CN104804702A - Silane modified two-component acrylate structure adhesive - Google Patents
Silane modified two-component acrylate structure adhesive Download PDFInfo
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- CN104804702A CN104804702A CN201410042393.2A CN201410042393A CN104804702A CN 104804702 A CN104804702 A CN 104804702A CN 201410042393 A CN201410042393 A CN 201410042393A CN 104804702 A CN104804702 A CN 104804702A
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Abstract
The invention discloses a silane modified two-component acrylate structure adhesive. The adhesive is composed of a first component and a second component, and the first component comprises 100 parts of a polymerizable metacrylate monomer, 0.1-2 parts of a reducing agent, and 0.1-10 parts of a silane modified acrylate and a silane modified polymer; and the second component comprises 1-5 parts of peroxide or hydroperoxide capable of composing an oxidation-reductions system together with the reducing agent of the first component. The silane modified two-component acrylate structure adhesive improves the temperature resistance of a traditional two-component acrylate structure adhesive, reduces common acidic monomers having a tackifying effect in traditional systems, and improves the hydrolysis resistance of adhesives, so the application field of the silane modified two-component acrylate structure adhesive is enlarged.
Description
Technical field
The present invention relates to a kind of tackiness agent, particularly relate to a kind of silane-modified two-component acrylate structural adhesive stick.
Background technology
Two-component acrylate structural adhesive stick is usually by (methyl) acrylic ester monomer, organo-peroxide and can form the reductive agent of redox system with this organo-peroxide, and the component composition such as tackifier, thixotropic agent, toughner and colorant.The feature of bi-component acrylic tackiness agent is, can at room temperature can fast setting after two component Homogeneous phase mixing, and does not need strict stoichiometric ratio mixing, simple to operate.After E.I.Du Pont Company's invention in 1975 is the so-called s-generation acrylate structural adhesive (SGA) of main component by methyl methacrylate and chlorosulfonated polyethylene, the research of two-component acrylate structural adhesive and industrialization have had rapid progress.Research direction concentrates on: the oxidation-reduction trigger system that (1) is suitable for and Synergist S-421 95.System is selected to determine the speed, stability in storage, resistance to the oxygen inhibiting polymerization etc. of solidifying and can reach.Oxygenant mostly is superoxide or hydroperoxide, reductive agent or promotor of a great variety, comprise amine, Thiourea, metallic compound, sulfocompound, phosphorus species, ketone; 2) combination of monomers.Monomer as main component determines the smell of system before solidifying completely, the fundamental property etc. of cured product; 3) macromolecular elastomer.This component mainly plays the effects such as toughness reinforcing, thickening, has remarkably influenced to curing action.Two-component acrylicester adhesive is because of its strong adhesion, and bulk strength is high, can be used as being adhesively fixed between parts that structure element is widely used in the fields such as electron trade, communications and transportation, electromechanics, new forms of energy; Because its solidification is rapid, be especially applicable to pipelining.Therefore just applied more and more widely.
The basic material of two-component acrylate structural adhesive stick concentrates on organic materials category, and the agent structure after solidification is made up of C-C, and bond energy is general, easily by the destruction such as ultraviolet, heat; Acrylate materials hydrolytic resistance is not good, has especially often added the acid monomer (as methacrylic acid, acid phosphoric acid ester etc.) of viscosifying action in system, therefore should not use in wet environment for a long time; For the redox system of superoxide-amine composition, the consumption of increasing amine of having to due to adding of acid monomer, its smell will bring more sense of discomfort for user, and amine easily oxidized, variable color itself.Above-mentioned factor constrains the range of application of two-component acrylate structural adhesive stick.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of silane-modified two-component acrylate structural adhesive stick, it improves the heat resistance of traditional double component acrylic ester structure tackiness agent, reduce the acid monomer for viscosifying action that traditional system is common, improve the hydrolytic resistance of tackiness agent, thus expand the use field of product.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of silane-modified two-component acrylate structural adhesive stick, it is characterized in that, it is made up of the first component and second component, first component must comprise polymerisable methacrylate-based monomer 100 parts, reductive agent 0.1-2 part, silane-modified acrylic ester monomer and silane modified polymer, total number of silane-modified acrylic ester monomer and silane modified polymer is 0.1-10 part; Second component comprises and can form superoxide or hydroperoxide 1-5 part of oxidation-reduction system with the reductive agent of the first component.
