amount is about 0.2-1 weight % of composition weight, useful crosslinking agent comprises ethylene glycol dimethacrylate, glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol (DEG) dimethyl allene acyloxy carbonic ester, polyethyleneglycol diacrylate, tetraethylene glycol dimethacrylate, the diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylol-propane trimethacrylate and other polyethers diacrylate and dimethylacrylate.

Also can randomly comprise peroxide with the polymerization speed of regulating composition or make polymerization complete.

Also can use a spot of inhibitor as quinhydrones and so on to prevent or to reduce the degraded of acrylic monomers in storage.The amount of the inhibitor that can add does not reduce the speed of polymerisation in fact or by the bond properties of its composition that makes, typically is about 0.1-5% of polymerisable monomer weight.

Can add various plasticizer and elastic filler (promptly based on polyisoprene, polybutadiene, polyolefin, the rubber polymer of polyurethane and polyester) to improve pliability or toughness.Other possible additive comprises non-reacted colouring agent, filler (for example carbon black) etc.

The amount of employed optional additives is with to polymerization process or can not produce remarkable adverse influence by the desirable performance of its composition that makes and be as the criterion.

As described below, polymerizable acrylic composition of the present invention is particularly useful for the base material of bonding low surface energy, and this in the past if do not use complex surfaces technology of preparing, priming etc. once be difficult to very much bonding.The base material of low-surface-energy is meant that the surface can be less than 45mJ/m ², more typically less than 40mJ/m ²Or less than 35mJ/m ²Material.This material comprises polyethylene, polypropylene, and acrylonitrile-butadiene-styrene (ABS), polyamide and fluorinated polymer such as surface can be less than 20mJ/m ²Polytetrafluoroethylene (PTFE) (TEFLON).Other may be used for the present composition bonding have slightly slightly that the polymer of high surface energy comprises Merlon and polymethyl methacrylate.Yet the present invention is not limited thereto; Composition can be used for bonding any thermoplastic and timber, pottery, the metal of concrete and priming.

Polymerisable compound of the present invention is easy to as two-part adhesive.The component of polymerisable compound is mixed, do so when just as usually using this material.The acid constituents of polymerization initiator system is contained in this mixture usually, comes so that it is divided from the organo-borane amine complex, has obtained the first in two parts composition like this.The organo-borane amine complex of polymerization initiator system provides the second portion of composition, and before needs use composition it is added in the first at short notice.But complex can directly add in the first or predissolve in suitable carriers such as a spot of methyl methacrylate.In case two parts are mixed, should use composition, reason fast is that the order of magnitude of the useful working life of binding agent may be about about 1/4th hours, looks the mixed of monomer, the quantity of complex and carry out bonding temperature and decide.

Polymerisable composition is applied on one or two base material, and pressurization links together base material then, forces excessive composition to be extruded from cementing line.This also is favourable for being exposed to airborne ejecting with the composition that may begin oxidation.Usually, should carry out bondingly in the short time after applying composition, be about preferably in 10 minutes.Typical cementing line thickness is about 0.1-0.3mm, and adhesion process is easily at room temperature carried out and in order to improve the degree of polymerization, wished temperature is remained below about 40 ℃, preferably for being lower than 30 ℃, is preferably lower than about 25 ℃.

Adherend, can allow to fetch to suitable immature intensity with curable in about 2-3 hour.Reach intensity completely at room temperature about 24 hours; If the words of wishing can use heating to carry out after-hardening.

When bonding fluoro-containing plastic, it is favourable before adding the organo-borane amine complex first of two parts composition being cooled to 0-5 ℃.Should after applying composition, finish bonding as early as possible; It also is favourable carrying out bonding operation under less than the temperature of room temperature.

Polymerization initiator system is also very useful in preparation priming paint.The organo-borane amine complex is dissolved in inert organic solvents such as pentane, hexane, benzinum, petroleum solvent, benzene, toluene, ethyl acetate, can make primer solution in the butyl acetates etc., although any above-mentioned organo-borane amine complex all can be used for making priming paint, those that confirm to have extra stability in organic solvent are preferably such as the complex based on the tripropyl monoborane.

The effective dose concentration of complex in solvent is about 5-15wt.%, is about 10wt.% preferably.At about 80-100g/m ²The primer solution that applies 10wt.% down is suitable.If concentration is too low, be inadequate concerning polymerization priming paint with after-applied acrylic acid composition effectively.If concentration is too high, then polymerisation is carried out too soon.Under above-mentioned any situation, the gained adherend all shows low shear adhesion power.

Priming paint should be applied on the surface of two adhesive substrate, on a surface, apply acrylic acid composition although only need subsequently.In case the solvent evaporation applies composition, at once to prevent the oxidative degradation of priming paint after in fact priming paint may deposit.Yet, use priming paint that the advantage of such uniqueness is provided, can make using of acrylic acid composition put off several hrs, but about 7 hours of as many as or longer.In addition, above-mentioned adhesion process is used two parts composition.

Except its remarkable application as adhesive, the polymerisable acrylic acid composition of the present invention also can be used as fluid sealant, coating and injection molding resin, they also can be in resin transfer molded operation for example together with glass and metallic fiber bunch as matrix resin.They also can be used as making component, the sealer in the printed circuit board (PCB) etc. and element is closed in potting compound in the insulating vessel.

The present invention is described in more detail with reference to following unrestricted embodiment, and all wt that wherein provides all is to be the percetage by weight (wt.%) of benchmark in composition total weight (its value is 100%).Listed data are all calculated by a metric position effective digital among the following embodiment.Therefore, be not the summation of all compositions all just in time be 100.0%.

