CN110396392A - UV/ heat/moisture triple curable organic silicon adhesive - Google Patents
UV/ heat/moisture triple curable organic silicon adhesive Download PDFInfo
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- CN110396392A CN110396392A CN201910709390.2A CN201910709390A CN110396392A CN 110396392 A CN110396392 A CN 110396392A CN 201910709390 A CN201910709390 A CN 201910709390A CN 110396392 A CN110396392 A CN 110396392A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The invention discloses a kind of UV/ heat/moisture triple curable organic silicon adhesives, based on parts by weight, the adhesive or sealant include the alkoxyl silicone terminated dimethyl silicone polymer of 100 parts of (methyl) acryloxyalkyl urea groups, 0.5 ~ 5 part of photoinitiator, 0.5 ~ 5 part of moisture-curable catalyst, 0.5 ~ 5 part of free radical thermal initiator, 1.0 ~ 40 parts of fumed silicas.The organic silicon adhesive can be used for being bonded or encapsulating purposes, the aerial part of exposure can carry out rapid curing by ultraviolet light, shadow region or lighttight part can be solidified by moisture or heating, the problem of substantially increasing production efficiency, avoiding simple moisture-curable or cure silicone curing time long low efficiency.
Description
Technical field
The invention belongs to adhesive preparation fields, and in particular to it is a kind of can UV/ heat/moisture triple curable no-solvent type have
Machine silicon adhesive/sealant.
Background technique
Organosilicon material has many excellent performances due to its unique molecular structure, and such as resistant of high or low temperature is weather-proof
Property, low-surface-energy and chemical stability etc..These performances make organosilicon material be increasingly subject to the attention of people, are answered extensively
With.
The features such as UV-curing technology has high-efficient, and pollution is few, easy, energy saving, is a kind of environmental-friendly green
Technology.If introducing on polysiloxane strand has photosensitive group, photo curable poly- silicon oxygen is made
Alkane, then curing efficiency will greatly improve.
The combination of organosilicon material and UV-curing technology not only can promote the development of organosilicon material, and be purple
Outer photo-curing material adds new varieties.It can polymerize under ultraviolet light, there are two main classes for the reactive group of crosslinking: freely
Base ultraviolet curing group and cation photocuring group.Mainly (methyl) acrylate-based or (methyl) acrylamido for the former.
The latter is mainly epoxy group, vinyl ether group and styryl.At present, synthesize Photocurable Silicone Material main method be
(methyl) acrylate photosensitive group or epoxy photosensitive group are introduced in polysiloxane strand.(methyl) acrylate light
Quick group belongs to free radical Photoinitiated reactions, and raw material are cheap and easy to get, and the silane containing (methyl) acrylate photosensitive group is even
Connection agent and hydroxyl-terminated injecting two methyl siloxane end capping reaction be simple and efficient be mildly photo-curable silicone preferred option,
It is one of the method being most widely used at present.
Although photo-curable silicone has the advantages that high-efficient, pollution is few, Simple energy-saving, for complicated electronics member device
Part or industrial products, often because having shadow region or glued material is opaque causes to solidify bad or be unable to photocuring.For
It solves the problems, such as that shadow region does not solidify, generally requires to introduce in silicone molecules structure moisture cured or heat-setting
Functional group assigns organosilicon UV/ heat or UV/ moisture dual cure mechanism, meets rapid curing Gao Sheng in industrial processes
While producing efficiency, the hidden danger such as product caused by avoiding shadow region from failing to solidify is bad.
Although dual UV curable paint can solve the not cured problem in shadow region, UV/ moisture dual cure systems are still deposited
The problems such as shadow region curing time is long.Especially in winter of the temperature compared with low humidity very little, the use deeper for cured thickness
On the way, it may cannot be all fully cured up to a couple of days, seriously affect the shipment period.The hot dual UV curable paint of UV/ can be to avoid moisture
Curing time long even not cured risk, can be at a certain temperature than solidifying, but due to free radical polymerization in the short period
The influence of the intrinsic oxygen inhibition effect of system, the permeability of organosilicon material is higher, and dissolved oxygen ability is stronger, shows
Surface cure it is often more worse than acrylic UV curing materials, often there is one layer of viscosity even oiliness on solidification initial stage surface
Substance, cannot abundant surface drying, the dust being easy in absorption air cannot be superimposed between workpiece in order to avoid adhesion, under the influence of
One step process is gone on smoothly.
