CN103980847A - Self-curing polyacrylate-epoxy resin adhesive as well as preparation method and application of self-curing polyacrylate-epoxy resin adhesive - Google Patents
Self-curing polyacrylate-epoxy resin adhesive as well as preparation method and application of self-curing polyacrylate-epoxy resin adhesive Download PDFInfo
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- CN103980847A CN103980847A CN201410216131.3A CN201410216131A CN103980847A CN 103980847 A CN103980847 A CN 103980847A CN 201410216131 A CN201410216131 A CN 201410216131A CN 103980847 A CN103980847 A CN 103980847A
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Abstract
The invention discloses a self-curing polyacrylate-epoxy resin adhesive as well as a preparation method and application of the self-curing polyacrylate-epoxy resin adhesive. The preparation method comprises the steps of (1) weighing a polyacrylic polymer (A) with the glass transition temperature of 65 DEG C below zero to 10 DEG C, epoxy resin (B) and an acid anhydride curing agent (C), wherein the molar ratio of (B) to (C) is 0.95-1.2, and the mass ratio of (A) to (B+C) is 0.5-2.0; (2) dissolving (A), (B) and (C) into a solvent to prepare a solution with the mass concentration of 40-60%. The self-curing polyacrylate-epoxy resin adhesive disclosed by the invention has favorable initial adhesion at normal temperature and can be cured after being applied to a high-temperature environment so as to have favorable bonding strength. The method disclosed by the invention is simple in preparation. The adhesive is independently packaged so as to be convenient to use.
Description
Technical field
The present invention relates to a kind of self cure Polyacrylic Ester and Epoxy Resin sizing agent and Preparation method and use.
Background technology
Sizing agent is widely used in all respects from daily life to high-technology field at present as a kind of functional high molecule material, and according to the difference of actual application environment and application conditions, people have constantly proposed new requirement to the performance of sizing agent.Pressure sensitive adhesive is one of kind of consumption maximum in sizing agent, and it is that material of main part is formulated that general employing has compared with the polymkeric substance of low Tg, so pressure sensitive adhesive has shown good tack.But in some practical application, require sizing agent to there is good tack on the one hand, on the other hand also need to be after bonding process complete, bonded structure has good weather resistance, high thermal resistance etc.Like this, common pressure sensitive adhesive just can not meet application requiring.
In fact, adopt acrylic ester polymer and modifier thereof, epoxy resin, resol, urethane, cyanate, silicone based and heterocyclic polymer etc. all can realize resistant to elevated temperatures performance, but let us also need to consider the accessibility using.Mostly current high-temperature Resistance Adhesives is on the market hot melt adhesive, or bi-component package, uses very inconvenient.
The most frequently used low Tg polymkeric substance is polyacrylic ester.Acrylate monomer is of a great variety, has the monomer of different structure by homopolymerization or copolymerization, second-order transition temperature that can modulation polymer.The polyacrylic ester of suitable molecular weight and molecular structure can show good adhesiveproperties (comprise tack and hold viscosity).But polyacrylic ester has a disadvantage, along with the rising of environment for use temperature, the polyacrylic ester of low Tg, by deliquescing, even occurs to flow, the intensity of itself can significantly decline with temperature rise, and this has just limited the application of polyacrylic ester in temperature tolerance sizing agent.Certainly, also can adopt polyacrylate blending thing or the multipolymer of high glass transition temperature and low Tg to prepare sizing agent, but have this specific character sizing agent tack and hold viscosity and be conventionally difficult for obtaining best balance, may occur that tack is good and heatproof is bad, or temperature tolerance is fine and result that tack is not good.
Another material conventional in sizing agent is exactly epoxy resin, and epoxy resin is in fact a kind of oligopolymer, has solid-state or liquid-state epoxy resin kind, and general liquid-state epoxy resin molecular weight is lower, but the content of epoxy group(ing) is higher; Solid-state epoxy resin has higher molecular weight and lower epoxy group content.After solid epoxy resin is heated, can soften, melting, become thickness state or liquid state; The liquid resin reduced viscosity that is heated.But be only common being heated, epoxy resin can't occur crosslinked or curing, and its molecular weight can't enlarge markedly, thereby does not possess the mechanical property of actual needs.Only add suitable solidifying agent compositing formula resin, and be cured reaction under certain condition, generating three-dimensional tridimensional network.Now epoxy resin, by changing into a kind of insoluble not molten macromolecular solid compound, just can show various good performances.But the common fragility of epoxy resin adhesive is large, be unsuitable for preparing pressure sensitive adhesive.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide one to there is at normal temperatures good tack, after being applied in hot environment, can progressively be subject to thermofixation, improve and hold viscosity and bonding strength, thereby there is the self cure Polyacrylic Ester and Epoxy Resin sizing agent of good bonding intensity.