Embodiment 1-13

Embodiment 1-13 has exemplified the incendivity of various organo-boranes and organo-borane amine complex.Mix the organo-borane amine complex cools off organo-borane and amine in the inert argon atmosphere under and form complex and prepare.The incendivity of various organo-boranes and organo-borane amine complex is estimated in " carbonization time " test and " ignition time " test.

Carbonization time is to measure like this: an organo-borane or organo-borane amine complex are applied on 30mm * 30mm bafta sheet, measure the time that fabric begins charing or catch fire (no matter which kind of takes place earlier) experienced.Be to measure like this ignition time, and the bafta sheet with another 30mm * 30mm under inert atmosphere immerses in organo-borane or the organo-borane amine complex, and fabric is exposed in the air, measures the time up to fabric catches fire and experienced.If charing does not take place or catches fire then end test after about 24 hours.Result of the test is listed in the table below in 1.

According to the form below defines term used among these embodiment:

Term definition

The Bu butyl

The i-Bu isobutyl group

The Et ethyl

The Pr propyl group

Table 1

The embodiment sequence number	Organo-borane or organo-borane amine complex	Carbonization time (second)	Ignition time (second)
				1	Pr 3B	1*	1
2	i-Bu 3B	1	1
				3	Bu 3B	1	1
4	Pr 3B·NH 3	4-6	10
				5	Pr 3B·HNEt 2	3*	1
6	Pr 3B·H 2NBu-i	55	104
				7	i-Bu 3B·NH 3	4	4
8	i-Bu 3B·HNEt 2	2	1
				9	i-Bu 3B·H 2NBu-i	12	20
10	2Pr 3B·H 2N(CH 2) 6NH 2	Not charing or catch fire	Do not catch fire
				11	2i-Bu 3B·H 2N(CH 2) 6NH 2	Not charing or catch fire	Do not catch fire
12	Pr 3B·H 2N(CH 2) 6NH 2	Not charing or catch fire	Do not catch fire
				13	i-Bu 3B·H 2N(CH 2) 6NH 2	Not charing or catch fire	Do not catch fire

* catch fire

Table 1 shows that the organo-borane (embodiment 1-3) that cooperates itself very easily do not ignited, and makes these materials and ammonia, and diethylamine or isobutyl amine (embodiment 4-9) cooperate and can not reduce its intrinsic incendivity fully and the complex of gained is become be easy to use.Yet, in embodiment 10-13, organo-borane and 1 wherein, the 6-hexamethylene diamine cooperates, and bafta neither charing is also missing of ignition.The organo-borane amine complex of embodiment 10-13 be do not ignite and can keep stable when at room temperature under other environmental condition, being stored in the airtight container at least about 2 week.Like this, the organo-borane amine complex of embodiment 10-13 is " air-stable ", and can be in the present invention for the usefulness of polymerization initiator system and the composition that makes thus.

Embodiment 14-53

Embodiment 14-53 shows when use adding the polymerizable acrylic adhesive composition of polymerization initiator system, the cohesive of that may have and excellence low surface energy substrates such as polytetrafluoroethylene (PTFE) and polyethylene (PE).

Unless outside pointing out below, in each embodiment, with methacrylate monomers, acrylate monomer and thickener (" Thickener ") stir together, until dissolving fully, heating in case of necessity promotes its dissolving.Add and mixed acid organo-borane amine complex and the extra organo-borane that does not cooperate basically then.In about 10 minutes after preparation of compositions is good, they are applied on polytetrafluoroethylene (PTFE) and the polyethylene base material, and at room temperature carry out the test of overlapping shear strength by (preceding) Soviet Union (GOST) 14759-69 national standard method (" method of shear strength is determined in the bonding connection of metal ").

More specifically, except other has explanation, composition is applied to the thick base material of 60mm * 20mm * 2mm measures on the sample.Spread 200mm to sample ²The overlapping region and the thick adherend of about 0.1-0.3mm.Usually made bonding sample solidifies about 24 hours, and then it was installed in cupping machine and estimates its performance down in the crosshead speed (crosshead speed) of 20mm/min.Listed data are the mean value of five samples.Result of the test is listed in the table below in 2 with megapascal (MPa) (MPa) expression.

For poly bonding, overlapping shear strength value is lower than about 5MPa and is considered to unfavorable usually, and this value is acceptable reluctantly in the scope of about 5-8MPa, and this value then is considered to well greater than about 8MPa.Bonding for polytetrafluoroethylene (PTFE), overlapping shear strength value is lower than about 3MPa and is considered to unfavorable usually, and this value is considered to acceptable reluctantly in the scope of about 3-5MPa, and this value surpasses 5MPa and then is considered to goodish.

Table 2 has equally also been listed the failure mode of various compounds after bonding." A " is meant adhesion failure (being the destruction at interface between base material and the adhesive), and " S " is meant that wood destruction (being the fracture or the elongation of at least one base material) and " M " are meant that mixing destroys (being that the interior destruction of wood destruction and adherend is had both at the same time).Best failure mode is wood destruction and mixes and destroy.

Unless point out in addition below, in each embodiment, methacrylate monomers is a methyl methacrylate, acrylate monomer is a n-butyl acrylate, the organo-borane amine complex is for being the complex that the tripropyl monoborane was cooperated in 1: 1 with monoethanolamine with nitrogen-atoms with the ratio of boron atom, additional organo-borane is the tripropyl monoborane, and thickener is poly-methyl methacrylate acid.

