CN115558111B - UV/moisture dual-curing organic silicon resin and synthetic method and application thereof - Google Patents
UV/moisture dual-curing organic silicon resin and synthetic method and application thereof Download PDFInfo
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- CN115558111B CN115558111B CN202110749049.7A CN202110749049A CN115558111B CN 115558111 B CN115558111 B CN 115558111B CN 202110749049 A CN202110749049 A CN 202110749049A CN 115558111 B CN115558111 B CN 115558111B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 230000009977 dual effect Effects 0.000 claims abstract description 26
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- -1 polysiloxane Polymers 0.000 claims description 71
- 239000003054 catalyst Substances 0.000 claims description 44
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229920002050 silicone resin Polymers 0.000 claims description 30
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 29
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001723 curing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 17
- 238000013008 moisture curing Methods 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 8
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 claims description 2
- 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 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000002210 silicon-based material Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 16
- 238000000016 photochemical curing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the field of organic silicon materials, and discloses UV/moisture dual-curing organic silicon resin, and a synthesis method and application thereof. According to the invention, the siloxane group and the acrylic ester group are simultaneously introduced into the organic silicon material, so that the aim of dual curing is fulfilled: the acrylate groups are UV light curable; the siloxane groups react with the water vapor in the air to give the chain ends-Si (OR) 3 OR-SiR (OR) 2 The silylated polymer of the structure undergoes hydrolysis at the chain ends and crosslinks to a cured product having a Si-O-Si network structure. As the molecule contains a plurality of acrylate groups and siloxane groups, the curing speed is high, the crosslinking degree is high, and the cured material has excellent hydrophobicity, heat resistance, transparency and adhesive force, and has wide application in the fields of batch glue, circuit board filling, protection and the like.
Description
Technical Field
The invention belongs to the field of organic silicon materials, and particularly relates to UV/moisture dual-curing organic silicon resin, and a synthesis method and application thereof.
Background
The photocuring technology is a high-efficiency, environment-friendly, energy-saving and high-quality surface treatment technology, and is known as a new technology of the 21 st century green industry. The organic silicon material has lower surface energy, excellent flexibility, low temperature resistance, moisture resistance, weather resistance and electrical property, and is widely applied to industries such as building, transportation, chemical industry, textile, food, light industry, medical treatment and the like. Along with the development of the electronic industry, the organic silicon material is widely applied to the protection of electronic circuit boards and main parts by virtue of the excellent high and low temperature resistance and dielectric properties. Photo-curing organosilicon materials are favored because of the excellent properties of low surface tension, good flexibility and the like of the organosilicon materials, and the high efficiency and energy saving of photo-curing technology.
Currently, most of UV light-curable silicone materials are cured by free radicals, so that the UV light-curable silicone materials have some disadvantages of free radical light curing: 1. thick coating, difficult to cure completely; 2. the colored coating is difficult to cure; 3. the side and shadow portions of the three-dimensional coating cannot be cured. To overcome these disadvantages, other curing means than photo-curing, such as moisture curing, heat curing, etc., are introduced, and constructing a dual curing system is a simple and effective solution. The Ultraviolet (UV) light curing organosilicon material can be used for rapidly achieving surface drying by light curing, and the shadow part or the bottom layer part can be completely dried by other curing modes, so that the defect of the UV light curing organosilicon material can be overcome.
Chinese patent publication CN104193996a provides a method for preparing a UV/moisture dual-cure silicone glue, in which the polymer contains both double bonds capable of photo-curing and alkoxy groups and epoxy groups capable of moisture-curing. Chinese patent publication CN105348536a provides a method for synthesizing a UV/moisture dual-cure polymer having an acryloyloxy group in the structural formula, having photocuring properties, and having an alkoxy group, having moisture curing properties. Chinese patent publication CN111234234a provides a UV/moisture dual-curable polysiloxane, and a preparation method and use thereof, which is a linear polysiloxane having epoxy groups in side chains and alkoxy groups and acrylate groups in end groups. The above texts are all UV/moisture dual-curing organosilicon polymers prepared by an esterification reaction or polycondensation method, and the prepared products have low functionality, insufficient photo-curing speed and low crosslinking degree, which affect the performance of the cured materials.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a method for preparing a multifunctional UV/moisture dual curable silicone resin. The UV/moisture dual-curable organic silicon resin achieves the aim of dual curing by simultaneously introducing siloxane groups and acrylate groups into an organic silicon material: the acrylate groups are UV light curable; the siloxane groups react with the water vapor in the air to give the chain ends-Si (OR) 3 OR-SiR (OR) 2 The silylated polymer of the structure undergoes hydrolysis at the chain ends and crosslinks to a cured product having a Si-O-Si network structure.