Summary of the invention
In view of existing UV/ moisture it is double solidify with the disadvantages mentioned above of UV/ heat dual curing system, the present invention provides one kind can
UV/ heat/moisture triple curable no-solvent type organic silicon adhesive, which can be used for being bonded or encapsulating purposes,
The aerial part of exposure can carry out rapid curing by ultraviolet light, and shadow region or lighttight part can pass through
Moisture or heating are solidified, and production efficiency is substantially increased, and avoid simple moisture-curable or cure silicone is solid
The problem of changing time long low efficiency.
A kind of UV/ heat of the present invention/moisture triple curable organic silicon adhesive/sealant based on parts by weight should
Adhesive or sealant include the alkoxyl silicone terminated dimethyl silicone polymer of 100 parts of (methyl) acryloxyalkyl urea groups,
0.5~5 part of photoinitiator, 0.5~5 part of moisture-curable catalyst, 0.5~5 part of free radical thermal initiator, 1.0~40 parts of gas phases
Silica.
Further, the alkoxyl silicone terminated dimethyl silicone polymer of (methyl) acryloxyalkyl urea groups has as follows
Structure:
Wherein,
R1For H or methyl；
R2For CH2, CH2CH2, CH2CH2CH2Or CH2CH2OCH2CH2；
R3For H or methyl；
R4For methyl, ethyl, propyl, butyl or phenyl；
R5For CH2Or CH2CH2CH2；
R6For methyl, methoxy or ethoxy；
R7For methyl, methoxy or ethoxy；
The integer that n is 200~2000.
Further, photoinitiator is selected from 2- hydroxy-2-methyl -1- phenyl -1- acetone (1173), 2,4,6- trimethylbenzenes
Mixture (the Esacure of formoxyl-diphenyl phosphine oxide (TPO), 2,4,6- tri-methyl benzophenones and 4- methyl benzophenone
TZT), benzoin dimethylether (651), benzophenone, 1- hydroxy-cyciohexyl Benzophenone (184), α, α '-acetophenone
(DEAP) one or more of mixing or in α-amine alkyl phenones, preferably 2- hydroxy-2-methyl -1- phenyl -1- acetone (1173)
Or one or more of mixing in 2,4,6- trimethylbenzoy-dipheny phosphine oxide (TPO).
Further, moisture-curable catalyst is organo-tin compound, titanate ester compound, α silane coupling agent, Louis
In any one or a few in this acids or Louis's alkaloid compound, preferably organo-tin compound or Louis's alkaloid compound
Any one or two kinds.
Further, free radical thermal initiator includes azo-initiator and organic peroxide evocating agent, and azo draws
Send out the preferred AIBN of agent, AIBME；The preferred lauroyl peroxide of organic peroxide evocating agent, benzoyl peroxide, benzoyl peroxide first
Tert-butyl acrylate.
Further, fumed silica is hydrophobicity aerosil, preferably AEROSIL hydrophobic silica
R972。
The alkoxyl silicone terminated dimethyl silicone polymer of (methyl) acryloxyalkyl urea groups of the present invention closes
Be at method: the silane coupling agent and 100 parts by weight hydroxy silicon oils that 1.0~10 parts by weight contain secondary amine are in 0.01~2.0 weight
It under the action of measuring part catalyst catalyst, reacts at 80 ± 5 DEG C, reaches 1.0~10 parts by weight of addition after certain viscosity
(methyl) acryloyloxyalkyl isocyanate obtains the poly- diformazan that both-end is (methyl) acryloxyalkyl urea groups alkoxyl silicone
Radical siloxane.
In synthetic method, reach addition (methyl) acryloyloxyalkyl isocyanate after certain viscosity, the certain viscosity
Different and different according to initial feed viscosity, usually 2.0~5.0 times of initial feed hydroxy silicon oil viscosity are advisable.
