CN105384906A - Photocuring prepolymer tackiness agent and preparation method thereof - Google Patents
Photocuring prepolymer tackiness agent and preparation method thereof Download PDFInfo
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- CN105384906A CN105384906A CN201510970121.3A CN201510970121A CN105384906A CN 105384906 A CN105384906 A CN 105384906A CN 201510970121 A CN201510970121 A CN 201510970121A CN 105384906 A CN105384906 A CN 105384906A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a photocuring prepolymer tackiness agent. The photocuring prepolymer tackiness agent is prepared from, by weight, 80%-98% of photocuring prepolymer, 2%-10% of modified polymercaptan and 0.005%-1% of photoinitiator. The photocuring prepolymer is prepared from, by weight, 70%-85% of polymer polyhydric alcohol, 10%-25% of diisocyanate, 1%-10% of vinyl ether containing hydroxyl and 0.01%-1% of addition agent. According to the photocuring prepolymer tackiness agent, the polyhydric alcohol in the prepolymer is pretreated, and the polymercaptan is modified, so that under the conditions that the content of the initiator is low and the amount of ultraviolet light energy needed by surface curing is small, it is guaranteed that the curing thickness is still kept large under the low ultraviolet light energy, the storage time is long, the production cost is greatly lowered, and application in actual production can be better facilitated.
Description
Technical field
The present invention relates to curable adhesive, particularly relate to a kind of prepolymer containing vinyl ether and the photo curable tackiness agent formed with mercaptan thereof.
Background technology
Curable adhesive is also known as UV glue, and essentially consist is: (1) prepolymer; (2) reactive monomer; (3) light trigger; (4) auxiliary agent.The ultimate principle of curable adhesive is: main gel is at UV-irradiation several tens of seconds, and light trigger decomposes generation radical makes its polymerizing curable, and makes it change reticulated structure into by linear structure.
Photocuring prepolymer, also known as oligopolymer, is the low-molecular(weight)polymer containing unsaturated functional group, most oligopolymer for end acrylate, and prepolymer is the main body of light-cured resin, and its performance determines the salient features of the rear material of solidification substantially.The curable adhesive prepared by such prepolymer can be subject to the impact of oxygen in air.Because in top layer, the concentration of oxygen is the highest, the restraining effect of oxygen often causes lower floor to be solidified, and top layer is still uncured and be clamminess.
Mercaptan/alkene photocuring system is insensitive to oxygen, and the light-initiated dosage that needs add is little, therefore can carry out the solidification of more deep layer, increases the cured thickness of goods.But mercaptan/alkene system also exists some shortcomings, the prepolymer as being applicable to this system is less, and the finished product shelf lives is short, and these limitation limit the application of mercaptan/alkene photocuring system.
Summary of the invention
In order to overcome above-mentioned technical problem, the invention provides a kind of prepolymer containing vinyl ether and the photo curable tackiness agent formed with mercaptan thereof, it has good chemical stability and adhesive solidification characteristic, greatly reduces production cost.
The photo curable prepolymer of one of the present invention, by weight percentage, is polymerized by following component:
Polymer polyatomic alcohol 70 ~ 85%
Vulcabond 10 ~ 25%
The vinyl ether 1 ~ 10% of hydroxyl
Auxiliary agent 0.01 ~ 1%.
Further, described polymer polyatomic alcohol is the mixture of any one or more in polyether glycol, polyester polyol, polyolefin polyhydric alcohol, and carries out pre-treatment through following method:
C is added by 100g polymer polyatomic alcohol
12-C
16the ratio of alkyl alkoxy sulfate 10g is by polymer polyatomic alcohol and C
12-C
16the abundant hybrid reaction of alkyl alkoxy sulfate, temperature of reaction is 60-82 DEG C, and reaction times 1-2 hour, namely completes pretreatment technology.
Further, each component is preferably:
Polymer polyatomic alcohol 78 ~ 80%
Vulcabond 15 ~ 20%
The vinyl ether 1 ~ 5% of hydroxyl
Auxiliary agent 0.01 ~ 0.5%.
Further, described vulcabond is that 1,6-di-isocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate are a kind of or two kinds.