Table 2

The embodiment sequence number	Methacrylate monomers wt.%	Acrylate monomer wt.%	Complex wt.%	Organo-borane wt.%	Acid		Thickener wt.%	Shear strength (MPa)		Failure mode
																	Structural formula	wt.％		PTFE	PE	PTFE	PE
14	61.5	26.0	0.5	1.5	SnCl 4	0.5	10.0	0.6	1.5	A	S
												15	54.5	23.0	0.5	1.5	SnCl 4	0.5	20.0	5.2	10.2	A	S
16	49.1	21.4	0.5	1.5	SnCl 4	0.5	27.0	5.2	12.0	A	S
												17	42.1	18.4	0.5	1.5	SnCl 4	0.5	37.0	5.3	12.0	A	S
18	49.1	21.4	0.5	1.5	SnCl 4	0.5	27.0	5.2	11.7	A	S
												19	49.1	21.4	0.5	1.5	SnCl 4	0.5	27.01 (1)	5.2	11.7	A	S
20	49.1	21.4	0.5	1.5	SnCl 4	0.5	27.0 (2)	5.3	11.2	A	S
												21	54.5	23.0	0.5	1.5	SnCl 4	0.5	20.0 (3)	5.3	11.9	A	S
22	54.5	23.0	0.5	1.5	SnCl 4	0.5	20.0 (2)	4.9	10.2	A	S
												23	54.5	23.0 (4)	0.5	1.5	SnCl 4	0.5	20.0	5.2	12.2	A	S
24	54.5	23.0 (5)	0.5	1.5	SnCl 4	0.5	20.0	5.2	10.4	A	S
												25	54.5 (6)	23.0	0.5	1.5	SnCl 4	0.5	20.0	5.0	9.9	A	S
26	37.2	24.8	5.0	1.0	HCl (8)	5.0	27.0	5.1	11.2	A	S
												27	39.9	26.6	3.0	0.5	HCl (8)	3.0	27.0	1.5	11.4	A	S
28	37.7	25.2	5.0	0.1	SnCl 4	5.0	27.0	3.2	12.0	A	S
												29	40.1	26.8	3.0	1.0	SnCl 4	3.0	27.0	5.0	11.5	A	S
30	47.7	18.5	0.5	3.0	SnCl 4	0.5	30.0	5.3	12.4	A	S
												31	37.7	25.2	5.0	0.1	TiCl 4	5.0	27.0	3.0	11.9	A	S
32	37.2	24.8	5.0	1.0	H 2SO 4	5.0	27.0	4.2	10.8	A	S
												33	38.1	25.9	5.0	1.0	H 3PO 4	3.0	27.0	4.0	10.5	A	S
34	39.8	26.2	3.0	1.0	H 3PO 4	3.0	27.0	4.5	11.3	A	S
												35	13.9	63.6	0.5	1.5	H 3PO 4	0.5	20.0	5.3	12.2	A	S
36	47.5	20.0	0.5	1.5	H 3PO 4	0.5	30.0	5.3	11.5	A	S
												37	38.0	38.5	1.0	1.5	SnCl 4	1.0	20.0	4.8	12.1	A	S
38	69.0	5.0	0.5	5.0	SnCl 4	0.5	20.0	3.6	9.1	A	S

The embodiment sequence number	Methacrylate monomers wt.%	Acrylate monomer wt.%	Complex wt.%	Organo-borane wt.%	Acid		Thickener wt.%	Shear strength (MPa)		Failure mode
												39	72.5	5.0	0.5	1.5 (8)	SnCl 4	0.5	20.0	5.1	11.9	A	S
40	44.1	29.4	3.0	0.5	CH 3- COOH	3.0	20.0	4.2	11.2	A	S
												41	44.1	29.4	3.0	0.5	CH 2＝ CCOOH	3.0	20.0	3.6	10.8	A	S
42	44.1	29.4	3.0	0.5	CH 2＝ C(CH 3) -COOH	3.0	20.0	3.2	10.5	A	S
												43	49.6	21.4	0.0	2.0	SnCl 4	2.0	25.0	0.5	1.1	A	A
44	51.0	20.4	0.0	1.2	SnCl 4	0.4	27.0	0.8	1.3	A	A
												45	50.7	20.3	0.0	1.6	SnCl 4	2.4	25.0	0.8	1.2	A	A
46	52.1	20.9	0.0	1.6	SnCl 4	0.4	25.0	0.7	1.1	A	A
												47	47.2	17.8	0.0	7.0	SnCl 4	3.0	25.0	0.1	0.4	A	A
48	47.6	16.4	0.0	4.0	SnCl 4	7.0	25.0	0.1	0.2	A	A
												49	49.6	21.4	2.0	0.0	SnCl 4	2.0	25.0	0.5	1.1	A	A
50	68.1	30.0	0.0	1.4 (8)	NA	0.0	0.0	0.0	0.0	NA	NA
												51	49.0	0.0	0.0	2.0 (8)	NA	0.0	49.0	0.0	0.0	NA	NA
52	50.0	21.2	0.4	0.05	SnCl 4	0.4	27.0	0.3	0.9	A	A
												53	61.0	31.5	0.5	1.5	SnCl 4	0.5	5.0	0.1	0.3	A	A

NA=can't use 5 olefin(e) acids 1,1,5-three hydrogen octafluoro pentyl esters

1 quartz powder, 6 butyl methacrylates

7 1.1 moles of 2 polystyrene-butylene

3 fused silicas, 8 tributyl monoboranes

4 methyl acrylates

Embodiment 14-17 has illustrated the change methacrylate monomers, the effect of acrylate monomer and thickener relative quantity, in embodiment 14, said composition is used insufficient thickener, the result causes a runny acryloid cement, and this adhesive does not demonstrate extraordinary overlapping shear strength to polytetrafluoroethylene (PTFE) and polyethylene.Remaining embodiment demonstrates the cohesive of comparatively improving.It is useful that the polymethyl methacrylate thickener of about 20-40wt.% is added in the composition of the present invention.In a word, thickener needs, and decides on the selection of acrylic monomers.If use monomer, then may not need thickener with enough high viscositys and enough high-vapor-pressures.