In synthetic method, the hydroxy silicon oil preferred viscosities used is the hydroxy silicon oil of 400mPas~200000mPas, hydroxyls
The structure of silicone oil is as follows:
The integer that n is 200~2000.
In synthetic method, the silane coupling agent containing secondary amine is selected from N- (methyl)-γ-aminopropyltrimethoxysilane,
N- (ethyl)-γ-aminopropyltrimethoxysilane, N- (propyl)-γ-aminopropyltrimethoxysilane, N- (normal-butyl)-γ-
Aminopropyl trimethoxysilane, N- (phenyl)-γ-aminopropyltrimethoxysilane, N- (methyl)-γ-aminopropyl trimethoxy
Silane, N- (ethyl)-gamma-aminopropyl-triethoxy-silane, N- (propyl)-gamma-aminopropyl-triethoxy-silane, N- (positive fourth
Base)-gamma-aminopropyl-triethoxy-silane, N- (cyclohexyl)-γ-aminopropyltrimethoxysilane, N- (phenyl)-γ-aminopropyl
Triethoxysilane, n-butylaminomethyl triethoxysilane, n-butylaminomethyl methyldiethoxysilane, aminopropyltriethoxysilane
Triethoxysilane, any one or a few mixing in aminopropyltriethoxysilane trimethoxy silane etc..
In synthetic method, (methyl) acryloyloxyalkyl isocyanate is selected from acryloyloxyethyl isocyanate, methyl
Acryloyloxyethyl isocyanate, acryloyl-oxy ethyl glycol isocyanates, methacryloxy ethylene glycol isocyanates
Any one or a variety of mixtures in.
In synthetic method, catalyst catalyst is selected from organo-tin compound, bismuth organic compound, titanate ester compound, road
The mixing of any one or a few in Lewis acid class or Louis's alkaloid compound.
Compared with prior art, the invention has the advantages that
(1) compared with simple moisture-curable or the organic silicon adhesive of heat cure, the present invention provides one kind can UV/
Heat/moisture triple curable mechanism organic silicon adhesive.Have photo-curing material Rapid high-efficiency energy-saving it is environmentally friendly the advantages that.
(2) compared with the organic silicon adhesive of simple ultraviolet curing, the present invention provides the second third curing mechanism,
The not cured problem in shadow region, which passes through moisture or is heating and curing, to be resolved.
(3) compared with the double cured silicone systems of ultraviolet light/moisture, it is provided by the invention can UV/ heat/moisture it is triple solid
Change mechanism organic silicon adhesive, avoid shadow region ultraviolet light cannot solidify and moisture-curable the time required to it is very long even very
For a long time can not cured predicament, can be greatly shortened curing time, improve production efficiency.
(4) compared with ultraviolet light/heat dual curing organosilicon systems, it is provided by the invention can UV/ heat/moisture triple curable
The organic silicon adhesive of mechanism does not fear oxygen inhibition effect to free radical machine due to being provided simultaneously with surface moisture solidification function
The photocuring of reason or the baneful influence of heat cure, surface cure are significantly improved, and solidification quality is improved significantly.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail.
In organic silicon adhesive of the present invention, the free radical thermal initiator of use includes azo-initiator and organic
Peroxide initiator, wherein
Azo initiator refers to that the radical initiator containing nitrogen nitrogen double bond in molecule structure, general general formula are R-N
=N-R, wherein R-N key is weak bond, is easily broken off to form free radical, decomposition temperature is related with alkyl structure.If both ends are pair
Claim polarized substituent group in alkyl structure or alkyl (such as-CN ,-COOH ,-COOR etc.), then decomposition temperature declines.Azo
The decomposition almost all of initiator is first order reaction, a kind of free radical is only formed, without side reaction.Azo initiator property is steady
It is fixed, convenient for storage and transport.Oil-soluble azo-initiator has azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN)
Deng.But this kind of initiator contains cyano, there is certain toxicity.The oil-soluble azo for having been developed for not cyano-containing in recent years draws
Agent is sent out, such as azo-bis-iso-dimethyl (AIBME).It is preferred that AIBN, AIBME.