Second object of the present invention is to provide a kind of preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent.
The 3rd object of the present invention is to provide a kind of purposes of self cure Polyacrylic Ester and Epoxy Resin sizing agent.
Technical scheme of the present invention is summarized as follows:
The preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent, comprises the steps:
(1) getting second-order transition temperature is the polyacrylate polymers (A) of-65 DEG C～10 DEG C; Epoxy resin (B) and acid anhydride type curing agent (C); Described (B) and mol ratio (C) are 0.95～1.2, and described (A) is 0.5～2.0 with mass ratio (B+C);
(2) by (A), (B) and (C) be dissolved in that in solvent, to make mass concentration be 40%～60% solution.
Solvent ethyl acetate, acetone and DMF at least one.
Second-order transition temperature is that the polyacrylate polymers (A) of-65 DEG C～10 DEG C is made by the following raw material of quality:
(1) get the Isooctyl acrylate monomer of 0～93 part, the butyl acrylate of 0～65 part, the methyl methacrylate of 0～54 part, the vinyl acetate of 0～35 part; And when Isooctyl acrylate monomer, butyl acrylate, methyl methacrylate and vinyl acetate are different, be 0;
(2) linking agent of the initiator of 0.2～5 part and 0～2 part is joined in the liquid that 100 parts of steps (1) obtain, mix, obtain mixed solution;
(3) mixed solution step (2) being obtained splashes in the 60-400 part organic solvent under nitrogen atmosphere, at 60～80 DEG C, reacts 4～6.5 hours, obtains second-order transition temperature and be the polyacrylate polymers (A) of-65 DEG C～10 DEG C.
The preferred Phthalic acid, diallyl ester of linking agent, Vinylstyrene or N,N methylene bis acrylamide.
Organic solvent is preferably ethyl acetate, toluene, dimethylbenzene or acetone.
Preferably 200～the 3800g/mol of epoxy equivalent (weight) of epoxy resin (B).
Acid anhydride type curing agent (C) is made by following method:
(1) MALEIC ANHYDRIDE is dissolved in dimethylbenzene or toluene to logical N
2and stirring is warming up to 60～80 DEG C;
(2) by being added dropwise to continuously after vinylbenzene, butyl acrylate and initiator blend in the liquid that step (1) obtains, dropwised in 1.5～2.5 hours, be incubated 4.5～6.5 hours, by the white precipitate suction filtration obtaining, dry and obtain acid anhydride type curing agent; Described MALEIC ANHYDRIDE, cinnamic mol ratio are 1:1; The quality of described butyl acrylate accounts for 0～35% of MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass; The consumption of initiator is 0.2%～5% of MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass.
Preferably 200～the 400g/mol of anhydride equivalent of acid anhydride type curing agent (C).
The preferred dibenzoyl peroxide of initiator, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl.
Self cure Polyacrylic Ester and Epoxy Resin sizing agent prepared by aforesaid method.
Above-mentioned self cure Polyacrylic Ester and Epoxy Resin sizing agent is in the purposes of preparing self cure Polyacrylic Ester and Epoxy Resin pressure sensitive adhesive.
Advantage:
Self cure Polyacrylic Ester and Epoxy Resin sizing agent of the present invention has good tack at normal temperatures, has good bonding intensity thereby can occur to solidify after being applied in hot environment.Method preparation of the present invention is simple.Sizing agent independent packaging, easy to use.
Embodiment
The embodiment of the present invention is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
Embodiment 1～3 second-order transition temperature is the preparation of the polyacrylate polymers (A) of-65 DEG C～10 DEG C:
(1) fill a prescription by table 1, get Isooctyl acrylate monomer, butyl acrylate, methyl methacrylate, vinyl acetate;
(2) initiator and linking agent are joined in the liquid of step (1) acquisition, mix, obtain mixed solution;
(3) mixed solution step (2) being obtained splashes in the organic solvent ethyl acetate under nitrogen atmosphere, at 70 DEG C, reacts 6 hours, obtains respectively second-order transition temperature and be the polyacrylate polymers (A) of-65 DEG C ,-30 DEG C and 10 DEG C.