It is another object of the present invention to provide a multifunctional UV/moisture dual curable silicone resin prepared by the above method.
It is a further object of the present invention to provide the use of the above-described multifunctional UV/moisture dual curable silicone resins. As the molecule contains a plurality of acrylate groups and siloxane groups, the curing speed is high, the crosslinking degree is high, and the cured material has excellent hydrophobicity, heat resistance, transparency and adhesive force, and has wide application in the fields of batch glue, circuit board filling, protection and the like.
The aim of the invention is achieved by the following scheme:
a method for preparing a UV/moisture dual curable silicone resin comprising the steps of: firstly, performing a first hydrosilylation reaction by utilizing hydrogen-terminated polysiloxane and multifunctional acrylate, and grafting acrylate groups at two ends of a polysiloxane chain; then the obtained product and alkoxy silane are subjected to a second hydrosilylation reaction, and siloxane groups are introduced, so that acrylate groups and siloxane groups are simultaneously introduced at the end of the polysiloxane chain, and UV and moisture dual-curing can be simultaneously carried out.
Preferably, the multifunctional UV/moisture dual-curable silicone resin is prepared by the following method: after uniformly mixing hydrogen-terminated polydimethylsiloxane, acrylic ester, a catalyst, a polymerization inhibitor and a solvent, heating to perform a first-step hydrosilylation reaction, adjusting the temperature after a period of reaction, adding alkoxy silane to perform a second-step hydrosilylation reaction, and removing the solvent by rotary evaporation after the reaction is finished to obtain the UV/moisture dual-curing organic silicon resin.
The hydrogen-terminated polydimethylsiloxane was purchased from Weng Jiang reagent and had the structural formula H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO]nSi(CH 3 ) 2 H, wherein mn=2000-6000.
The acrylic ester is one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate.
The catalyst is at least one of Karstedt catalyst or Spier catalyst.
The polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, o-methyl hydroquinone, p-tert-butyl catechol and p-benzoquinone.
The solvent is at least one of toluene, xylene and isopropanol.
The first hydrosilylation reaction is to raise the temperature to 80-110 ℃ for 4-8 hours; preferably at 100℃for 6 hours.
The alkoxy silane is at least one of trimethoxy silane, triethoxy silane, dimethoxy hydrogen silane or diethoxy hydrogen silane.
The second hydrosilylation reaction is carried out at 60-80 ℃ for 4-8 hours, preferably at 80 ℃ for 6 hours.
The dosages of the hydrogen-terminated polydimethylsiloxane, the acrylic ester, the catalyst, the polymerization inhibitor, the solvent and the alkoxy silane are as follows: the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the acrylate is 1:2 to 1:2.5, preferably 1:2; the catalyst concentration is 4-20ppm, preferably 10ppm, where ppm means the mass of catalyst as a percentage of the total mass of reactants including hydrogen-terminated polydimethylsiloxane and acrylate; the mass of the polymerization inhibitor is 0.01% -0.1% of the total mass of reactants, preferably 0.1%, wherein the reactants comprise hydrogen-terminated polydimethylsiloxane and acrylic ester; the mass of the solvent is 50% -150%, preferably 50% of the total mass of the reactants, wherein the reactants comprise hydrogen-terminated polydimethylsiloxane and acrylic ester; the addition amount of the alkoxysilane depends on the functionality of the acrylate, three acrylate groups remain after the first hydrosilylation reaction of the tetra-functional pentaerythritol tetraacrylate, two double bonds need to be reserved for photocuring, and therefore only one acrylate group performs the second hydrosilylation reaction, i.e. the mass ratio of the pentaerythritol tetraacrylate to the alkoxysilane is 1:1. By analogy, the ratio of the mass of dipentaerythritol pentaacrylate to the mass of the alkoxysilane is 1:1-1:2, and the ratio of the mass of dipentaerythritol hexaacrylate to the mass of the alkoxysilane is 1:1-1:3.