The principal item of organic peroxide has hydroperoxides (ROOH), dialkyl peroxide (ROOR), diacyl
Peroxide (RCOOOOCR), peroxy esters (RCOOOR), peroxycarbonates (ROCOOOOCOR) and ketone peroxide [R2C
(OOH)2] etc..Benzoyl peroxide (BPO) is most common organic peroxide, is grain crystalline solid, normal to improve safety
Being commonly incorporated into 25% water becomes wet product, to reduce flammable and vibration sensitivity.In addition there is the peroxide of 50% plasticizer of concentration
Change benzoyl.Peroxide esters activity is higher and common peroxide.Such as the new enanthic acid 1 of peroxidating, 1- dimethyl -3- hydroxyl fourth
Ester, cumyl peroxyneodecanoate, the peroxides esters such as peroxidating neodecanoic acid tert-pentyl ester and t-butylperoxy pivarate are that most have
The compound of reactivity, all these peroxide esters are both needed to cryogenic freezing storage.Peroxide esters such as excessively sad tert-pentyl ester and mistake
Octanoic acid ter-butyl ester reactivity is slightly lower, can refrigerated storage.Benzylhydroperoxide tert-pentyl ester and this kind of peroxy esters of t-butyl perbenzoate are anti-
Answer activity minimum, thermostabilization is best, temperature can store at normal temperature.It is preferred that lauroyl peroxide, benzoyl peroxide, peroxidating
T-butyl perbenzoate.
In organic silicon adhesive of the present invention, the photoinitiator and free radical thermal initiator of use are if it is solid
, certain density solution being dissolved into low boiling point solvent in advance and being added to inside organosilicon constituent, last vacuum is stirred
It mixes removing and falls residual solvent.The method is common method in Adhesive Manufacturing Process, will no longer be repeated in example of the invention.
In organic silicon adhesive of the present invention, the photoinitiator or free radical thermal initiator of use cannot contain water
Point, in order to avoid cause moisture-curable.
In organic silicon adhesive of the present invention, the fumed silica (country is commonly called as fume colloidal silica) of use is
Using halosilanes through amorphous silica product a kind of made from oxyhydrogen flame pyrohydrolysis, the primary partial size of the product is 7
Between~40nm, specific surface area is generally in 100m2/ g~400m2It is a kind of extremely important inorganic nanometer powder material in/g range
Material.It is reinforcing due to its superior stability, thickening property and thixotropy and in rubber, plastics, electronics, coating, the neck such as adhesive
It is used widely in domain.Organosilicon material intensity itself is not high, and fumed silica is optimal reinforced filling.Hydrophily and
Hydrophobicity aerosil has good reinforcing effect to organosilicon, but hydrophilic fumed silica contains certain water
Divide and easily cause thickening or solidification, so the present invention selects hydrophobicity aerosil, preferably AEROSIL hydrophobicity titanium dioxide
Silicon R972.
In organic silicon adhesive of the present invention, the moisture-curable catalyst of use, or synthesis (methyl) acryloyl
The method of the alkoxyl silicone terminated dimethyl silicone polymer of oxygroup alkyl urea groups, the catalyst catalyst of use:
Common organic tin catalyst includes: dibutyl tin dilaurate, dibutyltin diacetate, two fourth of diethyl caproic acid
Ji Xi, two sad dibutyl tins, dimethyl maleic acid dibutyl tin, dibutyitin maleate, dioctyl tin diacetate, distearyl
Sour dioctyl tin, tin dilaurate dioctyl tin, dimethyl dibutyl tin, two phenoxy group dibutyl tins, two butanone oximido silicon, two fourth
Ji Xi, dibutyl tin diacetyl acetonate (referred to as chelating tin), ethyl diacetoacetate dibutyl tin, double two fourths of triethoxy silicic acid
The tetravalent tins such as the reaction product of Ji Xi, double triethoxy silicic acid dioctyl tins and diketone oximido tin oxide and silicate compound
Class compound；Stannous octoate, aphthenic acids tin, the divalent tin compound such as stearic acid tin；Three sad Monobutyltins, three isopropoxies
But one of or several mixing of the butyl tins such as butyl tin or single octyl tin compound or above-mentioned organotin.