Embodiment 16 has illustrated the effect (polymethyl methacrylate of embodiment 18 is from different sources) that changes thickener types in the situation that prescription is identical in addition with 18-20.Just changed bonding force a little to polyethylene and polytetrafluoroethylene (PTFE).Except the polymethyl methacrylate thickener, also can use quartz powder, fused silica and polystyrene-butylene.Embodiment 15,21 and 22 can be made comparisons similarly.When using these different thickeners, very little to the change of bonding force.

Embodiment 15,23 and 24 has illustrated and has changed acrylate monomer into methyl acrylate or acrylic acid 1,1 from n-butyl acrylate that 5-three hydrogen octafluoro pentyl esters can not influence significantly to polytetrafluoroethylene (PTFE) or poly overlapping shear strength.Embodiment 15 and 25 explanations can successfully add methyl methacrylate and butyl methacrylate monomer in the polymerisable composition of the present invention.

Embodiment 26-39 has illustrated owing to change methacrylate monomers, acrylate monomer, the organo-borane amine complex, during the relative quantity of organo-borane and thickener, for the influence of the overlapping shear strength of polytetrafluoroethylene (PTFE) and the prepared adherend of polyethylene.Embodiment 39 uses the tributyl monoborane, but not the tripropyl monoborane demonstrates thus and can use alternative boron alkyl alkanes in addition.The effect of using the various acid (stannic chloride, titanium chloride, hydrochloric acid, sulfuric acid and phosphoric acid) of different amounts also has been described.Although embodiment 30 is different in many aspects with 35, all provide cohesive to polytetrafluoroethylene (PTFE) and poly excellence.Polytetrafluoroethylene (PTFE), a kind of is to be difficult to very much bonding material in the past, it is compared with polyethylene, seems that the variation to composition has bigger sensitiveness.Change the organo-borane amine complex, the relative quantity of organo-borane and acid can have the influence of cohesive force more than two times to the polytetrafluoroethylene (PTFE) bonding force, and is then obviously less to the influence of polyethylene bonding force.

Embodiment 40-42 explanation is in previous embodiment the used inorganic acid, and various organic acids (for example acetate, acrylic acid and methacrylic acid) also can be used for polymerisable compound of the present invention.Organic acid because it is easily handled preferably.

Embodiment 43-48 has illustrated the effect for preparing various adhesive compositions when not comprising the organo-borane amine complex.Polyethylene and polytetrafluoroethylene (PTFE) had only minimum bonding force.

Embodiment 49 has shown when comprising the organo-borane source that does not provide additional based on the organo-borane amine complex of monoethanolamine, polyethylene has been obtained acceptable adhesion force, and polytetrafluoroethylene (PTFE) is only observed minimum bonding force.Like this, when complex was based on monoethanolamine, the additional organo-borane source that is not cooperation basically was essential to the excellent bonding of polytetrafluoroethylene (PTFE), and quite different to polyethylene.Organo-borane can provide with above-mentioned any organo-borane, uses altogether with complex.Those complexs of using for organo-borane preferably also can be used as the source of additional organo-borane preferably.Molal quantity in the acrylic acid degree of functionality is a benchmark, and the amount of the organo-borane that does not cooperate is about 0.1-7mol% preferably basically, is about 0.2-6mol% better, is about 1-3mol% best.Yet, as shown below, change amine into 1, during the 6-hexamethylene diamine, even when not being provided, additional organo-borane source also can obtain bonding force to the excellence of polytetrafluoroethylene (PTFE).

Embodiment 50 and 51 has illustrated to provide and has comprised that neither the organo-borane amine complex does not comprise the result that adhesive composition obtained of acid and optional thickener (embodiment 50) or optional acrylate monomer (embodiment 51) yet.Polyethylene or polytetrafluoroethylene (PTFE) all there is not cohesive.The composition of these embodiment comprises the tributyl monoborane.

Embodiment 52 and 53 composition have illustrated and have used the organo-borane (embodiment 52) and the effect of thickener (embodiment 53) very little very little.

From the foregoing description as seen, desirable especially polymerisable compound of the present invention comprises, gross weight in composition is a benchmark, the alkyl acrylate monomer of about 5-65wt.% (being butyl acrylate preferably), the organo-borane amine complex of about 0.5-5wt.% (being tripropyl monoborane-monoethanolamine complex preferably), the additional organo-borane (being the tripropyl monoborane preferably) of about 0.1-5wt.%, the acid of about 0.5-5wt.%, the thickener of about 20-40wt.% (being polymethyl methacrylate preferably), remaining (about 10-65wt.%) are alkyl methacrylate (being methyl methacrylate preferably).

Embodiment 54

Being particularly suitable for bonding fluorinated polymer and poly adhesive composition can be by mixed 42.1wt.% methyl methacrylate, and 18.4wt.% butyl acrylate and 37.0wt.% polymethyl methacrylate thickener make until dissolving fully.Add 0.5wt.%SnCl4 acid then, add the mixture of 1.5wt.% tripropyl monoborane and 0.5wt.% monoethanolamine subsequently.In case mixed, composition is applied on polyethylene base material and the polytetrafluoroethylene (PTFE) base material.Connect two blocks of base materials, under environmental condition, solidified 24 hours, and carry out the test of overlapping shear strength by GOST 14759-69 in the above described manner.Overlapping shear strength under wood destruction is 5.1Mpa.