A UV/moisture dual curable silicone resin prepared by the above method.
Preferably, the structural formula of the UV/moisture dual-curable silicone resin is specifically shown as follows:
wherein n=25 to 80, R is one of the following structures, R 1 、R 2 、R 3 Relatively independent methyl or ethyl;
the UV/moisture dual-curing organic silicon resin is uniformly stirred by adding a small amount of photoinitiator and moisture curing agent, then is coated on the surface of metal, glass, paper or plastic, and can be completely surface-dried after being placed indoors for less than half an hour after short UV irradiation (such as 5 s). The cured organic silicon resin has good hydrophobicity, heat resistance and transparency, and good adhesive force, and can be widely applied in the fields of coating glue, circuit board filling, protection and the like.
The photoinitiator is a compound capable of generating free radicals under ultraviolet irradiation, and is at least one of 2-hydroxy-2-methyl propiophenone (Darocur 1173), 1-hydroxy-cyclohexyl benzophenone (Darocur 184), 2-methyl 1- (4-methylthiophenyl) -2-morpholinone (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369) and Benzophenone (BP); the addition amount of the photoinitiator is 1 to 4 percent of the mass of the organic silicon resin.
The moisture curing catalyst is an organic metal catalyst, and the organic metal catalyst is at least one of an organic tin catalyst, an organic bismuth catalyst, an organic zirconium catalyst or an organic titanium catalyst. Such as dibutyltin dilaurate, dibutyltin dioctoate, tetraisopropyl orthotitanate, tetrabutoxyorthotitanate, diisopropoxytitanium bis (ethylacetoacetate). The addition amount of the moisture curing catalyst is 0.1-1% of the mass of the organic silicon resin.
Compared with the prior art, the invention has the following advantages:
the organic silicon resin prepared by the invention has the advantages of simple preparation method, simultaneously introduces the acrylic ester group capable of photo-curing and the siloxane group capable of moisture-curing, contains a plurality of acrylic ester groups and siloxane groups in the molecule, is crosslinked into a cured product with a Si-O-Si network structure, has high curing speed and high crosslinking degree, and the cured material has excellent hydrophobicity, heat resistance, transparency and adhesive force and has wide application in the fields of batch glue application, circuit board filling, protection and the like.
Drawings
FIG. 1 is an infrared spectrum of a UV/moisture dual curable silicone resin prepared in example 1.
FIG. 2 is an infrared spectrum of a UV/moisture dual curable silicone resin prepared in example 2.
FIG. 3 is an infrared spectrum of a UV/moisture dual curable silicone resin prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The hydrogen-terminated polydimethylsiloxanes used in the present invention were purchased from Guangdong Weng Jiang chemical company, inc.; the Spiecer catalyst is self-made and the preparation method is as follows: 0.1328g of chloroplatinic acid hexahydrate and 50.00g isopropanol are accurately weighed, placed in a beaker, stirred for 1 hour, and filled into a 100mL brown bottle for storage for later use. Other materials or instruments to which the present invention relates are commercially available. For process parameters not specifically noted, reference may be made to conventional techniques.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 7.04g of pentaerythritol tetraacrylate, the mass ratio of the two substances being 1:2, 0.27g of Spiecer catalyst, 0.03g of p-methoxyphenol and 13.52g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dropwise adding 2.44g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
FIG. 1 is an infrared spectrum of the UV/moisture dual curable silicone resin prepared in example 1, as can be seen in FIG. 1: 2128cm -1 And 909cm -1 The disappearance of the Si-H peak at the site indicates the progress of the hydrosilylation reaction. 1731cm -1 C=o peak at and 1632cm -1 The c=c peak at this point appears, indicating the introduction of acrylate groups. 2840cm -1 And 1187cm -1 Si-OCH at 3 Peaks appear, indicating the introduction of a silylmethoxy group. Thus, UV-curable acrylate groups and moisture-curable silylmethoxy groups were successfully grafted onto the polysiloxane segments by a continuous two-step hydrosilylation reaction.