Further, the vinyl ether of described hydroxyl is 4-hydroxy butyl vinyl ether.
Further, described auxiliary agent is catalyzer and stopper, and catalyzer is dibutyl tin laurate and/or sad sub-alkene, and stopper is Resorcinol, para benzoquinone and/or p-ten.-butylcatechol.The weight ratio of catalyzer and stopper is 1-2:1.
Present invention also offers a kind of tackiness agent comprising above-mentioned prepolymer, be made up of according to weight percent following component:
Above-mentioned photocurable prepolymer 80-98%
Modified polysulfide alcohol 2-10%
Light trigger 0.005-1%.
Further, described modified polysulfide alcohol is tetramethylolmethane four (3-thiohydracrylic acid) ester, trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (2-mercaptoacetate), three [2-(3-thiohydracrylic acid base) ethyl] chlorinated isocyanurates, four (3-mercaptobutyric acid) pentaerythritol ester, preferably four (3-mercaptobutyric acid) pentaerythritol ester.
Or described polythiol is the modified polysulfide alcohol obtained through modification:
By polythiol and dicyclohexyl methane diisocyanate in mass ratio 1:0.05-0.1 put into container, pass into rare gas element, stir, be then heated to 60-70 DEG C of return stirring 4-5 hour, obtain modified polysulfide alcohol.
Further, described light trigger is one or more in 1-hydroxy-cyclohexan benzoylformaldoxime, 1-hydroxy-cyciohexyl phenyl ketone, benzoin dimethylether, 2,4,6-trimethylbenzoy-dipheny phosphine oxides.
Further, each component is preferably:
Above-mentioned photocurable prepolymer 93-98%
Modified polysulfide alcohol 2-7%
Light trigger 0.005-0.2%.
Present invention also offers the preparation method of above-mentioned photo curable prepolymer tackiness agent, specific as follows:
(1) preparation of prepolymer: polymer polyatomic alcohol is vacuumized at 120-150 DEG C dehydration 1-3 hour, polymer polyatomic alcohol after dehydration, vulcabond are put into reactor together, add catalyzer, 3-5 hour is reacted at 75-80 DEG C, add vinyl ether and the stopper of hydroxyl, continue to react 2 hours at 75-80 DEG C, be cooled to 45 DEG C of dischargings.
(2) modification of polythiol: by polythiol and dicyclohexyl methane diisocyanate in mass ratio 1:0.05-0.1 put into container, pass into rare gas element, stir, be then heated to 60-70 DEG C of return stirring 4-5 hour, obtain modified polysulfide alcohol product.
(3) synthesis of tackiness agent: add modified polysulfide alcohol and light trigger in prepolymer, is uniformly mixed until evenly, vacuumizing and defoaming, discharging in planet stirring tank.
Further, the modification procedure to polymer polyatomic alcohol is also comprised in step (1): add C by 100g polymer polyatomic alcohol
12-C
16the ratio of alkyl alkoxy sulfate 10g is by polymer polyatomic alcohol and C
12-C
16the abundant hybrid reaction of alkyl alkoxy sulfate, temperature of reaction is 60-82 DEG C, and reaction times 1-2 hour, namely completes pretreatment technology.
Advantage of the present invention and effect are:
1, select photo curable prepolymer, polythiol, light trigger containing vinyl ether, carry out proportioning according to a specific ratio, prepare curable adhesive.Modification is carried out to the polyvalent alcohol in prepolymer and polythiol, improves chemical stability and the solidification effect of tackiness agent, greatly reduce production cost.
2, compared with propenoic acid ester photocureable tackiness agent, this curable adhesive photoinitiator levels is few, and the UV energy needed for surface cure is few, and under low ultraviolet energy, cured thickness is also very large, and curing depth reaches more than 9mm.
3, compared with the photocuring system disclosed in the past, the storage time is long, stores more than six months gel-free phenomenons, be more conducive to the application in actual production under constant temperature.
Embodiment
Below in conjunction with embodiment and embodiment, the present invention will be further described.