Embodiment 55-57

Use listed percetage by weight in the table 3, by mixed methyl methacrylate monomer, Butyl Acrylate Monomer and polymethyl methacrylate thickener prepare a series of adhesive composition of the present invention until dissolving fully.Under agitation add acid and then add the organo-borane amine complex.Unless outside pointing out in addition below, acid is methacrylic acid, the organo-borane amine complex is based on tripropyl monoborane and 1,6-hexamethylene diamine (nitrogen-atoms is 1: 1 with the ratio of boron atom).Method by aforesaid GOST 14759-69, polyethylene (PE) is used in preparation, polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are the bonding compound of base material (each base material is bonded on another base material of same material), under environmental condition, solidified 48 hours, overlapping shear strength is tested, be the results are shown in the following table 3.Also listed the failure mode of bonded composite as defined above in the table 3.

Table 3

The embodiment sequence number	Methyl methacrylate monomer wt.%	Butyl Acrylate Monomer wt.%	Organo-borane amine complex wt.%	Acid wt.%	Thickener wt.%	Shear strength (MPa)			Failure mode
												PE	PTFE	PVC	PTFE	PE	PVC
						55	40.8	28.2	0.5	0.5	30.0							12.1	8.8	11.5	S	S	S
56	37.9	27.2	2.9	2.9	29.1							11.8	9.0	11.7	S	S	S
						57	36.2	25.7	4.8	4.8	28.6							11.5	9.3	11.3	S	S	S
58	34.6	24.3	6.5	6.5	28.0							10.9	8.4	10.7	S	S	S
						59	35.6	28.7	3.0	3.0	29.7							12.2	10.1	11.7	S	S	S
60	39.8	30.1	2.9	2.9	24.3							10.8	9.5	10.5	S	S	S
						61	30.0	27.0	3.0	3.0	37.0							11.7	9.7	11.4	S	S	S
62	39.3	13.1	6.5	6.5	34.6							11.5	8.1	10.3	M	S	S
						63	35.6	38.6	0.5	0.5	24.8							10.5	7.8	9.6	M	S	S
64	11.8	52.9	2.9	2.9	29.4							11.0	8.9	10.4	S	S	S
						65	36.9	28.2	2.9 (1)	2.9	29.1							11.2	9.2	10.8	S	S	S
66	36.9	28.2	2.9	2.9 (2)	29.1							10.7	8.4	10.8	S	S	S
						67	36.9	28.2	2.9	2.9	29.1							12.3	9.9	11.0	S	S	S
68	36.9	28.2	2.9	2.9	29.1							10.8	9.3	11.6	S	S	S
						69	36.9	28.2	2.9 (3)	2.9	29.1							11.2	9.3	10.1	S	S	S
70	36.9	28.2	2.9 (4)	2.9	29.1							11.4	9.0	10.5	S	S	S
						71	41.5	27.9	0.4	0.4	29.9							5.3	3.2	4.3	A	A	S
72	31.2	24.8	8.3	8.3	27.5							1.2	0.7	1.5	A	A	A
						73	44.7	30.1	2.9	2.9	19.4							3.6	2.3	3.8	A	A	A
74	9.9	54.5	3.0	3.0	29.7							3.5	2.0	3.1	A	A	A
						75	52.1	10.4	3.1	3.1	31.3							2.5	1.8	2.9	A	A	A

¹Based on triisobutyl monoborane and 1,6-hexa-methylene two ³Based on tri-n-butyl borane and 1, (nitrogen-atoms: ratio=1 of boron atom: complex 1) is by (nitrogen-atoms: ratio=1 of boron atom: complex 1) for the 6-hexamethylene diamine

²Acrylic acid ⁴Nitrogen-atoms: ratio=2 of boron atom: 1

Embodiment 55-59 has illustrated when changing methyl methacrylate monomer, Butyl Acrylate Monomer, and during the relative quantity of methacrylic acid and polymethyl methacrylate thickener, to polyethylene, the fusible influence of polytetrafluoroethylene (PTFE) and polyvinyl chloride.Embodiment 60-64 has done similar comparison, has also changed the amount of complex.

Embodiment 65-70 has illustrated change organo-borane amine complex, the result that acid and thickener obtain.In embodiment 65, the ratio that the organo-borane amine complex is based on nitrogen-atoms and boron atom is 1: 1 a triisobutyl monoborane and 1, the 6-hexamethylene diamine.In embodiment 66, acid is acrylic acid.Embodiment 67 and the 68 polymethyl methacrylate thickeners that use from separate sources.

Embodiment 69 uses based on tri-n-butyl borane and 1,6-hexamethylene diamine (ratio=1 of nitrogen-atoms and boron atom: alkyl monoborane amine complex 1).The ratio that the organo-borane amine complex of embodiment 70 is based on nitrogen-atoms and boron atom is 2: 1 a tripropyl monoborane and 1, the 6-hexamethylene diamine.

Embodiment 71 and 72 has illustrated and has contained in adhesive composition very little or too many complex and very little or too many sour effect.Embodiment 73 has confirmed the cohesive of the difference that obtained when using insufficient thickener.Therefore the viscosity of the adhesive composition of embodiment 73 is too low and begin oxidation prematurely.Embodiment 73 is opposite with the embodiment 15 that overcomes premature oxidation with the organo-borane that existence adds.Embodiment 74 has confirmed the use of a small amount of methacrylate monomers and relatively large acrylate monomer.Embodiment 75 has illustrated relativeness.