Example 2
Adding 40.00g of hydrogen-terminated polydimethylsiloxane, mn=4000, 7.04g of pentaerythritol tetraacrylate, the mass ratio of which is 1:2, 0.47g of Spiecer catalyst, 0.05g of p-methoxyphenol and 23.52g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dropwise adding 2.44g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and spin-evaporating to remove the solvent to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
FIG. 2 is an infrared spectrum of the UV/moisture dual curable silicone resin prepared in example 2, as can be seen in FIG. 2: 2128cm -1 And 909cm -1 The disappearance of the Si-H peak at the site indicates the progress of the hydrosilylation reaction. 1731cm -1 C=o peak at and 1632cm -1 The c=c peak at this point appears, indicating the introduction of acrylate groups. 2840cm -1 And 1187cm -1 Si-OCH at 3 Peaks appear, indicating the introduction of a silylmethoxy group. Thus, UV-curable acrylate groups and moisture-curable silylmethoxy groups were successfully grafted onto the polysiloxane segments by a continuous two-step hydrosilylation reaction.
Example 3
60.00g of hydrogen-terminated polydimethylsiloxane, mn=6000, 7.04g of pentaerythritol tetraacrylate, the mass ratio of which is 1:2, 0.67g of Spier catalyst, 0.07g of p-methoxyphenol and 33.52g of toluene are added into a reaction vessel, the mixture is stirred uniformly and then heated to 100 ℃ for a first hydrosilylation reaction, the temperature is reduced to 80 ℃ after the reaction is carried out for 6 hours, 2.44g of trimethoxysilane is added dropwise for a second hydrosilylation reaction, the reaction is carried out for 6 hours, and the solvent is removed by spin evaporation, so that the multifunctional UV/moisture dual-curable organic silicon resin is obtained.
FIG. 3 is an infrared spectrum of the UV/moisture dual curable silicone resin prepared in example 3, as can be seen in FIG. 3: 2128cm -1 And 909cm -1 The disappearance of the Si-H peak at the site indicates the progress of the hydrosilylation reaction. 1731cm -1 C=o peak at and 1632cm -1 The c=c peak at this point appears, indicating the introduction of acrylate groups. 2840cm -1 And 1187cm -1 Si-OCH at 3 Peaks appear, indicating the introduction of a silylmethoxy group. Because ofIn this way, UV-curable acrylate groups and moisture-curable silylmethoxy groups were successfully grafted onto the polysiloxane segments by a two-step sequential hydrosilylation reaction.
Example 4
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 10.48g of dipentaerythritol pentaacrylate, the mass ratio of which is 1:2, 0.30g of Spiecer catalyst, 0.03g of p-methoxyphenol and 15.24g of toluene into a reaction vessel, uniformly stirring, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dropwise adding 2.44g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
Example 5
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 10.48g of dipentaerythritol pentaacrylate, the mass ratio of which is 1:2, 0.30g of Spiecer catalyst, 0.03g of p-methoxyphenol and 15.24g of toluene into a reaction vessel, uniformly stirring, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dropwise adding 4.88g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
Example 6
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 11.56g of dipentaerythritol hexaacrylate, the mass ratio of substances being 1:2, 0.32g of Spiecer catalyst, 0.03g of p-methoxyphenol and 15.78g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dripping 2.44g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
Example 7
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 11.56g of dipentaerythritol hexaacrylate, the mass ratio of substances is 1:2, 0.32g of Spiecer catalyst, 0.03g of p-methoxyphenol and 15.78g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dripping 4.88g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
Example 8
Adding 20.00g of hydrogen-terminated polydimethylsiloxane, 11.56g of dipentaerythritol hexaacrylate, the mass ratio of substances is 1:2, 0.32g of Spiecer catalyst, 0.03g of p-methoxyphenol and 15.78g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for a first hydrosilylation reaction, cooling to 80 ℃ after 6 hours of reaction, dripping 7.32g of trimethoxysilane for a second hydrosilylation reaction, reacting for 6 hours, and removing the solvent by rotary evaporation to obtain the multifunctional UV/moisture dual-curable organic silicon resin.