Embodiment 1
The synthesis of prepolymer PreP-1: by 200 gram molecular weights (Mn) 2000, hydroxyl value be about 56 polyester diol at 120 DEG C, vacuumize dehydration 1 hour, by dehydration after polyether Glycols, 44.46 gram 1,6-di-isocyanate puts into reactor together, add 0.1 gram of dibutyl tin laurate, 78 DEG C of reactions 4 hours, add 23.2 grams of 4-hydroxy butyl vinyl ethers, 0.1 gram of Resorcinol is as stopper, continue 78 DEG C of reactions 2 hours, be cooled to 45 DEG C of dischargings, be referred to as PreP-1.
Embodiment 2
The synthesis of prepolymer PreP-2: get 300 gram molecular weights (Mn) 3000, hydroxyl value is the polyether Glycols of about 37, adds C by 100g polyether Glycols
12-C
16the ratio of alkyl alkoxy sulfate 10g is by polyether Glycols and C
12-C
16the abundant hybrid reaction of alkyl alkoxy sulfate, temperature of reaction is 70 DEG C, in 2 hours reaction times, namely completes pretreatment technology.Modified polyether Glycols vacuumizes dehydration 2 hours at 130 DEG C, polyether Glycols after dehydration, 45 grams of Methylcyclohexyl diisocyanates are put into reactor together, add 0.2 gram of dibutyl tin laurate, 80 DEG C of reactions 3 hours, add 26 grams of 4-hydroxy butyl vinyl ethers, 0.1 gram of Resorcinol, as stopper, continues 78 DEG C of reactions 2 hours, be cooled to 45 DEG C of dischargings, be referred to as PreP-2.
Embodiment 3
The synthesis of prepolymer PreP-3: by 200 gram molecular weights (Mn) 2000, hydroxyl value be about 56 polyether Glycols at 120 DEG C, vacuumize dehydration 1 hour, polyether Glycols after dehydration, 44.46 grams of isophorone diisocyanates are put into reactor together, add 0.1 gram of dibutyl tin laurate, 78 DEG C of reactions 3 hours, add 26 grams of hydroxyethyl methylacrylates, 0.1 gram of Resorcinol is as stopper, continue 78 DEG C of reactions 2 hours, be cooled to 45 DEG C of dischargings, be referred to as PreP-3.
Embodiment 4
Get 100 weight part PreP-1,10 weight part tetramethylolmethane four (3-thiohydracrylic acid) esters, 0.2 weight part 1-hydroxycyclohexyl phenyl ketone is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Embodiment 5
Get 100 weight part PreP-2,10 weight part tetramethylolmethane four (3-thiohydracrylic acid) esters, 0.2 weight part 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Embodiment 6
By tetramethylolmethane four (3-thiohydracrylic acid) ester and dicyclohexyl methane diisocyanate in mass ratio 1:0.05 put into container, pass into rare gas element, stir, be then heated to 60 DEG C of return stirrings 5 hours, obtain modification tetramethylolmethane four (3-thiohydracrylic acid) ester.
Get 100 weight part PreP-1,10 part by weight modified tetramethylolmethane four (3-thiohydracrylic acid) esters, 0.1 weight part 1-hydroxycyclohexyl phenyl ketone is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Embodiment 7
By four (3-mercaptobutyric acid) pentaerythritol esters and dicyclohexyl methane diisocyanate in mass ratio 1:0.05 put into container, pass into rare gas element, stir, be then heated to 60 DEG C of return stirrings 5 hours, obtain modification four (3-mercaptobutyric acid) pentaerythritol ester.
Get 100 weight part PreP-2,3 part by weight modified four (3-mercaptobutyric acid) pentaerythritol ester, 0.005 weight part 2; 4; 6 (trimethylbenzoyl) diphenyl phosphine oxide is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Embodiment 8
By four (3-mercaptobutyric acid) pentaerythritol esters and dicyclohexyl methane diisocyanate in mass ratio 1:0.1 put into container, pass into rare gas element, stir, be then heated to 60 DEG C of return stirrings 5 hours, obtain modification four (3-mercaptobutyric acid) pentaerythritol ester.