Table 1(mass ratio)
Experimental results show that, the dibenzoyl peroxide of the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl alternate embodiment 1 is made to initiator, also can prepare the polyacrylate polymers (A) of second-order transition temperature within the scope of-65 DEG C～10 DEG C.
Linking agent is the compound that molecule contains multiple unsaturated double-bonds, experimental results show that, by Vinylstyrene and N, the Phthalic acid, diallyl ester of N-methylene-bisacrylamide alternate embodiment 1 is made linking agent, also can prepare the polyacrylate polymers (A) of second-order transition temperature within the scope of-65 DEG C～10 DEG C.
Experiment showed, the ethyl acetate of toluene, dimethylbenzene or acetone alternate embodiment 1 is made to organic solvent, also can prepare the polyacrylate polymers (A) of second-order transition temperature within the scope of-65 DEG C～10 DEG C.
Experiment showed, that, with 60 DEG C of reactions 6.5 hours, 70 DEG C of reactions of 4 hours alternate embodiments 1 of 80 DEG C of reactions 6 hours, also can also can prepare the polyacrylate polymers (A) of second-order transition temperature within the scope of-65 DEG C～10 DEG C.
Second-order transition temperature is that the polyacrylate polymers (A) of-65 DEG C～10 DEG C can also directly be bought commercial goods, as long as second-order transition temperature just can be applied to the present invention at the polyacrylate polymers of-65 DEG C～10 DEG C.
The preparation of embodiment 4～6 acid anhydride type curing agents:
Adopt MALEIC ANHYDRIDE and vinylbenzene and other monomer copolymerizations, can prepare the multipolymer of different anhydride equivalents, the proportioning raw materials of preparing anhydride curing agent is as shown in table 2.
(1) MALEIC ANHYDRIDE is dissolved in to logical N in dimethylbenzene
2and stirring is warming up to 70 DEG C;
(2) by dripping continuously after vinylbenzene, butyl acrylate and the blend of initiator dibenzoyl peroxide in the liquid that step (1) obtains, dropwised in 2 hours, be incubated 6 hours, by the white precipitate suction filtration obtaining, dry and obtain acid anhydride type curing agent;
MALEIC ANHYDRIDE, cinnamic mol ratio are 1:1;
The quality of described butyl acrylate accounts for MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass and is respectively 0,10%, 35%; The consumption of initiator is respectively 0.2%, 2.5%, 5% of MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass.
The basic recipe (mass ratio) of table 2 anhydride curing agent
Experiment showed, that the other the same as in Example 4, can obtain acid anhydride type curing agent equally with 70 DEG C in 60 DEG C or 80 DEG C of alternate embodiment 4 steps (1).
Dropwise with 1.5 hours, be incubated 6.5 hours, or dropwise with 2.5 hours, be incubated dropwising for 2 hours in 5 hours alternative embodiment 4 steps (2), be incubated 6 hours, the other the same as in Example 4, can obtain acid anhydride type curing agent equally.
By the dibenzoyl peroxide in the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl alternate embodiment 4, the other the same as in Example 4, can obtain equally acid anhydride type curing agent.
The preparation of embodiment 7～13 a kind of self cure Polyacrylic Ester and Epoxy Resin sizing agent
A kind of preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent:
(1), by polymer A, epoxy resin B and acid anhydride type curing agent C, mix; In table 3, be proportioning raw materials, the consumption indicating in table is mass ratio, and corresponding in bracket be the equivalence ratio of epoxy resin and anhydride curing agent.
(2) mixture step (1) being obtained is dissolved in and in solvent, is mixed with sizing agent.
The stripping strength of test Pressuresensitive Tape to stainless steel plate.Separately utilize self cure Polyacrylic Ester and Epoxy Resin pressure sensitive adhesive of the present invention (sizing agent) to overlap stainless steel plate, and solidify 4 hours at 120 DEG C, the shearing resistance of test sizing agent.The data obtained is all listed in table 3.
From table 3, the result of test can be found out, adopts self cure Polyacrylic Ester and Epoxy Resin pressure sensitive adhesive of the present invention being subject to have certain original viscosity before thermofixation, and at 120 DEG C, be heated 4 hours curable, and there is good shearing resistance.
