CN112680175B - But dual curing silica gel of UV moisture - Google Patents
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- CN112680175B CN112680175B CN202011474290.5A CN202011474290A CN112680175B CN 112680175 B CN112680175 B CN 112680175B CN 202011474290 A CN202011474290 A CN 202011474290A CN 112680175 B CN112680175 B CN 112680175B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 40
- 239000000741 silica gel Substances 0.000 title claims abstract description 40
- 230000009977 dual effect Effects 0.000 title claims description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 42
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 31
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 28
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 22
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 9
- 229910021485 fumed silica Inorganic materials 0.000 claims description 10
- 125000002071 phenylalkoxy group Chemical group 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 11
- 238000003848 UV Light-Curing Methods 0.000 abstract description 9
- 238000013008 moisture curing Methods 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000004839 Moisture curing adhesive Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000012974 tin catalyst Substances 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention discloses UV (ultraviolet) moisture dual-curing silica gel which comprises 60-100 parts of vinyl alkoxy end-capped polydimethylsiloxane, 40-60 parts of mercapto end-capped polydimethylsiloxane, 5-20 parts of cross-linking agent, 5-30 parts of filler, 1-10 parts of catalyst and 1-10 parts of photoinitiator. The invention takes vinyl alkoxy end-capped polydimethylsiloxane as main resin, contains vinyl groups and alkoxy groups, takes vinyl groups as UV curing groups and mercapto end-capped polydimethylsiloxane to undergo click chemical reaction under the promotion of a photoinitiator so as to form a crosslinked curing film, and takes alkoxy groups as moisture curing groups to undergo crosslinking polymerization with a crosslinking agent under the action of a catalyst. The invention firstly achieves quick primary curing by UV curing, solves the problem of low initial curing speed, secondly avoids the existence of acrylic acid in the traditional UV moisture curing adhesive, solves the problem of corrosion of the acrylic acid to materials such as devices, circuit boards and the like, and can be widely applied to bonding and sealing of electronic devices.
Description
Technical Field
The invention belongs to the technical field of adhesive materials, and particularly relates to UV (ultraviolet) moisture dual-curing silica gel.
Background
Silica gel is widely applied to the field of bonding and sealing, but the existing silica gel is single moisture curing type silica gel, and has the problem of low initial curing speed. The UV curing coating is a novel environment-friendly coating and has the advantages of small pollution, low energy consumption, short curing time and the like.
The invention patent with application number 201911365460.3 discloses a UV moisture dual-curing organic silicon coating adhesive, which comprises the following components in parts by mass: 60-150 parts of acrylic modified organic silicon resin; 40-60 parts of acrylic acid modified alkoxy end-capped silicone oil; 10-40 parts of acrylic modified silicone oil; 2-8 parts of a curing accelerator; 0.02-3.0 parts of curing catalyst; 0.02-3.0 parts of UV initiator; the purpose of the method is to provide the organic silicon resin which is synthesized by utilizing isocyanate and acrylic acid monomers and has moderate molecular weight and excellent heat resistance, and the polymer chain end in the polymer has a large number of double bond structures and hydroxyl groups, so that the prepared resin can be subjected to UV curing at room temperature and moisture curing, and the defect that the traditional organic silicon resin needs to be cured at high temperature is overcome. However, UV moisture curable adhesives contain a large amount of acrylic polymers and acrylic monomers, and there is a risk of corrosion of materials such as devices and circuit boards.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the UV-moisture dual-curing silica gel so as to solve the problems in the prior art. The vinyl alkoxy end-capped polydimethylsiloxane and the mercapto end-capped polydimethylsiloxane are crosslinked and cured under the action of the photoinitiator, so that the ultraviolet curable polyurethane does not contain acrylic acid polymers and acrylic acid monomers, and the problem that materials such as devices and circuit boards are corroded is solved.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a UV moisture dual curable silicone gel comprising: vinyl alkoxy end-capped polydimethylsiloxane, mercapto end-capped polydimethylsiloxane, filler, cross-linking agent, catalyst and photoinitiator.
The specific composition is as follows in parts by weight:
further, the vinyl alkoxy end-capped polydimethoxyl siloxane contains a vinyl and alkoxy difunctional structure, and the specific structure is as follows:
wherein R is 1 Is vinyl, R 2 、R 3 、R 4 、R 5 Independently of one another, selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms, preferably methylalkoxy, ethylalkoxy, methylalkoxy having a faster inversion than ethylalkoxy, other longer-chain alkoxy groupsThe response speed;
R 6 、R 7 independently of each other, any one group selected from the group consisting of methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy;
m is an integer of 10 to 500, preferably an integer of 10 to 100, and has more excellent tensile properties than a product of a larger molecular weight.