Preferably, described polymerisable methacrylate-based monomer comprises following one or more: methacrylic acid and methyl esters, ethyl ester, propyl ester, positive butyl ester, different monooctyl ester, lauryl, 13 esters, octadecyl ester, cyclohexyl, benzene oxygen ethyl ester, isobornyl thiocyanoacetate, tetrahydrofurfuryl alcohol ester, methoxyethyl ester, ethoxyethyl ester, glycidyl ester, hydroxyl ethyl ester, hydroxypropyl acrylate, diethylene glycol dilaurate, triethylene Glycol dibasic acid esters, dimethyltrimethylene glycol dibasic acid esters, trimethylolpropane triester, N-tertiary butyl acid amides, lauryl methacrylate(LMA).
Preferably, described reductive agent comprises following one or more: amine, Thiourea, low-valent metal compound, phosphorus species, ketone.
Preferably, toughness reinforcing polymkeric substance is added in described first component.
Preferably, oxidation inhibitor is added in described first component.
Preferably, the tackifying resin containing different quantities vinyl functionality is added in described first component.
Preferably, in described first component, thixotropic agent is added in the second component.
Preferably, in described first component, colorant is added in second component.
Positive progressive effect of the present invention is: the present invention improves the heat resistance of traditional double component acrylic ester structure tackiness agent, reduce the acid monomer for viscosifying action that traditional system is common, improve the hydrolytic resistance of tackiness agent, thus expand the use field of product.
Embodiment
The silane-modified two-component acrylate structural adhesive stick of the present invention is made up of the first component and second component, first component must comprise polymerisable methacrylate-based monomer 100 parts, reductive agent 0.1-2 part, silane-modified acrylic ester monomer and silane modified polymer, total number of silane-modified acrylic ester monomer and silane modified polymer is 0.1-10 part; Second component comprises and can form superoxide or hydroperoxide 1-5 part of oxidation-reduction system with the reductive agent of the first component.
Polymerisable methacrylate-based monomer comprises following one or more: methacrylic acid and methyl esters, ethyl ester, propyl ester, positive butyl ester, different monooctyl ester, lauryl, 13 esters, octadecyl ester, cyclohexyl, benzene oxygen ethyl ester, isobornyl thiocyanoacetate, tetrahydrofurfuryl alcohol ester, methoxyethyl ester, ethoxyethyl ester, glycidyl ester, hydroxyl ethyl ester, hydroxypropyl acrylate, diethylene glycol dilaurate, triethylene Glycol dibasic acid esters, dimethyltrimethylene glycol dibasic acid esters, trimethylolpropane triester, N-tertiary butyl acid amides, lauryl methacrylate(LMA) etc.
Reductive agent comprises following one or more: amine is (as triethylamine, Triethanolamine 99(TEA 99), N, accelerine, N, N-dimethyl-p-toluidine, N, N-hydroxyethyl para-totuidine, N-hydroxyethyl-N-methyl para-totuidine etc.), Thiourea is (as ethylene thiourea, trimethyl thiourea, phenylthiourea, tetramethyl thiourea, asccharin etc.), low-valent metal compound is (as cobalt, manganese, the naphthoate of the metallic elements such as vanadium, naphthenate, octylate etc.), phosphorus species is (as triphenylphosphine, trioctyl phosphate etc.), ketone is (as methyl ethyl diketone, benzoyl acetone etc.).