Common bismuth organic compound includes: Bismuth Octoate, bismuth naphthenate, bismuth stearate etc..
Common titanate ester compound includes: tetra isopropyl titanate, and tetra-n-butyl titanate esters, (two is pungent for isopropyl three
Base pyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, two oleic acid acyloxy (two of isopropyl
Octylphosphonic acid acyloxy) titanate esters, single ketones oximido unsaturated fatty acid titanate esters, bis- (two octyloxy pyrophosphoric acid ester groups) ethylene titaniums
The chelate of acid esters and triethanolamine, Di(dioctylpyrophosphato) ethylene titanate, pyrophosphoric acid type single ketones oximido class titanium
Acid esters, two (octyl phenol polyoxyethylene ether) phosphides, tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters or above-mentioned
One or more of mixing of compound etc..
Common lewis acid compound includes: long chain fatty acids, alkyl benzene sulphonate, acid phosphatase esters compound, and three
It is fluorinated diethyl etherate, boron trifluoride acetic acid complex compound, boron trifluoride tetrahydrofuran complex compound, boron trifluoride methanol complexing
Object, Boron Trifluoride Ethylamine complex compound, boron trifluoride acetonitrile complex compound, boron trifluoride-phenol complex, boron trifluoride is to methyl
Phenol complexes, boron trifluoride benzylamine complex compound, boron trifluoride methyl ether complex compound, boron trifluoride ether complex, boron trifluoride
Carbonic acid dimethyl ester complex or corresponding Boron tribromide, one or more of triiodide boron complex or above compound
Mixing.Particularly preferred boron trifluoride etherate, Boron Trifluoride Ethylamine complex compound, boron trifluoride acetonitrile complex compound, trifluoro
Change the mixing of boron carbonic acid dimethyl ester complex one or more.
Common lewis base compound includes: triethylamine, trihexylamine, the aliphatic tertiary amines class compound such as trioctylamine；Ten
Dialkyl aniline, octadecyl aniline, the aromatic tertiary amines compound such as triphenylamine；Ethanol amine, diethanol amine, triethanolamine,
Diethyl triamine, trientine, cyclohexylamine, benzyl amine, hexamethylene diamine, guanidine compound, Ma beautiful jade class compound, imidazoles
Class compound, the other cyclic annular or amine with substituted functional group of 1,8- diazabicyclo (5,4,0) endecatylene -7 (DBU) etc.
The mixing of one or more of class compound or above compound.
The alkoxyl silicone terminated dimethyl silicone polymer synthetic method of (methyl) acryloxyalkyl urea groups of the invention
It is as follows:
100 parts by weight of hydroxy silicon oil that viscosity is 1000mPa.s by [synthesis -1], N- (normal-butyl)-γ-aminopropyl front three
5 parts by weight of oxysilane, 0.05 parts by weight of dibutyl tin dilaurate are added to N2The three of the cooling and reflux device of protection
It is below 80 DEG C with oil bath heating to pot temperature inside mouthful flask, every 10 minutes test reaction fluid viscosities, once viscosity
Reach 2000mPas addition 4 parts by weight of methylacryoyloxyethyl isocyanates at once, stops heating after reaction 1h.It has reacted
It is complete to be evaporated under reduced pressure the small molecule alcohol reactant for taking off generation, obtain the methylacryoyloxyethyl urea groups that viscosity is 2655mPas
The silicone terminated dimethyl silicone polymer of dimethylamine oxygroup, abbreviation oligomer -1.
100 parts by weight of hydroxy silicon oil that viscosity is 2000mPa.s by [synthesis -2], N- (methyl)-γ-aminopropyl trimethoxy
4 parts by weight of base silane, 0.1 parts by weight of Bismuth Octoate are added to N2Inside the three-necked flask of the cooling and reflux device of protection, under
Face oil bath heating to pot temperature be 80 DEG C, every 10 minutes test reaction fluid viscosities, once viscosity reaches 4000mPas
Addition 4 parts by weight of methylacryoyloxyethyl isocyanates at once, reaction 1h stop heating later.End of reaction vacuum distillation is de-
The small molecule alcohol reactant for falling generation obtains the methacryloxyethyl ureido-propyl dimethoxy that viscosity is 4880mPas
The silicone terminated dimethyl silicone polymer of base, abbreviation oligomer -2.