From the foregoing description as seen, the desirable especially polymerisable compound of the present invention comprises, gross weight in composition is a benchmark, the alkyl acrylate of about 10-55wt.% (being butyl acrylate preferably), the alkyl methacrylate of about 10-50wt.% (being methyl methacrylate preferably), the organo-borane amine complex of about 0.5-7wt.% (is a tripropyl monoborane-1 preferably, 6-hexamethylene diamine complex), the thickener of the acid of about 0.5-5wt.% (being acrylic or methacrylic acid preferably) and about 25-40wt.% (being polymethyl methacrylate preferably).

Embodiment 76-98

Embodiment 76-98 has exemplified the another kind mode preferably of using polymerization initiator system of the present invention.In these embodiments, treat bonding base material with the priming paint that is contained in the organo-borane amine complex in the organic solvent and carry out preliminary treatment (for example spraying or brushing).In case after applying, the evaporation of priming paint solvent is with after-applied polymerisable acrylic adhesive composition.Pave base material then, made it to solidify 24-48 hour, then carry out the test of overlapping shear strength by the method for above-mentioned GOST14759-69.Use polyethylene (PE), the result of the test of polyvinyl chloride (PVC) and polytetrafluoroethylene (PTFE) base material (each base material is bonded on second base material of same material) to be listed in the table below in 4 these." open-assembly time " be meant priming paint be applied on the base material after and adhesive apply before that priming paint is exposed to the airborne time.

More specifically, unless following have outside the explanation in addition, the organo-borane amine complex is for based on the ratio of nitrogen-atoms and boron atom (N: B) be 1: 1 tripropyl monoborane and 1, the 6-hexamethylene diamine; Complex is dissolved in pentane (solvent) and becomes 10% solution; Polymerizable binder comprises the methyl methacrylate monomer of 39wt.%, the Butyl Acrylate Monomer of 35wt.%, the polymethyl methacrylate thickener of the methacrylic acid of 1wt.% and 25wt.%.

Table 4

The embodiment sequence number	The paint base composition remarks	Open-assembly time (branch)	Shear strength (MPa)
									PE	PVC	PTFE
76	5% solution	10	9.4	8.2	8.2
						77	8% solution	10	10.1	8.8	9.5
78	No remarks	10	10.2	8.2	9.4
						79	12% solution	10	10.3	8.7	9.6
80	No remarks	30	12.1	9.1	9.6
						81	No remarks	60	11.3	8.8	9.5
82	No remarks	120	10.8	8.9	9.4
						83	No remarks	180	10.5	8.7	9.8
84	No remarks	360	9.8	8.5	8.5
						85	No remarks	420	9.7	8.6	8.3
86	No remarks	480	5.7	5.3	4.3
						87	N∶B＝2.5∶1	20	9.8	8.5	8.4
88	N∶B＝2∶1	20	10.1	8.2	8.7
						89	N∶B＝1.3∶1	20	10.5	8.8	9.1
90	N∶B＝0.9∶1	20	9.7	8.4	8.9
						91	Complex uses triisobutyl monoborane and 1,6-hexamethylene diamine	20	11.3	8.9	9.5

92	Complex uses triisobutyl monoborane and 1,6-hexamethylene diamine N: B=2: 1	20	10.3	8.0	8.5
						93	Hexane solvent	20	11.5	8.9	9.1
94	Petroleum ether solvent	20	11.3	8.7	9.0
						95	Petroleum solvent	20	11.1	8.6	9.2
96	Benzene solvent	20	10.9	8.4	9.5
						97	Toluene solvant	20	11.0	8.5	8.7
98	Butyl acetate solvent	20	10.7	8.3	8.4

Embodiment 76-79 has exemplified and concentration can be used for the present invention for the primer solution of about 5%-12%.Embodiment 78 and 80-86 pointed out in case applied priming paint, the base material of having gone up priming paint can be exposed in the air to reach at least 7 hours, and can not produce adverse influence to the intensity of adherend subsequently.In embodiment 78 and 87-90, the ratio of the nitrogen-atoms in the organo-borane amine complex and boron atom is 0.9: 1-2.5: change in 1 the scope, and can be to bonding generation adverse influence.

Embodiment 91 and 92 points out that useful organo-borane amine complex can be by triisobutyl monoborane and 1, and the 6-hexamethylene diamine makes.Embodiment 93-98 has exemplified the useful organic solvent that a large amount of can be used for prepares paint base composition of the present invention.

Embodiment 99-106

Embodiment 99-106 has further exemplified the preparation and the use of priming paint of the present invention.Priming paint is prepared and uses by the method described in embodiment 76-98 (the tripropyl monoborane and 1 in pentane, 6-hexamethylene diamine).Except embodiment 99 (N: B=4: 1) and embodiment 100 (N: B=0.8: 1), the ratio (N: B) be 1: 1 of nitrogen-atoms and boron atom.The concentration of primer solution, open-assembly time, " hardening time " (promptly bonding compound solidifies the time of being experienced before test) and overlapping shear strength test result (by GOST 14759-69) is listed in the table below in 5.

Bonding compound is by the adhesive composition that is prepared and uses described in the embodiment 76-98 among these embodiment.

Table 5

The embodiment sequence number	The concentration of primer solution (wt.%)	Open-assembly time (branch)	Hardening time	Shear strength (MPa)
											PE	PVC	PTFE
99	10	20	24 hours	2.1	2.3	1.7
							100	10	20	24 hours	2.5	2.7	1.9
101	3	20	24 hours	3.2	2.5	1.3
							102	15	20	24 hours	5.6	4.9	4.1
103	15	420	60 hours	9.6	8.5	8.4
							104	15	420	10 days	9.7	8.4	8.3
105	15	420	30 days	9.8	8.2	8.5
							106	15	420	June	9.5	8.3	8.6

Influence when embodiment 99 has illustrated when the ratio too high (4: 1) of nitrogen-atoms and boron atom bonding influence and embodiment 100 illustrated this ratio too low (0.8: 1).This ratio should be about 1: 1-2: in 1 the scope, be about 1 preferably: 1-was about 1: 1-1.5 less than 2: 1 better: 1, and be about 1: 1 best.