Silane-modified acrylic ester monomer refers to the acrylate monomer containing alkoxyl group, as commercially available γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, and the monomer with polymerization activity that the acrylate monomer of hydroxyl (as hydroxyethyl methylacrylate, hydroxypropyl acrylate) reacts with the silane (as commercially available isocyanate group propyl trimethoxy silicane, isocyanate group propyl-triethoxysilicane) containing isocyanate group (NCO).Above-mentioned reaction, usually needing a small amount of catalyzer (0.01%-2%wt, based on acrylic ester monomer and silane total amount), room temperature 90 DEG C, obtains in water-less environment reaction 0.1-10h.Also by the acrylic ester monomer of above-mentioned hydroxyl and polyisocyanates (as tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI) etc.) recommend 2 ~ 4 with n (NCO)/n (OH) >1() ratio mixing after, react under above-mentioned catalyst condition, then add containing primary amine, the silane of secondary amine is (as aminopropyl trimethoxysilane, aminopropyl triethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane etc.) react obtained, but the mole number of the hydroxyl of total reaction and amino mole number sum and NCO should be close, that is: n (OH)+n (amino) ≈ n (NCO).
Silane modified polymer can select commercially available silane modified polymer (as 203,303, SAT400 of Zhong Yuan; Step 1050,1015 of figure; 2458 etc. of Bayer).But commercially available prod mainly for be the application of single-component moisture-curable series products, therefore many vinyl groups do not possessed needed for radical polymerization.Following methods can be adopted to obtain double bond containing silane modified polymer: by polyether glycol and polyisocyanates, as tolylene diisocyanate (TDI), 4,4'-methylene-bis (phenylcarbimide) (MDI), isophorone diisocyanate (IPDI) etc., with the mixing of the ratio of n (NCO): n (OH) >1 (recommending ratio 1.5 ~ 3), add appropriate metal catalyst (0.01 ~ 1%wt of total reactant), recommendation response temperature is 20 ~ 100C.When viscosity increases to stirring at need, add the acrylate monomer of hydroxyl (as hydroxyethyl methylacrylate, hydroxypropyl acrylate), the mole number sum that its mole number and former polyether glycol contain OH should lower than NCO mole number, the total mole number recommending hydroxyl is 50% ~ 90% of NCO mole number, when continuing to react constant to stable viscosity, add the siloxanes (aminopropyl trimethoxysilane containing primary amine or secondary amine, aminopropyl triethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane etc.), concrete consumption meets n (OH)+n (amine) ≈ n (NCO).Namely the silane modified polymer with polymerization activity is obtained after reaction 1 ~ 60min.When the acrylate monomer design quantity of hydroxyl is less, be not enough to dilution polyvalent alcohol and polyisocyanates and react when generating dope, can add after the dilution of the acrylate of hydroxyl.Thinner is other acrylic ester monomers (as methyl methacrylate) or softening agent of not reacting with NCO, and the weight ratio of the acrylic ester monomer of itself and hydroxyl, without strict restriction, is recommended as (1 ~ 30): 1.
Superoxide comprises following one or more: benzoyl peroxide, peroxidation two (2-toluyl), peroxidation two (2,4 dichloro benzene formyl), dilauroyl peroxide, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate isopropyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxidized t-butyl perbenzoate, dicumyl peroxide etc.
Hydroperoxide comprise following one or both: tertbutyl peroxide, isopropyl benzene hydroperoxide etc.
For improving the resistance to impact shock of material, toughness reinforcing polymkeric substance can be added in first component, spendable material comprises: chlorosulfonated polyethylene, paracril, acrylic elastomer, and the multipolymer such as styrene-butadiene-styrene block polymer (SBS), MBS (MBS) polymkeric substance, consumption is 10-300 part.
For improving the stability in storage of the first component, suitably can add oxidation inhibitor in the first component, as quinhydrones, 2,6 ditertiary butyl p cresol etc., consumption 0-500ppm is advisable.Too much oxidation inhibitor will cause adhesive solidification difficulty.
For increasing tackiness agent to the bonding force of various material, expand bonding scope; Improve curing action, as improved or delaying solidification rate, the first component can add other tackifying resins containing different quantities vinyl functionality, as pure acrylic resin, and epoxy, phenolic aldehyde, polyester, polyurethane modified acrylic resin etc., consumption 10-100 part.
Consider thixotropy, in the present invention first component, suitably can add the thixotropic agent such as aerosil, consumption 0.1-30 part.