Further, the mercapto-terminated polydimethoxyl siloxane has the following specific structure:
wherein X is 1 、X 2 Independently of one another, selected from any one of the groups methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy, X 3 、X 4 Independently of each other, any one of methyl, ethyl and vinyl groups;
n is an integer of 10 to 500.
Further, the filler is one or more of fumed silica, calcium carbonate, quartz powder and silicon micropowder, preferably fumed silica, so that the filler can play a role in reinforcing a product, and the tensile strength and the shearing strength of the product after the filler is added can be improved, and the hardness of the product can be also improved.
Further, the cross-linking agent is one or more of methyltrimethoxysilane, vinyltrimethoxysilane, aminopropyl trimethoxysiloxane, gamma-methacryloxypropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and gamma-glycidoxypropyl trimethoxysilane. The crosslinking agent not only has the crosslinking function, but also has the function of adhesion promotion. Preferably one or more of methyltrimethoxysilane, aminopropyl trimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, the adhesion promoting effect is better, and the ratio of the aminopropyl trimethoxysiloxane to the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:2 the effect is best.
Further, the catalyst is one or more of an organic titanium catalyst, an organic bismuth catalyst, an organic zirconium catalyst and an organic tin catalyst, preferably one or more of an organic tin catalyst and an organic zirconium catalyst. The organic zirconium catalyst has outstanding effect in catalyzing moisture curing reaction, has higher activity compared with other catalysts, so that the reaction speed is faster, the mechanical property of the prepared product is better, and the organic zirconium catalyst is more environment-friendly.
Further, the photoinitiator is one or more of 2-hydroxy-methyl phenyl propane-1-ketone, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, and is preferably 2-hydroxy-methyl phenyl propane-1-ketone.
The UV moisture dual-curing silica gel provided by the invention is characterized in that vinyl alkoxy end-capped polydimethylsiloxane is used as a main resin, and simultaneously contains vinyl groups and alkoxy groups, wherein the vinyl groups are UV curing groups, and can undergo click chemical reaction with mercapto end-capped polydimethylsiloxane under the promotion of a proper photoinitiator to form a crosslinked curing film, and the alkoxy groups are moisture curing groups and can undergo crosslinking polymerization with a crosslinking agent under the action of a catalyst.
The invention has the beneficial effects that:
1. the UV-moisture dual-curing silica gel provided by the invention can be subjected to quick primary curing through UV curing, and the problem of low initial curing speed is solved.
2. According to the UV moisture dual-curing silica gel provided by the invention, the vinyl alkoxy end-capped polydimethylsiloxane and the mercapto end-capped polydimethylsiloxane are crosslinked and cured under the action of the photoinitiator, so that the UV moisture dual-curing silica gel does not contain acrylic polymers and acrylic monomers, and the risk of corrosion to materials is avoided.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a UV moisture dual-curable silica gel, comprising: vinyl alkoxy end-capped polydimethylsiloxane, mercapto end-capped polydimethylsiloxane, filler, cross-linking agent, catalyst and photoinitiator.
The specific composition is as follows in parts by weight:
wherein the vinyl alkoxy end-capped polydimethoxyl siloxane contains a vinyl and alkoxy difunctional structure, and the specific structure is as follows:
wherein R is 1 Is vinyl, R 2 、R 3 、R 4 、R 5 Independently of one another, alkoxy groups having 1 to 4 carbon atoms, preferably methylalkoxy, ethylalkoxy, methylalkoxy having a faster reaction rate than ethylalkoxy and other longer-chain alkoxy groups;
R 6 、R 7 independently of each other, any one group selected from the group consisting of methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy;
m is an integer of 10 to 500, preferably an integer of 10 to 100, and has more excellent tensile properties than a product of a larger molecular weight.
Wherein the specific structure of the mercapto-terminated polydimethoxyl siloxane is as follows:
wherein X is 1 、X 2 Independently of one another, selected from any one of the groups methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy, X 3 、X 4 Independently of each other, any one of methyl, ethyl and vinyl groups;
n is an integer of 10 to 500.
