CN100424109C - Preparation method of amino silane modified urethane acrylate resin - Google Patents
Preparation method of amino silane modified urethane acrylate resin Download PDFInfo
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- CN100424109C CN100424109C CNB2006100352203A CN200610035220A CN100424109C CN 100424109 C CN100424109 C CN 100424109C CN B2006100352203 A CNB2006100352203 A CN B2006100352203A CN 200610035220 A CN200610035220 A CN 200610035220A CN 100424109 C CN100424109 C CN 100424109C
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Abstract
The present invention discloses a preparation method of amino silane modified polyurethane acrylic resin. In the preparation method, epoxy radical silicane is dropwise added to primary amino silane at 40 to 100 DEG C for 15 to 60 minutes to finish the addition, and then the reaction is carried out for 1 to 3 hours at 40 to 100 DEG C of heat preservation to obtain modified silane coupling agents. Polyether polylol is uniformly mixed with hydroxy-acrylic resin and then is vacuumized, and isocyanate is added to the mixtures at 20 to 50 DEG C to react for 1 to 3 hours at raised temperature of 60 to 100 DEG C after heat release is finished; in this way, end-isocyanate prepolymers can be obtained, and the modified silane coupling agents are added to the prepolymers drop by drop to react for 1 to 3 hours at 60 to 100 DEG C to obtain amino silane modified polyurethane acrylic resin. The present invention has the advantages of stable modifying process, simple operation, no need of using specific equipment and low production cost; secondary amino silane coupling agents obtained by the modifying means have the advantages of low viscosity and high stability.
Description
Technical field
The present invention relates to a kind of preparation method of organo-silicon coupling agent modified urethane acrylate resin, particularly a kind of preparation method of amino silane modified polyurethane acrylate resin.
Background technology
Silane coupling agent can be tied two kinds of materials of different nature in the adhesive bond of two weak adhesive interfaces by " molecule bridge " formation firm stable.The molecular structure of silane generally is expressed as follows:
(RO)
3Si-(CH
2)
3-X
R=alkyl (methyl, ethyl etc.)
X=organo-functional group (sulfydryl, amino, epoxy group(ing) etc.)
From above-mentioned molecular structure as can be seen, contain the organoalkoxysilane that under certain humidity, hydrolysis can take place and the silane polycondensation takes place in the silane coupling agent, and organo-functional group X and organic resin have certain consistency, and the two can be tied by chemical reaction or physical-chemical reaction (hydrogen bond, polymer interpenetration network, electrostatic force).
X in the hydrolyzable organo silane coupling agent contains the active H atom that can react with isocyanate terminated polyurethane acrylate prepolymer aggressiveness, is to contain NH and use many
2The perhaps silane coupling agent of NH, the coupling agent that contains sulfydryl SH also has application.
Be applied in GB-A-1102251, EP-A-0018094, DE-A-1162818, USP3590065, USP3849471, USP4082790, USP4012403, the USP4401286 etc. that contain the silane coupling agent of SH functional group occurred, but, thereby cause because the existence of remaining SH makes organic resin also have one to be difficult to the taste of hearing and can't use because the sulfydryl SH of this silane coupling agent produces a kind of very niff.
The application of primary amino silane coupling agent is the most widely, has a lot of patents to use amino silicane coupling agent.For example: DE-A-1152695, DE-A-1271712, DE-A-2161716, DE-A-2408480, DE-A-2521399, DE-A-2749316, USP2832754, USP2971864, USP4481364.But all mention such problem simultaneously in above-mentioned patent documentation: the speed of response of remaining isocyanate-monomer is quite fast in primary amino silane coupling agent and the performed polymer, and the reaction that takes place thus can cause system consistency and homogeneity very poor, the viscosity of resin increase simultaneously is more, finally has influence on the reaction of silane coupling agent and prepolymer resin.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide a kind of preparation method of amino silane modified polyurethane acrylate resin.The present invention utilizes the primary amino silane coupling agent secondary amino group silane coupling agent that cost is relatively low through certain modified method obtained performance is good of production in enormous quantities, is applied in the polyurethane acrylic resin to solve the insufficient shortcoming of its thermotolerance and water tolerance.
The invention relates to a kind of new compound that contains secondary amino group and silicon alkoxyl group, is about the synthetic of it and the application in the polyurethane acrylate prepolymer polyimide precursor resin.The secondary amino group silane coupling agent reacts comparatively steady because its secondary amino group is more than the active reduction of primary amino, the shortcoming of primary amino silane coupling agent can not occur, can obtain good resin material.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of amino silane modified polyurethane acrylate resin comprises the steps:
(1) epoxy radicals silicone hydride is added drop-wise under 40～100 ℃ in the primary amino silane, dripped off in 15～60 minutes, 40～100 ℃ of following insulation reaction 1～3 hour, obtain modified silane coupler then; The mol ratio of described primary amino silane and epoxy radicals silicone hydride is 0.9～2: 1.