The superoxide of second component of the present invention or hydroperoxide, consider solvability, suitable liquid flux dilution can be used or dissolve, if softening agent (such as: phthalic ester etc.), polyvalent alcohol are (as glycerine, 1,4-butyleneglycol etc.) etc., consumption is 1-10 part, and thixotropic agent (as precipitated silica, aerosil, organic-silicon-modified liquid thixotropic agent etc.) also can be used to improve thixotropy, and consumption is 0.1-2 part.
According to application demand, optionally add colorant (comprising toner, look mother, mill base etc.) in first, second component, as ultramarine, sapphire blue, bright red etc., consumption is at 0.01 ~ 0.1 part.
The preparation of the present invention first component, second component, only need preserve airtight after respective raw material Homogeneous phase mixing, packaging.During use, by the first component, second component mixing, be coated in and need bonding position enforcement bonding.
Embodiment 1: the preparation of silane-modified acrylic ester monomer
In 1L tri-mouthfuls of reaction flasks, by hydroxyethyl methylacrylate 130.1g(1mol) and isocyanate group propyl-triethoxysilicane 247.0g(1mol), and 0.037g(0.01%wt) stannous octoate catalyst stir, under the condition of isolated moisture, in 90 DEG C of reaction 0.1h, obtain silane-modified acrylic ester monomer M1.
Embodiment 2: the preparation of silane-modified acrylic ester monomer
In 1L tri-mouthfuls of reaction flasks, by hydroxyethyl methylacrylate 260.2g(2mol) and isocyanate group propyl trimethoxy silicane 410.6g(2mol), and 15.1g(2%wt) isocaprylic acid bismuth catalyst stir, under the condition of isolated moisture, in room temperature reaction 10h, obtain silane-modified acrylic ester monomer M2.
Embodiment 3: the preparation of silane-modified acrylic ester monomer
In 500mL tri-mouthfuls of reaction flasks, by Rocryl 410 144.2g(1mol) and isocyanate group propyl trimethoxy silicane 205.3g(1mol), and 1.75g(0.5%wt) dibutyl tin dilaurate catalyzer stir, under the condition of isolated moisture, in 60 DEG C of reaction 2h, obtain silane-modified acrylic ester monomer M3.Detect through HPLC, in embodiment 1,2,3, productive rate is all more than 95%.
Embodiment 4: the preparation of silane-modified acrylic ester monomer
In 2L tri-mouthfuls of reaction flasks, by hydroxyethyl methylacrylate 260.2g(2mol), 348.3g TDI (2mol) and 6.1g(1%wt) dibutyl tin dioctoate mixing and stirring, n(NCO under this proportioning)/n(OH)=2.Under the condition of isolated moisture, after 40 DEG C of reaction 4h, dropwise add anilinomethyl trimethoxy silane 454.7g(2mol), drip off in 2h, then after 40 DEG C of reaction 1h, obtain silane-modified acrylic ester monomer M4.
Embodiment 5: the preparation of silane-modified acrylic ester monomer
In 2L tri-mouthfuls of reaction flasks, by Rocryl 410 144.2g(1mol), 375.4g MDI (1.5 mol) and 0.52g(0.1%wt) di-n-butylacetic acid tin mixing and stirring, n(NCO under this proportioning)/n(OH)=3.Under the condition of isolated moisture, after 60 DEG C of reaction 2h, in 1h, dropwise add anilinomethyl triethoxysilane 538.8g (2mol), after reacting 1h again after being added dropwise to complete, obtain silane-modified acrylic ester monomer M5.
Embodiment 6: the preparation of silane-modified acrylic ester monomer
In 250mL tri-mouthfuls of reaction flasks, by hydroxyethyl methylacrylate 13.0g(0.1mol), 44.4g IPDI (0.2mol) and 0.287g(0.5%wt) dibutyl tin dioctoate mixing and stirring, n(NCO under this proportioning)/n(OH)=4.Under the condition of isolated moisture, after 20 DEG C of reaction 10h, in 1h, dropwise add aminopropyl trimethoxysilane 53.8g (0.3mol), after reacting 2h again after being added dropwise to complete, obtain silane-modified acrylic ester monomer M6.