Get 100 weight part PreP-2,3 part by weight modified four (3-mercaptobutyric acid) pentaerythritol ester, 0.01 weight part 2; 4; 6 (trimethylbenzoyl) diphenyl phosphine oxide is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Comparative example
Get 100 weight part PreP-3,10 weight part tetramethylolmethane four (3-thiohydracrylic acid) esters, 0.2 weight part 1-hydroxycyclohexyl phenyl ketone is uniformly mixed until evenly in planet stirring tank, vacuumizing and defoaming, discharging.
Embodiment 4-8 and comparative example are tested, are specially:
1, surface drying situation: put a small amount of glue (about 1g) on sheet glass, is positioned over ultraviolet curing machine solidification, then with finger touching, is tack-freely ●, sticky hand is ▲;
2, curing depth: put a certain amount of glue in circular dishware, is positioned over ultraviolet curing machine solidification, then takes out the glue after measuring solidification thick.
3, stability in storage: glue is placed in black packing bottle, is placed in thermostatic chamber and (places under 23 ± 2 DEG C of conditions and to observe whether gel after 6 months.
Test result is see table 1.
Table 1
Owing to carrying out pre-treatment to polymer polyatomic alcohol surface, improve the surfactivity of polymer polyatomic alcohol, facilitate the chemical reaction between photocuring prepolymer and polythiol, cured adhesive stability has been had and significantly improves.Through carrying out modification to polythiol, make solidification rapidly, reactive behavior is high, and after the consumption significantly reducing solidification light trigger, its curing depth still keeps higher level.
The above embodiment only have expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a photo curable prepolymer, is characterized in that, by weight percentage, is polymerized by following component:
Polymer polyatomic alcohol 70 ~ 85%
Vulcabond 10 ~ 25%
The vinyl ether 1 ~ 10% of hydroxyl
Auxiliary agent 0.01 ~ 1%.
2. the photo curable prepolymer of one according to claim 1, it is characterized in that, described polymer polyatomic alcohol is the mixture of any one or more in polyether glycol, polyester polyol, polyolefin polyhydric alcohol, and carries out pre-treatment through following method: add C by 100g polymer polyatomic alcohol
12-C
16the ratio of alkyl alkoxy sulfate 10g is by polymer polyatomic alcohol and C
12-C
16the abundant hybrid reaction of alkyl alkoxy sulfate, temperature of reaction is 60-82 DEG C, and reaction times 1-2 hour, namely completes pretreatment technology.
3. the photo curable prepolymer of one according to claim 1 and 2, is characterized in that, each component is preferably:
Polymer polyatomic alcohol 78 ~ 80%
Vulcabond 15 ~ 20%
The vinyl ether 1 ~ 5% of hydroxyl
Auxiliary agent 0.01 ~ 0.5%.
4. the photo curable prepolymer of one according to claim 1 and 2, is characterized in that, described vulcabond is that 1,6-di-isocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate are a kind of or two kinds; The vinyl ether of described hydroxyl is 4-hydroxy butyl vinyl ether; Described auxiliary agent is catalyzer and stopper, and catalyzer is dibutyl tin laurate and/or sad sub-alkene, and stopper is Resorcinol, para benzoquinone and/or p-ten.-butylcatechol.The weight ratio of catalyzer and stopper is 1-2:1.
5. a photo curable prepolymer tackiness agent, is characterized in that, is made up of according to weight percent following component:
Photo curable prepolymer 80-98% described in any one of claim 1-4
Polythiol 2-10%
Light trigger 0.005-1%.
6. photo curable prepolymer tackiness agent according to claim 5, it is characterized in that, described polythiol is tetramethylolmethane four (3-thiohydracrylic acid) ester, trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (2-mercaptoacetate), three [2-(3-thiohydracrylic acid base) ethyl] chlorinated isocyanurates, four (3-mercaptobutyric acid) pentaerythritol ester, preferably four (3-mercaptobutyric acid) pentaerythritol ester;
Or described polythiol is the modified polysulfide alcohol obtained through modification:
By polythiol and dicyclohexyl methane diisocyanate in mass ratio 1:0.05-0.1 put into container, pass into rare gas element, stir, be then heated to 60-70 DEG C of return stirring 4-5 hour, obtain modified polysulfide alcohol.