The filler in the invention is one or more of fumed silica, calcium carbonate, quartz powder and silicon micropowder, preferably fumed silica, which can strengthen the product, and the tensile strength and the shearing strength of the product after the filler is added can be improved, and the hardness of the product can be also improved.
Wherein the cross-linking agent in the invention is one or more of methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (CAS# 2768-02-7), aminopropyl trimethoxysilane (APS), gamma-methacryloxypropyl trimethoxysilane (CAS# 2530-85-0), N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane (CAS# 1760-24-3) and gamma-glycidoxypropyl trimethoxysilane (CAS# 2530-83-8). The crosslinking agent not only has the crosslinking function, but also has the function of adhesion promotion. Preferably one or more of methyltrimethoxysilane, aminopropyl trimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, the adhesion promoting effect is better, and the ratio of the aminopropyl trimethoxysiloxane to the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:2 the effect is best.
Wherein the catalyst in the invention is one or more of organic titanium catalyst, organic bismuth catalyst, organic zirconium catalyst and organic tin catalyst, preferably one or more of organic tin catalyst and organic zirconium catalyst. The organic zirconium catalyst has outstanding effect in catalyzing moisture curing reaction, has higher activity compared with other catalysts, so that the reaction speed is faster, the mechanical property of the prepared product is better, and the organic zirconium catalyst is more environment-friendly.
Wherein the photoinitiator in the invention is one or more of 2-hydroxy-methyl phenyl propane-1-ketone, 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, and is preferably 2-hydroxy-methyl phenyl propane-1-ketone.
The following is a description of specific examples 1-22 and comparative examples 1-5.
Example 1
A UV moisture dual curable silicone gel comprising: vinyl alkoxy end-capped polydimethylsiloxane, mercapto end-capped polydimethylsiloxane, filler, cross-linking agent, catalyst and photoinitiator.
The specific composition is as follows in parts by weight:
wherein the vinyl alkoxy end-capped polydimethoxysiloxane in the embodiment contains a vinyl and alkoxy difunctional structure, and the specific structure is as follows:
wherein R is 1 Is vinyl, R 2 、R 3 、R 4 、R 5 Independently of each other selected from the group consisting of methylalkoxy and ethylalkoxy;
R 6 、R 7 independently of each other, any one group selected from the group consisting of methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy;
m is an integer of 10 to 100.
Wherein the specific structure of the mercapto-terminated polydimethoxysiloxane in this embodiment is as follows:
wherein X is 1 、X 2 Independently of one another, selected from any one of the groups methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy, X 3 、X 4 Independently of each other, any one of methyl, ethyl and vinyl groups;
n is an integer of 10 to 500.
Wherein the filler in this embodiment is fumed silica.
Wherein the cross-linking agent in the embodiment is aminopropyl trimethoxy siloxane (APS) and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane (CAS# 1760-24-3), and the mixture ratio is 1:2.
wherein the catalyst in this embodiment is an organotin-based catalyst.
Wherein the photoinitiator in this example was 2-hydroxy-methylphenyl propane-1-one.
Examples 2 to 14
The components of examples 2-14 are the same as in example 1, except for the proportions, as detailed in Table 1.
Examples 15 to 22
The proportions of examples 15 to 22 are the same as in example 1, and the components are different from each other, and are shown in Table 2.
Comparative examples 1 to 5
Comparative example 1: the other components and proportions of the mercapto-free end-blocked polydimethylsiloxane are the same as those of example 1, and are shown in Table 1.
Comparative example 2: the filler is not contained, and other components and proportions are the same as those of the embodiment 1, and are shown in the table 1 in detail.
Comparative example 3: the components and proportions of the components without cross-linking agent are the same as those of the example 1, and the details are shown in the table 1.
Comparative example 4: the catalyst is not contained, other components and proportions are the same as in example 1, and the details are shown in table 1.
Comparative example 5: the photoinitiator is not contained, other components and proportions are the same as those of the example 1, and the details are shown in the table 1.
The performance tests of examples 1-22 and comparative examples 1-5 were performed as follows:
(1) Surface dry time test
Tack free time test the test was performed according to the GB/T13477.5-2002 method.
(2) Hardness test
The hardness of the cured product was measured using a Shore A durometer.
(3) Intensity test
Strength test the test was carried out according to the method GB/T7124-86.
The test results are shown in Table 1 and Table 2.