Embodiment 7: the preparation of silane modified polymer
In 50mL there-necked flask, N210 polyethers 10g(0.01mol after dewatering) with TDI 2.6g(0.015mol) mix, add 0.063g(0.5%wt) dibutyl tin laurate, 50 DEG C of reactions, viscosity increases with reaction, to stirring at need, add 0.91g(0.007mol) mixture of hydroxyethyl methylacrylate and 3g methyl methacrylate, continue reaction about 30min viscosity basicly stable, now in 10min, be added dropwise to 0.66g(0.003mol) aminopropyl triethoxysilane, after being added dropwise to complete, continue at 50 DEG C of reaction 30min, the silane modified polymer of radical polymerization activity and the mixture P1 of methyl methacrylate must be had.
Embodiment 8:
In 10L reactor, N220 polyethers 2000g(2mol by after dehydration) mix with MDI 1502g (6mol), add 3.5g stannous octoate (0.1%wt), 20 DEG C of reactions, stirring is increased at need to viscosity, add 260.2g(2mol) mixture of hydroxyethyl methylacrylate and 260.2g methyl methacrylate, continue to react about about 5h viscosity substantially not in increase, in 30min, be now added dropwise to 1616.5g anilinomethyl triethoxysilane (6mol), after being added dropwise to complete, continue reaction 60min, obtain the mixture P2 of silane modified polymer and methyl methacrylate.
Embodiment 9:
In 1L reactor, N210 polyethers 200g(0.2mol by after dehydration) IPDI 111.1g(0.5mol) mix, add isocaprylic acid bismuth 3.11g(1%wt), 100 DEG C of reactions, stirring is increased at need to viscosity, add Rocryl 410 43.3g(0.3 mol) and plasticizer phthalic acid dioctyl ester 86.6g, continue to react about about 10min stable viscosity, now in 10min, be added dropwise to anilinomethyl trimethoxy silane 68.2g(0.3mol), after being added dropwise to complete, continue reaction 1min.After cooling, the silane modified polymer of radical polymerization activity and the mixture P3 of dioctyl phthalate (DOP) must be had.
Embodiment 10: the preparation of the silane-modified acrylate structural adhesive of two component
First component: methyl methacrylate 93 parts, methacrylic acid 5 parts, lauryl methacrylate(LMA) 2 parts, MBS 60 parts, polyurethane modified acrylic resin 20 parts, N, N-dimethyl-p-toluidine (reductive agent) 2 parts, quinhydrones 0.05 part, silane-modified acrylic ester monomer M1(number is in table 1), silane modified polymer P1(number is in table 1).
Second component: benzoyl peroxide 5 parts, dioctyl phthalate (DOP) 100 parts (dioctyl phthalate (DOP) is the softening agent for disperseing benzoyl peroxide), aerosil 5 parts.
After two components are mixed separately, after leaving standstill 24h, then by two component mixing.
Contrast sample 1:
First component increases by 3 parts of acid phosphoric acid esters, and the consumption of reductive agent amine increases to 2 parts, does not add silane-modified acrylic ester monomer and silane modified polymer.All the other components and second component same as described above.Its contrast test result is as shown in table 1 below:
Table 1
Test condition: shearing test batten is of a size of 120mm × 25mm, gluing overlap joint area 25mm × 8mm, bondline thickness 0.2mm, at 25 DEG C after batten completes, place in 55%RH environment after 3 days and carry out aging, boiling water boiling, batten after aging and poach, at 25 DEG C, is placed in 55RH environment after 3 days and is tested, shearing test speed: 2mm/min.
Embodiment 11: the silane-modified acrylate structural adhesive of two component
First component comprises methyl methacrylate 94 parts, methacrylic acid 3 parts, butyl methacrylate 3 parts, SBS 20 parts, paracril 20 parts, pure acrylic resin 30 parts, vanadium acetylacetonate (reductive agent) 0.1 part, 2,6 ditertiary butyl p cresol 0.03 part, silane-modified acrylic ester monomer M2(number is in table 2), silane modified polymer P2(number is in table 2).