The formula of table 3 embodiment 7～13 and the stripping strength of sizing agent and shearing resistance
Note: (1) epoxy resin B-1 is commercially available bisphenol A type epoxy resin E-51, and its epoxy equivalent (weight) is about 200g.mol
-1; Epoxy resin B-2 is the EPON of Momentive company
tMresin1009F, its epoxy equivalent (weight) scope is 2300～3800g.mol
-1, get experiment test value 2856g.mol
-1; Epoxy resin B-3 is the S903 of Akzo Nobel company, and its epoxy equivalent (weight) scope is 740～800g.mol
-1, get experiment test value 770g.mol
-1calculate.
(2) anhydride curing agent C-4 is commercially available dodecenylsuccinic anhydride (DDSA), and its anhydride equivalent is about 266g/mol.
(3) solvent EAc is ethyl acetate; ACK is acetone; DMF is DMF.
Sizing agent can be constructed in in-situ coating, also can in advance sizing agent solution be coated on the PP film of crossing by corona treatment, under room temperature, dries, and makes self cure Polyacrylic Ester and Epoxy Resin pressure sensitive adhesive.
Claims (8)
1. the preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent, is characterized in that comprising the steps:
(1) getting second-order transition temperature is the polyacrylate polymers (A) of-65 DEG C～10 DEG C; Epoxy resin (B) and acid anhydride type curing agent (C); Described (B) and mol ratio (C) are 0.95～1.2, and described (A) is 0.5～2.0 with mass ratio (B+C);
(2) by (A), (B) and (C) be dissolved in that in solvent, to make mass concentration be 40%～60% solution.
2. the preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent according to claim 1, it is characterized in that described solvent be ethyl acetate, acetone and DMF at least one.
3. the preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent according to claim 1, the epoxy equivalent (weight) that it is characterized in that described epoxy resin (B) is 200～3800g/mol.
4. the preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent according to claim 1, is characterized in that the following method of described acid anhydride type curing agent (C) makes:
(1) MALEIC ANHYDRIDE is dissolved in dimethylbenzene or toluene, logical N2 stirring are warming up to 60～80 DEG C;
(2) by being added dropwise to continuously after vinylbenzene, butyl acrylate and initiator blend in the liquid that step (1) obtains, dropwised in 1.5～2.5 hours, be incubated 4.5～6.5 hours, by the white precipitate suction filtration obtaining, dry and obtain acid anhydride type curing agent; Described MALEIC ANHYDRIDE, cinnamic mol ratio are 1:1; The quality of described butyl acrylate accounts for 0～35% of MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass; The consumption of initiator is 0.2%～5% of MALEIC ANHYDRIDE, vinylbenzene and butyl acrylate total mass.
5. according to the preparation method of the self cure Polyacrylic Ester and Epoxy Resin sizing agent described in claim 1 or 4, the anhydride equivalent that it is characterized in that described acid anhydride type curing agent (C) is 200～400g/mol.
6. the preparation method of self cure Polyacrylic Ester and Epoxy Resin sizing agent according to claim 4, is characterized in that described initiator is dibenzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl.
7. the self cure Polyacrylic Ester and Epoxy Resin sizing agent that prepared by the method for one of claim 1-6.
8. the self cure Polyacrylic Ester and Epoxy Resin sizing agent of claim 7 is in the purposes of preparing self cure Polyacrylic Ester and Epoxy Resin pressure sensitive adhesive.
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| CN104610897A (en) * | 2015-02-12 | 2015-05-13 | 矽照光电（厦门）有限公司 | Preparation method of acrylic acid modified epoxy resin for LED packaging |
| CN105732881A (en) * | 2016-05-16 | 2016-07-06 | 北京化工大学 | Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof |
| CN109627991A (en) * | 2018-12-04 | 2019-04-16 | 湖南工业大学 | A kind of molten type two-component composite adhesive of water-resistance ester and preparation method thereof |
| CN113755103A (en) * | 2021-09-18 | 2021-12-07 | 烟台德邦科技股份有限公司 | Epoxy adhesive with initial pressure sensitivity and preparation method thereof |
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| CN105732881B (en) * | 2016-05-16 | 2018-06-26 | 北京化工大学 | A kind of water-base epoxy/poly acrylate composite emulsion and preparation method thereof |
| CN109627991A (en) * | 2018-12-04 | 2019-04-16 | 湖南工业大学 | A kind of molten type two-component composite adhesive of water-resistance ester and preparation method thereof |
| CN113755103A (en) * | 2021-09-18 | 2021-12-07 | 烟台德邦科技股份有限公司 | Epoxy adhesive with initial pressure sensitivity and preparation method thereof |
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