100 parts by weight of hydroxy silicon oil that viscosity is 5000mPa.s by [synthesis -3], N- (cyclohexyl)-γ-aminopropyl front three
3.5 parts by weight of oxysilane, 0.1 parts by weight of tin dilaurate dioctyl tin are added to N2The three of the cooling and reflux device of protection
It is below 80 DEG C with oil bath heating to pot temperature inside mouthful flask, every 10 minutes test reaction fluid viscosities, once viscosity
Reach 10000mPas addition 3.5 parts by weight of acryloyloxyethyl isocyanate at once, stops heating after reaction 1h.It has reacted
It is complete to be evaporated under reduced pressure the small molecule alcohol reactant for taking off generation, obtain the acrylyl oxy-ethyl urea groups third that viscosity is 16650mPas
The silicone terminated dimethyl silicone polymer of base dimethoxy, abbreviation oligomer -3.
100 parts by weight of hydroxy silicon oil that viscosity is 5000mPa.s by [synthesis -4], N- n-butylaminomethyl triethoxysilicane
6.5 parts by weight of alkane, 0.1 parts by weight of tin dilaurate dioctyl tin are added to N2The three-necked flask of the cooling and reflux device of protection
The inside is below 80 DEG C with oil bath heating to pot temperature, every 10 minutes test reaction fluid viscosities, once viscosity reaches
Addition 5.5 parts by weight of methacryloxy ethylene glycol isocyanates, reaction 1h stop heating 10000mPas later at once.Instead
The small molecule alcohol reactant that generation is taken off in vacuum distillation should be finished, the methacryloxypropyl second that viscosity is 13580mPas is obtained
The silicone terminated dimethyl silicone polymer of glycol urea groups dimethoxy, abbreviation oligomer -4.
100 parts by weight of hydroxy silicon oil that viscosity is 1000mPa.s by [synthesis -5], N- n-butylaminomethyl methyl dimethoxy oxygen
4.5 parts by weight of base silane, 0.1 parts by weight of DBU lewis base are added to N2The three-necked flask of the cooling and reflux device of protection
The inside is below 80 DEG C with oil bath heating to pot temperature, every 10 minutes test reaction fluid viscosities, once viscosity reaches
Addition 4.5 parts by weight of acryloyloxyethyl isocyanate, reaction 1h stop heating 2000mPas later at once.End of reaction decompression
The small molecule alcohol reactant of generation is taken off in distillation, obtains the acrylyl oxy-ethyl urea groups mono methoxy silicon that viscosity is 2640mPas
The dimethyl silicone polymer of sealing end.
UV/ heat/moisture triple curable organic silicone adhesive agent prescription and its performance test
100 parts by weight of meter of oligomer -1 that [embodiment -1] prepares [synthesis -1], 1.0 parts by weight azodiisobutyronitriles,
1.0 parts by weight chelate tin catalyst, and 1.0 parts by weight photoinitiator TPO, 35 parts by weight fumed silica R972 are added to planet and stir
Machine is mixed, is stirred under vacuum and is uniformly mixed, obtain paste high slumpability organic silicon adhesive, test its moisture-curable, photo-curable
And Thermocurable, acquired results subordinate list.