(2) with behind polyether glycol and the Hydroxylated acrylic resin mixing,-0.2～-0.1Mpa, temperature vacuumized 2～3 hours under 90～120 ℃ the condition, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) of unreacted and remaining moisture; The weight ratio of described polyether glycol and Hydroxylated acrylic resin is 2～10: 1.
(3) mixture in the step (2) is cooled to 20～50 ℃, add vulcabond, treat to be warmed up to 60～100 ℃ of reactions 1～3 hour after heat release finishes,, obtain isocyanate terminated performed polymer up to reaction end; The mol ratio of described isocyanate group and hydroxyl is 1.5～2: 1.
(4) modified silane coupler in the step (1) is added drop-wise in the performed polymer of step (3),,, obtains amino silane modified polyurethane acrylate resin up to reaction end in 60～100 ℃ of reactions 1～3 hour; The mol ratio of remaining isocyanate group is 0.1～1.0: 1 in described modified silane and the performed polymer.
In order to realize the present invention better, the special preferred version of step (1): preferably under 60～80 ℃, be added drop-wise in the primary amino silane epoxy radicals silicone hydride, dripped off in 15～60 minutes, and 60～80 ℃ of following insulation reaction 1.5～2.5 hours, obtained modified silane coupler then; The mol ratio of described primary amino silane and epoxy radicals silicone hydride is 0.9～2: 1.
Described epoxy radicals silicone hydride is a γ-An Bingjisanyiyangjiguiwan; Described primary amino silane is γ-glycidyl ether oxygen propyl trimethoxy silicane.Described vulcabond comprises tolylene diisocyanate (TDI) or diphenylmethanediisocyanate (MDI) etc.
The mol ratio of primary amino silane and epoxy radicals silicone hydride is preferably 1.5～2 in the described step (1): 1.
The weight ratio of polyether glycol and Hydroxylated acrylic resin is preferably 2～4 in the described step (2): 1.
The mol ratio of isocyanate group and hydroxyl is preferably 1.8～2 in the described step (3): 1.
The mol ratio of remaining isocyanate group is preferably 0.2～0.5 in middle modified silane coupler of described step (4) and the performed polymer: 1.
The present invention compared with prior art has following advantage and beneficial effect: (1) can go out the secondary amino group silane coupling agent in modification under the laboratory condition, the experiment simple possible; (2) modifying process is steady, and is simple to operate, do not need to use special equipment, and production cost is low; (3) the secondary amino group silane coupling agent viscosity that obtains through modified method is low, good stability adopts that this silane coupling agent prepared organic silicon modified polyurethane acrylic resin can not occur being similar to that the speed of response of primary amino silane coupling agent is fast, consistency and homogeneity difference and the big shortcoming of viscosity.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 7.02g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 60 ℃; In 30 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 3 hours down at 60 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 100g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 30.62g diphenylmethanediisocyanate (MDI) after 30 minutes, treat to be warmed up to 80 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 2.41g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 2
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 7.02g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 40 ℃; In 60 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 3 hours down at 40 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 150g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 90 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 20 ℃ then, remove vacuum; Logical high pure nitrogen adds 30.76g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 70 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 4.81g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 3
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 4.5g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 50 ℃; In 60 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 2 hours down at 50 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 200g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 30 ℃ then, remove vacuum; Logical high pure nitrogen adds 41.08g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 60 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 60 ℃ after 15 minutes, added the 7.68g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 4
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 8.43g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 70 ℃; In 30 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 3 hours down at 70 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 100g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 120 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 22.50g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 90 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 1 hour obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, the 6.26g that added in 30 minutes in the step (1) stretches aminosilane, and stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 5
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 8.43g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 70 ℃; In 30 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 3 hours down at 70 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 150g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 32.38g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 70 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 2.82g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 2 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 6
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 8.43g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 90 ℃; In 30 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 1 hour down at 90 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 200g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 53.12g diphenylmethanediisocyanate (MDI) after 30 minutes, treat to be warmed up to 80 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 4.06g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 7
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 9.36g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 80 ℃; In 30 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 1.5 hours down at 80 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 100g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.1Mpa, vacuumized 2.5 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 23.68g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 70 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 3 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 2.66g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 2 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 8
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 9.36g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 80 ℃; In 50 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 2.5 hours down at 80 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 150g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.2Mpa, vacuumized 3 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 41.87g diphenylmethanediisocyanate (MDI) after 30 minutes, treat to be warmed up to 80 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 2 hours obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 80 ℃ after 15 minutes, added the 5.51g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 3 hours through the silane-modified polyurethane acrylate resin of secondary amino group.
Embodiment 9
(1) γ-An Bingjisanyiyangjiguiwan (KH550) of adding 9.36g in four-hole boiling flask connects thermometer and stirring rake, and logical high pure nitrogen 20 minutes is warmed up to 100 ℃; In 15 minutes, 5g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped off, be incubated 1 hour down at 100 ℃ then, obtain modified silane coupler secondary amino group silane.