Embodiment 101 has illustrated owing to use the adhesion results of the reduction that priming paint obtained that contains low concentration organo-borane amine complex.When primer solution concentration when 15% (embodiment 102) are brought up in 3% (embodiment 101), cohesive is improved significantly.

Embodiment 103-106 has confirmed primer solution of the present invention to be exposed to that (after being applied on the base material) reaches at least 7 hours in the air, and can not produce adverse influence to the adherend that makes subsequently.Even before test after aging 6 months the shear strength of adherend can not reduce significantly yet.

Embodiment 107-110

Embodiment 107-110 has exemplified to use and has contained the polymerizable acrylic composition effect that priming paint obtained of (also containing organic borine amine complex).

In embodiment 107 and 108, described in embodiment 99-106, with the tripropyl monoborane-1 that is contained in the pentane, 10% primer solution of 6-hexamethylene diamine complex is applied to polyethylene (PE), on polyvinyl chloride (PVC) and the polytetrafluoroethylene (PTFE) base material.Preparation contains the 44.1wt.% methyl methacrylate monomer, the 29.4wt.% Butyl Acrylate Monomer, the 3.0wt.% methacrylic acid, 20wt.% polymethyl methacrylate thickener, 0.5wt.% tripropyl monoborane and 3.0wt.% tripropyl monoborane-monoethanolamine complex (the N atom: polymerizable acrylic adhesive B atom=1: 1), and make it to be kept at one period that in following table 6, is called as " pot life " in the mixed container.Then acrylic adhesive composition is applied on the base material of going up priming paint.In each embodiment, 10 minutes after-applied acryloid cements have been applied at priming paint.Prepare bonding compound, solidify and test, the results are shown in the following table 6 by GOST 14759-69.Overlapping shear strength test result also lists in the table 6.

Except not being applied to priming paint on the base material, embodiment 109 and 110 is prepared in an identical manner and tests.

Table 6

The embodiment sequence number	Apply priming paint	Deposit a jar time (branch)	Shear strength (MPa)
									PE	PVC	PTFE
107	Have	20	10.3	8.7	8.4
						108	Have	30	10.5	9.1	8.7
109	Do not have	20	1.0	0.8	0.0
						110	Do not have	5	10.5	3.2	0.0

Embodiment 107-110 has illustrated and has used priming paint of the present invention can prolong the operating period of the composition that also comprises polymerization initiator.The useful operating period of embodiment 109 and 110 adhesive is 5-20 minute concerning polyethylene and polyvinyl chloride, is less than 5 minutes concerning polytetrafluoroethylene (PTFE).Yet concerning using priming paint, the operating period can extend to greater than 30 minutes.

Embodiment 111-114

Except using different priming paint and different adhesive, embodiment 111-114 and embodiment 107-110 are similar.Except the ratio of nitrogen-atoms and boron atom is 1.3: 1, similar among the priming paint among these embodiment (only in embodiment 111 and 112, applying) and the embodiment 107 and 108.Open-assembly time is 60 minutes.Polymerisable acryloid cement comprises the 40.8wt.% methyl methacrylate monomer, the 27.2wt.% Butyl Acrylate Monomer, the 1.0wt.% methacrylic acid, 30.0wt.% polymethyl methacrylate thickener and 1.0wt.% tripropyl monoborane-1,6-hexamethylene diamine complex (nitrogen-atoms: ratio=1 of boron atom: 1).By preparing bonding compound described in the foregoing description 107-110 and testing, the results are shown in the following table 7.

Table 7

The embodiment sequence number	Apply priming paint	Deposit a jar time (branch)	Shear strength (MPa)
						PE	PVC	PTFE
			111	Have	60				10.7	8.4	8.4
112	Have	120				10.3	8.1	8.8
			113	Do not have	20				0.9	1.2	0.7
114	Do not have	5				12.1	8.8	11.5

Owing to used priming paint, the operating period of the adhesive composition among these embodiment is from extending to greater than 2 hours less than 20 minutes.

Embodiment 115 and 116

Prepare a series of polymerisable acrylic monomers compositions to estimate the practicality of different amine in preparation organo-borane amine complex.Each composition contains the 19.2wt.% n-butyl acrylate, the 55.3wt.% methyl methacrylate, 22.4wt.% polymethyl methacrylate thickener, the ratio of the nitrogen-atoms of 0.8wt.% methacrylic acid and 2.2wt.% and boron atom are 1: 1 tripropyl monoborane amine complex.Used various amine and the overlapping shear strength test of polyethylene (PE) and polytetrafluoroethylene (PTFE) (solidifying in 24 hours) be the results are shown in the following table 8.

Table 8

The embodiment sequence number	Amine	Shear strength (MPa)
				PE	PTFE
		115	Aniline			1.5	0
116	Triethylamine			10.9	0

These embodiment do not show any cohesive to polytetrafluoroethylene (PTFE).And the organo-borane amine complex is ignited when testing by above-mentioned carbonization time and ignition time, thereby they are very inappropriate.