Subordinate list
| Embodiment -1 | Embodiment -2 | Embodiment -3 | Embodiment -4 | Embodiment -5 | Embodiment -6 | Comparative example -1 | Comparative example -2 | Comparative example -3 | Compare Example -4 | |
| Oligomer -1 | 100 | 100 | ||||||||
| Oligomer -2 | 100 | 100 | ||||||||
| Oligomer -3 | 100 | 100 | 100 | |||||||
| Oligomer -4 | 100 | 100 | ||||||||
| Oligomer -5 | 100 | |||||||||
| Fumed silica R972 | 35 | 25 | 20 | 20 | 30 | 30 | 35 | 25 | 20 | 20 |
| TPO | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |||
| DarOcure 1173 | 1 | 1 | 1 | 1 | 1 | 1 | ||||
| Chelate tin | 1 | 2 | 1 | 4 | 1 | |||||
| DBU | 2 | 1 | ||||||||
| Azodiisobutyronitrile | 1 | 1 | ||||||||
| Lauroyl peroxide | 0.5 | 1 | 0.5 | |||||||
| Benzoyl peroxide | 1 | 2 | 1 | |||||||
| Peroxidized t-butyl perbenzoate | 3 | 1 | 3 | |||||||
| High-pressure sodium lamp 1000mJ/cm2Solidfied material hardness | A49 | A48 | A44 | A42 | A50 | A46 | A44 | A41 | A39 | A39 |
| High-pressure sodium lamp 1000mJ/cm2Surface cure | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | △ | △ | △ | △ |
| Moisture-curable surface drying time | 6h | 3h | 6h | 9h | 9h | 6h | Do not solidify | Do not solidify | Do not solidify | It is not solid Change |
| 120 degree of 1h are heating and curing hardness | A44 | A46 | A39 | A39 | A47 | A44 | A39 | A39 | A37 | A35 |
| 120 degree of 1h heating surface curability | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | △ | △ | △ | △ |
It infuses, the meaning of each symbol is as follows in subordinate list:
◎: surface cure is good, and fingerprint is not stayed in finger touching, and surface is tack-free；
Zero: surface cure is general, and finger touching leaves fingerprint, the slightly viscous hand in surface；
△: surface cure is poor, and there is grease on surface, and fingerprint is obviously stayed in finger touching.
2~6 comparative example 1~4 of embodiment, which is all made of, prepares corresponding organic silicon adhesive with the identical method of embodiment 1
And it is as shown above to test its performance.
It is found by comparative example 1 and comparative example 1, does not add moisture-curable catalyst (chelating tin), photocuring in formula
(high voltage mercury lamp radiation dosage 1000mJ/cm2) surface cure by oxygen inhibition function influence clearly, after solidification
Surface is rendered obvious by out one layer of grease, is unfavorable for the continuous production of the next step, is also easily adhered the shadows such as dust foreign matter
Ring product quality.The case where 120 DEG C of heat cures, is similar with photocuring, does not add moisture-curable catalyst (chelating tin) in formula, Gu
The rear surface of change is rendered obvious by out one layer of grease.And it is added to the embodiment 1 of moisture-curable catalyst, the not only surface of photocuring
Curability is significantly improved, and the surface cure of heat cure is similarly improved.
From the embodiment of the present invention 1~6 as can be seen that simultaneously containing can be in the silicone molecules structure that synthesizes of the present invention
Ultraviolet light radically curing, the functional group of free radical heat cure and moisture-curable can carry out ultraviolet curing, heat cure respectively
With moisture-curable to obtain except good solidfied material, surface cure quality is also obviously improved, to raising electronic product
Production efficiency in assembling process, improving solidification quality has huge help.
Although the embodiment of the present invention 1~6 only lists the organic silicon adhesive of five kinds of structures, through experimental test,
Although the not isoplastic structure is slightly different to service performance, it is attained by solidification effect of the invention, so of the invention
It does not enumerate.
The present invention have photo-curing material Rapid high-efficiency energy-saving it is environmentally friendly the advantages that, heater can be passed through for shadow region
Skill carrys out rapid curing, simultaneously because having moisture-curable function, does not fear oxygen inhibition effect to the photocuring of free radical mechanism
Or the baneful influence of heat cure, surface cure are significantly improved, and yield is promoted, and are reduced and are solidified bad, quickening shipment speed
Degree, the curing process particularly suitable for e-factory are rapid and efficient.
Claims (10)
1.UV/ heat/moisture triple curable organic silicon adhesive, which is characterized in that based on parts by weight, which includes 100
The alkoxyl silicone terminated dimethyl silicone polymer of part (methyl) acryloxyalkyl urea groups, 0.5 ~ 5 part of photoinitiator, 0.5 ~ 5
Part moisture-curable catalyst, 0.5 ~ 5 part of free radical thermal initiator, 1.0 ~ 40 parts of fumed silicas.