The component parameters and performance test results for each of examples 1-14 and comparative examples 1-5 are detailed in Table 1 below:
TABLE 1 summary of the component parameters and Performance test results data for examples 1-14 and comparative examples 1-5
The component parameters and performance test results for example 1 and examples 15-22 are detailed in Table 2 below:
TABLE 2 summary of the component parameters and Performance test results data for example 1 and examples 15-22
As can be seen from Table 1, in examples 1 to 6, UV moisture dual-cure silica gel was obtained by adjusting the different proportions of the vinyl alkoxy-terminated polydimethylsiloxane and the mercapto-terminated polydimethylsiloxane, and the curing speed was faster, and the hardness, tensile strength and shear strength were better; examples 1 and 7 by adjusting the content of the filler (fumed silica), UV moisture dual-cured silica gel having different hardness, tensile strength and shear strength can be obtained, and when the content of the filler (fumed silica) is higher, the hardness, tensile strength and shear strength of the obtained UV moisture dual-cured silica gel are higher; example 1 and example 8 by adjusting the content of the crosslinking agent (APS: CAS #1760-24-3 (1:2)), a UV moisture dual-cure silica gel having different hardness, tensile strength, and shear strength can be obtained, and when the content of the crosslinking agent (APS: CAS #1760-24-3 (1:2)) is higher, the hardness, tensile strength, and shear strength of the obtained UV moisture dual-cure silica gel are higher; example 1 and example 9 by adjusting the content of the catalyst (organotin-based catalyst), UV moisture dual-cured silica gel having different tack-free times can be obtained, and when the content of the catalyst (organotin-based catalyst) is higher, the tack-free time is faster, but the influence on the hardness, tensile strength, and shear strength of the UV moisture dual-cured silica gel is smaller; example 1 and example 10 by adjusting the content of the photoinitiator (2-hydroxy-methylphenyl propane-1-one), UV moisture dual-cured silica gel having different hardness, tensile strength and shear strength can be obtained, and when the content of the photoinitiator (2-hydroxy-methylphenyl propane-1-one) is higher, the tack-free time is faster, and the hardness, tensile strength and shear strength of the obtained UV moisture dual-cured silica gel are higher; examples 11-14 by fixing the content of the vinyl alkoxy-terminated polydimethylsiloxane and the mercapto-terminated polydimethylsiloxane, different ratios of filler, cross-linking agent, catalyst and photoinitiator were adjusted to obtain UV moisture dual cure silica gels having different tack-free times, hardness, tensile strength and shear strength. By setting comparative example 1, the difference from example 1 is that no mercapto-terminated polydimethylsiloxane was added, and the resulting cured silica gel was not UV cured, longer tack-free time, and lower strength. By setting comparative examples 2 to 5, the obtained cured silica gel has a longer tack-free time and lower hardness, tensile strength and shear strength than in example 1 without the addition of the corresponding filler, crosslinking agent, catalyst and photoinitiator one by one. Wherein the comparative example 4 was not added with a catalyst, the moisture curing could not be performed, and the comparative example 5 was not added with a photoinitiator, the UV curing could not be performed, which resulted in a low strength.
As is clear from Table 2, the proportions of the vinyl alkoxy-terminated polydimethylsiloxane, the mercapto-terminated polydimethylsiloxane, the filler, the crosslinking agent, the catalyst and the photoinitiator in examples 15 to 22 were the same as in example 1, except that the specific components of the filler, the crosslinking agent, the catalyst and the photoinitiator were adjusted, and the UV-moisture dual-cured silica gel was obtained even though the fillers, the crosslinking agents, the catalysts and the photoinitiators of different components were selected. Specifically, the fillers in examples 1, 15 and 16 are fumed silica, quartz powder and silica micropowder respectively, and as a result, the fumed silica is used as the filler to obtain the UV moisture dual-cured silica gel which has higher curing speed and better hardness, tensile strength and shearing strength; the crosslinking agents in example 1, example 17 and example 18 were selected from APS: CAS#1760-24-3 (1:2), MTMS and APS, with APS: the UV moisture dual-cured silica gel obtained by taking CAS#1760-24-3 (1:2) as the cross-linking agent has higher curing speed and better hardness, tensile strength and shear strength; the catalysts in the embodiment 1, the embodiment 19 and the embodiment 20 are respectively selected from an organotin catalyst, an organobismuth catalyst and an organozirconium catalyst, and the result is UV moisture dual-cured silica gel obtained by taking the organozirconium catalyst as the catalyst, which has the advantages of higher curing speed and better hardness, tensile strength and shearing strength; the photoinitiators of example 1, example 21 and example 22 were selected from 2-hydroxy-methylphenyl propane-1-one, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, respectively, and as a result, 2-hydroxy-methylphenyl propane-1-one was used as the photoinitiator to obtain UV moisture dual-cured silica gel, which had a higher curing speed and better hardness, tensile strength and shear strength.