Embodiment 117 and 118

Being prepared as follows listed in the table 9 two kinds contains methacrylate monomers but does not contain the polymerisable compound of acrylate monomer.In each embodiment, methacrylate monomers is a methyl methacrylate, thickener is a polymethyl methacrylate, and acid is methacrylic acid and organo-borane amine complex for based on hexamethylene diamine and tripropyl monoborane (ratio=1 of nitrogen-atoms and boron atom: 1).As shown in table 9, the bonding compound by the above preparation use polyethylene and polytetrafluoroethylene (PTFE) solidified 24 hours under environmental condition before the overlapping shear strength of test.

Table 9

The embodiment sequence number	Methyl methacrylate wt.%	Acid wt.%	Organo-borane amine complex wt.%	Thickener wt.%	Shear strength (MPa)
							PE	PTFE
					117	52.2			6.6	6.6	34.6	10.7	2.3
118	56.3	3.2	3.2	37.4			0	0

Embodiment 117 and 118 has shown in the polymerisable compound that only contains methacrylate monomers, must use additional organo-borane amine complex and acid to reach the acceptable cohesive to polyethylene and polytetrafluoroethylene (PTFE).

Embodiment 119 and 120

Embodiment 119 and 120 has described the mode of other preparation priming paint of the present invention.Embodiment 119 comprises two (tributyl peroxy) antimony triphenyl, 73.1wt.% methyl methacrylate monomer and the 25.4wt.% Butyl Acrylate Monomers of 0.5wt.%.Composition to gained outgases, and adds the tripropyl boron of 1.0wt.% then therein.Then give polytetrafluoroethylene (PTFE) sample priming, and be adhered on the similar sample of using polyurethane binder priming with this composition.Overlapping shear strength (when when testing as mentioned above) is 6.3MPa.Priming does not demonstrate cohesive with reference to embodiment.Because composition outgases, peroxide provides oxygen source.If composition is without the degassing, then aerial oxygen does not enough need the peroxide that adds as oxygen source.

In embodiment 120, give polyethylene sample priming with a composition, described composition comprises the 39wt.% methyl methacrylate, the 25wt.% n-butyl acrylate, the 30wt.% polymethyl methacrylate, 3wt.% organo-borane amine complex (ratio of nitrogen-atoms and boron atom be 1: 11,6-hexamethylene diamine and tripropyl monoborane) and 3wt.% methacrylic acid.When bonding 0 to the similar base material that applies with epoxy adhesive the time, the overlapping shear strength that bonding compound demonstrates (when by above-mentioned the test) is 6.0MPa.Priming does not show cohesive with reference to embodiment.

This acrylic monomers that comprises, organo-borane and oxygen source or comprise acrylic monomers, the composition of organo-borane amine complex and acid can be used for to the fluoro-containing plastic priming to improve the cohesive with after-applied adhesive.

Embodiment 121-125

Embodiment 121-125 has shown the ratio (N: B) to the influence of polymerizable acrylic composition properties of the present invention of nitrogen-atoms and boron atom.Prepare a series of various nitrogen-atoms and boron atom ratio (listed) as following table 10 based on 1, the organo-borane amine complex of 6-hexamethylene diamine and tri-n-butyl borane.The 0.186g complex is added 5g by the 78g methyl methacrylate monomer, and 56g acrylic acid 2-butyl ester monomer is in the polymerizable acrylic composition that the polymethyl methacrylate thickener of 60g intermediate molecular weight and 6g methacrylic acid make.

Preparation has 161mm ²Overlapping area and 0.15mm bondline thickness based on polyethylene (PE), the bonding compound of polypropylene (PP) and polytetrafluoroethylene (PTFE) (each base material is adhered on the base material of same material), fix with adhesive tape and fastening clamp, under environmental condition, solidified 24 hours.It is thick that tested base material is about 25mm * 100mm * 3mm.On cupping machine, use the crosshead speed of 2.5mm/min that bonding compound is carried out destructive testing then.The results are shown in the following table, the value of wherein listing is the mean value of 3 samples.Embodiment 121 and 122 has shown wood destruction.Remaining embodiment is an adhesion failure.

Table 10

The embodiment sequence number	N∶B	Overlapping shear strength (MPa)
					PE	PP	PTFE
		121	1∶1	4.9				4.1	1.9
122	1.5∶1				5.3	3.0	1.4
		123	2∶1	2.4				2.5	0.3
124	3∶1				0.3	0.1	0.0
		125	4；1	0.3				0.2	0.0

These embodiment show when using polymerisable compound of the present invention, possible wondrous and beyond thought fusible improvement to various low surface energy substrates.

Under the precursor that does not depart from the spirit of the present invention that limits in the appended claims, the various changes and improvements of being done in above-mentioned specification scope are possible.

Claims (2)

1. bonding compound, it comprises first base material, the acrylic acid composition of the polymerization of second base material and polymerisable acrylic acid composition that first and second base materials are bonded together, wherein first base material have low surface can, described polymerisable acrylic acid composition comprises:

(a) at least a acrylic monomers;

(b) the organo-borane amine complex with following structural formula of effective dose: Wherein:

R ¹For containing the alkyl of 1-10 carbon atom;

R ²And R ³Be independently selected from the alkyl that contains phenyl groups and contain 1-10 carbon atom;

R ⁴For being selected from CH ₂CH ₂OH and (CH ₂) _xNH ₂Group, wherein x is the integer greater than 2;

R ⁵For hydrogen or contain the alkyl of 1-10 carbon atom; With

Nitrogen-atoms is 1 with the ratio of boron atom: 1-1.5: 1 He

(c) acid that is used to cause polymerizable acrylic monomer of effective dose.

2. bonding compound as claimed in claim 1, wherein first and second base materials all are independently selected from polyethylene, polypropylene, polyvinyl chloride and fluoro-containing plastic.