Second component comprises: hydrogen phosphide cumene (number is in table 2), dioctyl phthalate (DOP) 100 parts, aerosil 2 parts, sapphire blue 0.02 part.
After two components are mixed separately, after leaving standstill 24h, then by two component mixing.
Contrast sample 2:
First component increases by 3 parts of acid phosphoric acid esters, does not add silane-modified acrylic ester monomer and silane modified polymer.All the other components and second component same as described above.Its contrast test result is as shown in table 2 below:
Table 2
Test condition: shearing test batten is of a size of 120mm × 25mm, gluing overlap joint area 25mm × 8mm, bondline thickness 0.2mm, at 25 DEG C after batten completes, place in 55%RH environment after 3 days and carry out aging, boiling water boiling, batten after aging and poach, at 25 DEG C, is placed in 55RH environment after 3 days and is tested, shearing test speed: 2mm/min.
From the above results, when not using acid phosphoric acid ester and silane-modified monomer or polymkeric substance, two-component acrylicester glue is extremely weak to above-mentioned substrate bonding power.After the silane-modified monomer of use and silane modified polymer, bonding force is better than conventional formulation slightly.But the thermotolerance of structure glue, water tolerance, have obvious improvement relative to conventional formulation.Especially, owing to not introducing acid phosphoric acid ester, in the oxidation-reduction system therefore for superoxide-amine formation, the consumption of amine does not need to increase, and coloured product is more shallow, is beneficial to toning.In addition, when initiator amount increases to a certain degree, because reaction is too rapid, the unordered degree of polymerization process strengthens, and bonding net effect may be deteriorated (comparison see sample 8 and 9).
Those skilled in the art can carry out various remodeling and change to the present invention.Therefore, present invention covers the various remodeling in the scope falling into appending claims and equivalent thereof and change.
Claims (8)
1. a silane-modified two-component acrylate structural adhesive stick, it is characterized in that, it is made up of the first component and second component, first component must comprise polymerisable methacrylate-based monomer 100 parts, reductive agent 0.1-2 part, silane-modified acrylic ester monomer and silane modified polymer, total number of silane-modified acrylic ester monomer and silane modified polymer is 0.1-10 part; Second component comprises and can form superoxide or hydroperoxide 1-5 part of oxidation-reduction system with the reductive agent of the first component.
2. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, it is characterized in that, described polymerisable methacrylate-based monomer comprises following one or more: methacrylic acid and methyl esters, ethyl ester, propyl ester, positive butyl ester, different monooctyl ester, lauryl, 13 esters, octadecyl ester, cyclohexyl, benzene oxygen ethyl ester, isobornyl thiocyanoacetate, tetrahydrofurfuryl alcohol ester, methoxyethyl ester, ethoxyethyl ester, glycidyl ester, hydroxyl ethyl ester, hydroxypropyl acrylate, diethylene glycol dilaurate, triethylene Glycol dibasic acid esters, dimethyltrimethylene glycol dibasic acid esters, trimethylolpropane triester, N-tertiary butyl acid amides, lauryl methacrylate(LMA).
3. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, described reductive agent comprises following one or more: amine, Thiourea, low-valent metal compound, phosphorus species, ketone.
4. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, adds toughness reinforcing polymkeric substance in described first component.
5. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, adds oxidation inhibitor in described first component.
6. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, adds thixotropic agent in described first component.
7. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, adds the tackifying resin containing different quantities vinyl functionality in described first component.
8. silane-modified two-component acrylate structural adhesive stick as claimed in claim 1, is characterized in that, in described first component, adds colorant in second component.
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| CN105969211A (en) * | 2016-06-29 | 2016-09-28 | 哈尔滨永淇化工有限公司 | Flame-retardant storage battery sealing adhesive based on lauryl methacrylate and tridecyl methacrylate and production method of flame-retardant storage battery sealing adhesive |
| CN105969208A (en) * | 2016-06-29 | 2016-09-28 | 哈尔滨永淇化工有限公司 | Methoxy ethyl ester and ethoxy ethyl ester based high-elasticity sealant for storage batteries and manufacturing method of methoxy ethyl ester and ethoxy ethyl ester based high-elasticity sealant |
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