2. organic silicon adhesive according to claim 1, which is characterized in that (methyl) acryloxyalkyl urea groups alcoxyl
The structure of the silicone terminated dimethyl silicone polymer of base is as follows:
Wherein,
R1For H or methyl；
R2For CH2, CH2CH2, CH2CH2CH2Or CH2CH2OCH2CH2；
R3For H or methyl；
R4For methyl, ethyl, propyl, butyl or phenyl；
R5For CH2Or CH2CH2CH2；
R6For methyl, methoxy or ethoxy；
R7For methyl, methoxy or ethoxy；
The integer that n is 200 ~ 2000.
3. organic silicon adhesive according to claim 1, which is characterized in that photoinitiator is selected from 2- hydroxy-2-methyl -1-
Phenyl -1- acetone, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, 2,4,6- tri-methyl benzophenones and 4- methyl two
The mixture of Benzophenone, benzoin dimethylether, benzophenone, 1- hydroxy-cyciohexyl Benzophenone, α, α '-acetophenone or
Any one or a few mixing in α-amine alkyl phenones, preferably 2- hydroxy-2-methyl -1- phenyl -1- acetone and 2,4,6-
The mixing of any one or two kinds in trimethylbenzoy-dipheny phosphine oxide.
4. organic silicon adhesive according to claim 1, which is characterized in that moisture-curable catalyst is organotin chemical combination
Any one or a few in object, titanate ester compound, α silane coupling agent, Louis's acids or Louis's alkaloid compound,
It is preferred that any one in organo-tin compound or Louis's alkaloid compound or two kinds.
5. organic silicon adhesive according to claim 1, which is characterized in that free radical thermal initiator includes that azo causes
Agent and organic peroxide evocating agent, azo-initiator preferred AIBN, AIBME；The preferred peroxide of organic peroxide evocating agent
Change lauroyl, benzoyl peroxide, peroxidized t-butyl perbenzoate.
6. organic silicon adhesive according to claim 1, which is characterized in that fumed silica is hydrophobicity gas phase dioxy
SiClx, preferably AEROSIL hydrophobic silica R972.
7.(methyl) the alkoxyl silicone terminated dimethyl silicone polymer of acryloxyalkyl urea groups, which is characterized in that its structure
Formula is as follows:
Wherein,
R1For H or methyl；
R2For CH2, CH2CH2, CH2CH2CH2Or CH2CH2OCH2CH2；
R3For H or methyl；
R4For methyl, ethyl, propyl, butyl or phenyl；
R5For CH2Or CH2CH2CH2；
R6For methyl, methoxy or ethoxy；
R7For methyl, methoxy or ethoxy；
The integer that n is 200 ~ 2000.
8.(methyl) the alkoxyl silicone terminated dimethyl silicone polymer of acryloxyalkyl urea groups synthetic method, feature exists
In, include the following steps: silane coupling agent that 1.0 ~ 10 parts by weight contain secondary amine and 100 parts by weight hydroxy silicon oils 0.01 ~
It under the action of 2.0 parts by weight catalyst catalyst, reacts at 80 ± 5 DEG C, reaches 1.0 ~ 10 weights of addition after certain viscosity
Part (methyl) acryloyloxyalkyl isocyanate is measured, obtaining both-end is the poly- of (methyl) acryloxyalkyl urea groups alkoxyl silicone
Dimethyl siloxane.
9. method according to claim 8, which is characterized in that reach addition (methyl) acryloyloxyalkyl after certain viscosity
Isocyanates, the certain viscosity are 2.0 ~ 5.0 times for being hydroxy silicon oil viscosity.
10. method according to claim 8, which is characterized in that the structure of hydroxy silicon oil is as follows:
The integer that n is 200 ~ 2000.
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| CN116082642A (en) * | 2022-12-27 | 2023-05-09 | 广州回天新材料有限公司 | Acryloyloxy alkoxy-terminated polysiloxane, sealant and preparation method and application thereof |
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