7. the photo curable prepolymer tackiness agent according to claim 5 or 6; described light trigger is 1-hydroxy-cyclohexan benzoylformaldoxime, 1-hydroxy-cyciohexyl phenyl ketone, benzoin dimethylether, 2; one or more in 4,6-trimethylbenzoy-dipheny phosphine oxide.
8. the photo curable prepolymer tackiness agent according to claim 5 or 6, is characterized in that,
Photo curable prepolymer 93-98% described in any one of claim 1-4
Modified polysulfide alcohol 2-7%
Light trigger 0.005-0.2%.
9. a preparation method for photo curable prepolymer tackiness agent according to claim 6, is characterized in that, comprise the steps:
(1) preparation of prepolymer: polymer polyatomic alcohol is vacuumized at 120-150 DEG C dehydration 1-3 hour, polymer polyatomic alcohol after dehydration, vulcabond are put into reactor together, add catalyzer, 3-5 hour is reacted at 75-80 DEG C, add vinyl ether and the stopper of hydroxyl, continue to react 2 hours at 75-80 DEG C, be cooled to 45 DEG C of dischargings.
(2) modification of polythiol: by polythiol and dicyclohexyl methane diisocyanate in mass ratio 1:0.05-0.1 put into container, pass into rare gas element, stir, be then heated to 60-70 DEG C of return stirring 4-5 hour, obtain modified polysulfide alcohol product.
(3) synthesis of tackiness agent: add modified polysulfide alcohol and light trigger in prepolymer, is uniformly mixed until evenly, vacuumizing and defoaming, discharging in planet stirring tank.
10. the preparation method of photo curable prepolymer tackiness agent according to claim 9, is characterized in that, also comprises the pre-treatment step to polymer polyatomic alcohol: add C by 100g polymer polyatomic alcohol in step (1)
12-C
16the ratio of alkyl alkoxy sulfate 10g is by polymer polyatomic alcohol and C
12-C
16the abundant hybrid reaction of alkyl alkoxy sulfate, temperature of reaction is 60-82 DEG C, and reaction times 1-2 hour, namely completes pretreatment technology.
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CN105878054A (en) * | 2016-04-07 | 2016-08-24 | 广州市尤特新材料有限公司 | LED-UV phototherapy glue scrubbing-free sealing layer glue and preparation method thereof |
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CN109415512A (en) * | 2016-06-28 | 2019-03-01 | Prc-迪索托国际公司 | Bis- (alkenyl) ethers of amido-containing acid ester/urea, the prepolymer prepared using bis- (alkenyl) ethers of amido-containing acid ester/urea, and application thereof |
CN110540825A (en) * | 2019-09-16 | 2019-12-06 | 杭州得力科技股份有限公司 | Preparation method of high-refractive-index UV curing adhesive and product |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775732A (en) * | 1988-01-11 | 1988-10-04 | Allied-Signal Inc. | Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes |
JP2004035734A (en) * | 2002-07-03 | 2004-02-05 | Toagosei Co Ltd | Pressure-sensitive adhesive composition curable by actinic radiation |
CN102575009A (en) * | 2009-08-19 | 2012-07-11 | 株式会社普利司通 | Photocurable composition |
CN104497956A (en) * | 2014-12-18 | 2015-04-08 | 北京天山新材料技术有限公司 | Rapidly-cured double-component polyurethane elastic adhesive and preparation method thereof |
-
2015
- 2015-12-22 CN CN201510970121.3A patent/CN105384906B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775732A (en) * | 1988-01-11 | 1988-10-04 | Allied-Signal Inc. | Vinyl ether terminated ester and urethane resins from bis(hydroxyalkyl)cycloalkanes |
JP2004035734A (en) * | 2002-07-03 | 2004-02-05 | Toagosei Co Ltd | Pressure-sensitive adhesive composition curable by actinic radiation |
CN102575009A (en) * | 2009-08-19 | 2012-07-11 | 株式会社普利司通 | Photocurable composition |
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