(2) in four-hole boiling flask, add the polyether glycol (N-220) of 500g and the hydroxyl acrylic resin (hydroxyl value is 40.5mgKOH/g) of 50g, be warmed up to 60 ℃, be warmed up to 110 ℃ after mixing half an hour, under the vacuum tightness of-0.15Mpa, vacuumized 2 hours, to remove intact monomer (mainly being butyl acrylate and methyl methacrylate monomer) and the remaining moisture of unreacted in the mixture, up to no overhead product.
(3) cool to 50 ℃ then, remove vacuum; Logical high pure nitrogen adds 39.03g tolylene diisocyanate (TDI) after 30 minutes, treat to be warmed up to 100 ℃ after the exothermic peak end, and the insulation reaction discharging that outgases after 1 hour obtains faint yellow polyurethane acrylate prepolymer aggressiveness.
(4) in another four-hole boiling flask, add 50.0g polyurethane acrylate prepolymer aggressiveness in the step (2), logical nitrogen is warmed up to 100 ℃ after 15 minutes, added the 2.50g secondary amino group silane in the step (1) in 30 minutes, stirring reaction obtains after 1 hour through the silane-modified polyurethane acrylate resin of secondary amino group.
Claims (9)
1. the preparation method of an amino silane modified polyurethane acrylate resin is characterized in that comprising the steps:
(1) epoxy radicals silicone hydride is added drop-wise under 40～100 ℃ in the primary amino silane, dripped off in 15～60 minutes, 40～100 ℃ of following insulation reaction 1～3 hour, obtain modified silane coupler then; The mol ratio of described primary amino silane and epoxy radicals silicone hydride is 0.9～2: 1;
(2) with behind polyether glycol and the Hydroxylated acrylic resin mixing ,-0.2～-0.1Mpa, temperature vacuumized 2～3 hours under 90～120 ℃ the condition; The weight ratio of described polyether glycol and Hydroxylated acrylic resin is 2～10: 1;
(3) mixture in the step (2) is cooled to 20～50 ℃, add vulcabond, treat to be warmed up to 60～100 ℃ of reactions 1～3 hour after heat release finishes,, obtain isocyanate terminated performed polymer up to reaction end; The mol ratio of described isocyanate group and hydroxyl is 1.5～2: 1;
(4) modified silane coupler in the step (1) is added drop-wise in the performed polymer of step (3),,, obtains amino silane modified polyurethane acrylate resin up to reaction end in 60～100 ℃ of reactions 1～3 hour; The mol ratio of remaining isocyanate group is 0.1～1.0: 1 in described modified silane coupler and the performed polymer.
2. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1, it is characterized in that, described step (1) is carried out as follows: be added drop-wise to epoxy radicals silicone hydride in the primary amino silane under 60～80 ℃, dripped off in 15～60 minutes, 60～80 ℃ of following insulation reaction 1.5～2.5 hours, obtain modified silane coupler then; The mol ratio of described primary amino silane and epoxy radicals silicone hydride is 0.9～2: 1.
3. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that described epoxy radicals silicone hydride is a γ-An Bingjisanyiyangjiguiwan.
4. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that described primary amino silane is γ-glycidyl ether oxygen propyl trimethoxy silicane.
5. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that described vulcabond comprises tolylene diisocyanate or diphenylmethanediisocyanate.
6. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 and 2 is characterized in that, the mol ratio of primary amino silane and epoxy radicals silicone hydride is 1.5～2: 1 in the described step (1).
7. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that, the weight ratio of polyether glycol and Hydroxylated acrylic resin is 2～4: 1 in the described step (2).
8. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that, the mol ratio of isocyanate group and hydroxyl is 1.8～2: 1 in the described step (3).
9. the preparation method of a kind of amino silane modified polyurethane acrylate resin according to claim 1 is characterized in that, in the described step (4) in modified silane coupler and the performed polymer mol ratio of remaining isocyanate group be 0.2～0.5: 1.
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| CN103910847B (en) * | 2014-03-19 | 2016-10-05 | 华南理工大学 | A kind of silane end capped polyurethane oligomer and preparation method thereof |
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| CN105504787B (en) * | 2015-12-28 | 2017-12-12 | 广东普赛达密封粘胶有限公司 | A kind of silane end capped polyurethane composition and its preparation method and application |
| JP2020500230A (en) * | 2016-10-17 | 2020-01-09 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Stabilizers for adhesives, sealants and coating compositions |
| TWI656138B (en) * | 2018-03-31 | 2019-04-11 | 國家中山科學研究院 | Preparation method of bismuth-containing polyurethane composite |
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| CN1616514A (en) * | 2004-09-24 | 2005-05-18 | 中山大学 | Allyl ether modified polyurethane acrylate and its use |
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