In addition, as can be seen from tables 1 and 2, the UV moisture dual-curing silica gel provided by the invention has the advantages of high curing speed, high production efficiency, hardness greater than Shore A30 after complete curing, tensile strength greater than 3MPa, shearing strength greater than 2MPa, and good mechanical properties.
In summary, the UV moisture dual-curing silica gel provided by the invention uses the vinyl alkoxy-terminated polydimethylsiloxane as a main resin, and simultaneously contains vinyl groups and alkoxy groups, wherein the vinyl groups are UV curing groups, and can undergo click chemical reaction with the mercapto-terminated polydimethylsiloxane under the promotion of a proper photoinitiator to form a crosslinked curing film, and the alkoxy groups are moisture curing groups and can undergo crosslinking polymerization with a crosslinking agent under the action of a catalyst. The UV moisture dual-curing silica gel not only achieves quick primary curing through the primary UV curing, solves the problem of low initial curing speed, but also avoids the existence of acrylic acid polymers and acrylic acid monomers in the traditional UV moisture curing adhesive, solves the problem of corrosion of acrylic acid on materials such as devices, circuit boards and the like, and can be widely applied to the fields of bonding and sealing, in particular to bonding and sealing of electronic devices.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. A UV moisture dual cure silica gel comprising: vinyl alkoxy end-capped polydimethylsiloxane, mercapto end-capped polydimethylsiloxane, filler, cross-linking agent, catalyst and photoinitiator, and the specific composition is as follows in parts by weight:
the mercapto-terminated polydimethoxyl siloxane has the following specific structure:
wherein X is 1 、X 2 Independently of one another, selected from any one of the groups methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy, X 3 、X 4 Independently of each other, any one of methyl, ethyl and vinyl groups;
n is an integer of 10 to 500.
2. The UV moisture dual cure silica gel of claim 1 wherein the vinyl alkoxy terminated polydimethoxy siloxane comprises a vinyl and alkoxy difunctional structure, the specific structure being as follows:
wherein R is 1 Is vinyl, R 2 、R 3 、R 4 、R 5 Independently of one another, from alkoxy groups having 1 to 4 carbon atoms, R 6 、R 7 Independently of each other, any one group selected from the group consisting of methylalkoxy, ethylalkoxy, propylalkoxy, vinylalkoxy, phenylalkoxy, long-chain saturated alkoxy and long-chain unsaturated alkoxy;
m is an integer of 10 to 500.
3. A UV moisture dual cure silica gel as claimed in claim 2, wherein R 2 、R 3 、R 4 、R 5 Independently of one another, from methylalkoxy or ethylalkoxy.
4. The UV moisture dual cure silica gel of claim 1 wherein the filler is one or more of fumed silica, calcium carbonate, silica flour.
5. The UV moisture dual cure silica gel of claim 1 wherein the cross-linking agent is one or more of methyltrimethoxysilane, vinyltrimethoxysilane, aminopropyl trimethoxysiloxane, γ -methacryloxypropyl trimethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, γ -glycidoxypropyl trimethoxysilane.
6. The UV moisture dual cure silica gel of claim 5 wherein the cross-linking agent is aminopropyl trimethoxysiloxane and N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane in a ratio of 1:2.
7. the UV moisture dual cure silica gel of claim 1 wherein the catalyst is one or more of an organotitanium catalyst, an organobismuth catalyst, an organozirconium catalyst, and an organotin catalyst.
8. A UV moisture dual curable silica gel according to claim 1 wherein the photoinitiator is one or more of 2-hydroxy-methylphenyl propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
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| CN115820206B (en) * | 2022-12-23 | 2024-04-02 | 烟台德邦科技股份有限公司 | UV-cured organosilicon sealant |
| 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 |
| CN116589973B (en) * | 2023-05-22 | 2023-11-07 | 珠海市宏科光电子有限公司 | High-temperature-resistant COB packaging adhesive and preparation method thereof |
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