A photoinitiator Darocur1173 of 1% by mass of the silicone resin and a moisture curing agent dibutyltin dilaurate of 0.1% by mass of the silicone resin were added to the silicone resin obtained in the above examples, and UV/moisture dual curing was performed, and the curing times and properties of the cured films of the examples are shown in the following table.
TABLE 1 curing time and properties of the cured films of the examples
Wherein:
UV curing time refers to irradiation time of a commercially available high-pressure mercury lamp of 2 kilowatts, and irradiation energy of 300mj/cm in 5s 2 ；
The moisture curing time refers to the time for the room to reach 'surface dry', the curing is carried out by water vapor in the air, the room temperature is 28 ℃ and the relative humidity is 80% during the test; by "tack-free" is meant herein that a finger is pressed hard against a cured film obtained by UV and moisture curing without a hand mark remaining, which is evident if the cured film is not thoroughly "tack-free".
The hydrophobic angle is a contact angle measured by a common contact angle meter on the market by using water as a liquid, and the hydrophobic angle is more than 90 degrees, which indicates that the water-repellent material has good hydrophobicity;
the heat resistance was obtained by measuring the weight loss relationship of the cured film by a Metler thermal analyzer (Mettler TGA/DSC), under a nitrogen atmosphere, at a temperature rise rate of 10 ℃/min from 30℃to 800 ℃. Here T 5％ T represents the temperature at which the cured film loses 5% of weight max The temperature at which the rate of weight loss of the cured film was maximum was shown.
The transparency is the light transmittance of the cured film with the thickness of 20 micrometers measured by ultraviolet spectrum, the testing instrument is the UV-2600 of Shimadzu, and the testing wavelength is 400-800nm (visible light wavelength range);
the adhesion test was measured according to the cross-hatch method of GB/T9286-1998, with a rating of 0 indicating the best and a rating of 5 indicating the worst.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (14)
1. A method for preparing a UV/moisture dual-curable organic silicon resin, which is characterized by comprising the following steps: firstly, performing a first hydrosilylation reaction by utilizing hydrogen-terminated polysiloxane and multifunctional acrylate, and grafting acrylate groups at two ends of a polysiloxane chain; then carrying out a second hydrosilylation reaction on the obtained product and alkoxy silane, and introducing siloxane groups to obtain UV/moisture dual-cured organic silicon resin;
the acrylic ester is one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate;
the alkoxy silane is at least one of trimethoxy silane, triethoxy silane, dimethoxy hydrogen silane or diethoxy hydrogen silane;
the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the amount of the acrylate is 1:2-1:2.5;
the addition amount of the alkoxy silane depends on the functionality of the acrylate, and the ratio of the pentaerythritol tetraacrylate to the amount of the alkoxy silane is 1:1; the ratio of the dipentaerythritol pentaacrylate to the alkoxy silane is 1:1-1:2; the ratio of the mass of the dipentaerythritol hexaacrylate to the mass of the alkoxy silane is 1:1-1:3.
2. The method for preparing the UV/moisture dual-curable silicone resin according to claim 1, which is characterized by comprising the following steps:
and after uniformly mixing hydrogen-terminated polydimethylsiloxane, acrylic ester, a catalyst, a polymerization inhibitor and a solvent, heating to perform a first-step hydrosilylation reaction, then adjusting the temperature, adding alkoxy silane to perform a second-step hydrosilylation reaction, and removing the solvent by spin evaporation after the reaction is finished to obtain the UV/moisture dual-curing organic silicon resin.
3. A method for preparing a UV/moisture dual curable silicone resin according to claim 2, characterized in that:
the hydrogen-terminated polydimethylsiloxane has the structural formula of H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO]nSi(CH 3 ) 2 H，Mn=2000-6000；
The catalyst is at least one of Karstedt catalyst or Spier catalyst;
the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, o-methyl hydroquinone, p-tert-butyl catechol and p-benzoquinone;
the solvent is at least one of toluene, xylene and isopropanol;
the reaction condition of the first-step hydrosilylation reaction is that the reaction is carried out for 4-8 hours at the temperature of 80-110 ℃.
4. A method of preparing a UV/moisture dual curable silicone resin according to claim 3, wherein:
the reaction condition of the first step of hydrosilylation reaction is 100 ℃ for 6 hours.
5. A method for preparing a UV/moisture dual curable silicone resin according to claim 2, characterized in that:
the second hydrosilylation reaction is carried out at 60-80 ℃ for 4-8 hours.
6. The method for preparing the UV/moisture dual-curable silicone resin according to claim 5, wherein the method comprises the following steps: the second hydrosilylation reaction is carried out at 80 ℃ for 6 hours.
7. A method of preparing a UV/moisture dual curable silicone resin according to claim 3, characterized in that:
the dosages of the hydrogen-terminated polydimethylsiloxane, the acrylic ester, the catalyst, the polymerization inhibitor, the solvent and the alkoxy silane are as follows: the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the amount of the acrylate is 1:2-1:2.5;
the catalyst has a concentration of 4 to 20ppm, wherein ppm represents the mass of catalyst as a percentage of the total mass of reactants including hydrogen-terminated polydimethylsiloxane and acrylate;
the mass of the polymerization inhibitor is 0.01% -0.1% of the total mass of reactants, wherein the reactants comprise hydrogen-terminated polydimethylsiloxane and acrylic ester;
the mass of the solvent is 50% -150% of the total mass of reactants, wherein the reactants comprise hydrogen-terminated polydimethylsiloxane and acrylic ester.
8. The method for preparing a UV/moisture dual curable silicone resin according to claim 7, wherein:
the dosages of the hydrogen-terminated polydimethylsiloxane, the acrylic ester, the catalyst, the polymerization inhibitor, the solvent and the alkoxy silane are as follows: the ratio of the amount of the hydrogen-terminated polydimethylsiloxane to the acrylate is 1:2;
the catalyst concentration is 10ppm, wherein ppm represents the mass of catalyst as a percentage of the total mass of reactants including hydrogen-terminated polydimethylsiloxane and acrylate;
the mass of the polymerization inhibitor is 0.1% of the total mass of reactants, wherein the reactants comprise hydrogen-terminated polydimethylsiloxane and acrylic ester;
the mass of the solvent was 50% of the total mass of the reactants including hydrogen-terminated polydimethylsiloxane and acrylate.
9. A UV/moisture dual curable silicone resin prepared according to the method of any one of claims 1-8.
10. UV/moisture dual curable silicone resin according to claim 9, characterized by its specific structure as follows:
wherein n=25 to 80, R is one of the following structures, R 1 、R 2 、R 3 Relatively independent methyl or ethyl;
，
，
，
，
，
。
11. use of a UV/moisture dual curable silicone resin according to claim 9 in the areas of glue spreading, circuit board filling and protection.
12. The use of a UV/moisture dual curable silicone resin according to claim 11 in the areas of glue spreading, circuit board filling and protection, characterized in that:
the UV/moisture dual-curable silicone resin also requires the addition of a photoinitiator and a moisture curing catalyst for UV/moisture dual-curing during application.
13. The use of a UV/moisture dual curable silicone resin according to claim 12 in the areas of glue spreading, circuit board filling and protection, characterized in that:
the photoinitiator is a compound capable of generating free radicals under ultraviolet irradiation, and is at least one of 2-hydroxy-2-methyl propiophenone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl 1- (4-methylthiophenyl) -2-morpholinone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone and benzophenone;
the addition amount of the photoinitiator is 1% -4% of the mass of the organic silicon resin;
the moisture curing catalyst is an organic metal catalyst, and the organic metal catalyst is at least one of an organic tin catalyst, an organic bismuth catalyst, an organic zirconium catalyst or an organic titanium catalyst;
the addition amount of the moisture curing catalyst is 0.1% -1% of the mass of the organic silicon resin.
14. The use of a UV/moisture dual curable silicone resin according to claim 13 in the areas of glue spreading, circuit board filling and protection, characterized in that:
the moisture curing catalyst is an organic metal catalyst, and the organic metal catalyst is at least one of dibutyl tin dilaurate, dibutyl tin dioctanoate, tetraisopropyl orthotitanate, tetrabutoxyorthotitanate and diisopropoxy titanium bis (ethyl acetoacetate).
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