CN113528011A - Ultraviolet-curing organic silicon release agent and preparation method and application thereof - Google Patents
Ultraviolet-curing organic silicon release agent and preparation method and application thereof Download PDFInfo
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- CN113528011A CN113528011A CN202110710744.2A CN202110710744A CN113528011A CN 113528011 A CN113528011 A CN 113528011A CN 202110710744 A CN202110710744 A CN 202110710744A CN 113528011 A CN113528011 A CN 113528011A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 49
- 239000010703 silicon Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 66
- 238000001723 curing Methods 0.000 claims abstract description 55
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920002545 silicone oil Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 5
- 229920001296 polysiloxane Polymers 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000012952 cationic photoinitiator Substances 0.000 claims description 17
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229930007453 limonene-1,2-epoxide Natural products 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- -1 diphenyliodonium hexafluorophosphate Chemical compound 0.000 claims description 11
- 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 7
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 125000005409 triarylsulfonium group Chemical group 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
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 3
- SYFZCLMMUNCHNH-UHFFFAOYSA-N 2-(prop-2-ynoxymethyl)oxirane Chemical compound C#CCOCC1CO1 SYFZCLMMUNCHNH-UHFFFAOYSA-N 0.000 claims description 3
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 claims description 3
- UKTHULMXFLCNAV-UHFFFAOYSA-N 2-hex-5-enyloxirane Chemical compound C=CCCCCC1CO1 UKTHULMXFLCNAV-UHFFFAOYSA-N 0.000 claims description 3
- FCZHJHKCOZGQJZ-UHFFFAOYSA-N 2-oct-7-enyloxirane Chemical compound C=CCCCCCCC1CO1 FCZHJHKCOZGQJZ-UHFFFAOYSA-N 0.000 claims description 3
- KGYYLUNYOCBBME-UHFFFAOYSA-M 4-fluoro-2-phenyl-4-(4-propylcyclohexyl)cyclohexa-1,5-diene-1-carboxylate Chemical compound C1CC(CCC)CCC1C1(F)C=CC(C([O-])=O)=C(C=2C=CC=CC=2)C1 KGYYLUNYOCBBME-UHFFFAOYSA-M 0.000 claims description 3
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 description 26
- 229920002799 BoPET Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000000016 photochemical curing Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of an ultraviolet curing organic silicon release agent, which comprises the following steps: uniformly mixing and stirring epoxy organosilicon oligomer, reactive diluent and photoinitiator to obtain the ultraviolet curing organosilicon release agent; the epoxy organic silicon oligomer is generated by carrying out hydrosilylation reaction on an epoxy monomer containing a six-membered ring and lateral hydrogen silicone oil. The invention also discloses the ultraviolet curing organosilicon release agent prepared by the preparation method. The ultraviolet curing organosilicon release agent can be directly and quickly cured by ultraviolet irradiation at room temperature without inert gas protection, and has low stripping force and good adhesion to base materials after curing; the preparation method does not need a solvent in the synthesis process, avoids using a toxic solvent and greatly saves the cost.
Description
Technical Field
The invention relates to the field of photocuring functional coatings, in particular to an ultraviolet-curing organic silicon release agent and a preparation method and application thereof.
Background
The release agent is a kind of isolating film applied between the product and the mould to prevent the formed composite product from adhering on the mould, and is widely applied to the fields of adhesive products, die cutting and punching processing, electronic and electric appliance manufacturing and the like. The silicone polymer has very low surface energy, so most of release agents are prepared by taking the silicone polymer as a main body. The existing organic silicon release agent is mainly prepared by thermally curing hydrogen-containing silicone oil and vinyl silicone oil at high temperature, the energy consumption of the thermally cured release agent is high, and meanwhile, the high temperature is involved, and some materials which are not heat-resistant are not suitable for the method. The ultraviolet light cured organic silicon release agent can be cured at room temperature and is particularly suitable for heat-sensitive materials; meanwhile, the photocuring rate is high, no VOC is discharged, and the method has the advantages of energy conservation and environmental protection, and is the development direction of the future organic silicon release agent.
The ultraviolet light cured organosilicon release agent is an organosilicon polymer with polysiloxane as a main chain and an end group of epoxy group or acrylate group, wherein a polysiloxane chain segment endows low surface performance, and the epoxy group or the acrylate group has photocuring performance. The acrylate-based organic silicon release agent has an oxygen inhibition phenomenon in the photocuring process, and the better photocuring effect can be achieved only by introducing inert gas into an ultraviolet curing device, so that the operation steps and the cost are increased undoubtedly; meanwhile, the acrylate group can have a severe volume shrinkage phenomenon in the photocuring process, which results in a decrease in adhesion to the substrate. Easily causes 'desilication' phenomenon, thereby losing the function as a release agent, but the epoxy-based organosilicon release agent does not have the problems of oxygen inhibition and serious volume shrinkage.
The epoxy organosilicon release agent is photocured by using an epoxy group, belongs to a cationic curing mechanism, does not have the problem of oxygen inhibition, can be photocured in air, does not need inert gas protection, and saves the cost. Meanwhile, epoxy groups are subjected to ring-opening polymerization in the photocuring process, the problem of volume shrinkage is not obvious, the adhesive force to the base material is very good, and the epoxy groups have the low surface energy of the organic silicon polymer, so that the epoxy groups organic silicon release agent has very low release force after photocuring, and simultaneously has high residual adhesion rate and good release effect.
According to the Chinese patent authorization text CN108586754A, hydrogen-terminated silicone oil, polyfunctional acrylate and chloroplatinic acid isopropanol solution are uniformly mixed, then the mixture is reacted at the temperature of 110-115 ℃ to obtain silicone oil modified acrylate, then the silicone oil modified acrylate is uniformly mixed with a photoinitiator, and then the mixture is coated on a substrate and is subjected to ultraviolet irradiation to obtain the organic silicon acrylic resin. However, in the method, a large amount of organic solvent is used in the synthesis process, and meanwhile, the acrylate group can have a severe volume shrinkage phenomenon in the photocuring process, so that the silicon-containing release agent is transferred to one side of the adhesive layer of the protective film in the use process, the effect of the silicon-containing release agent as the release agent is lost, and the wide application of the silicon-containing release agent in the industry is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of an ultraviolet curing organosilicon release agent, a cycloaliphatic epoxy group organosilicon prepolymer is obtained by a hydrosilylation reaction one-step method, no solvent is needed in the synthesis process, and the cost is greatly saved while toxic solvent is avoided.
The invention also aims to provide the ultraviolet curing organic silicon release agent which can be directly and quickly cured by ultraviolet irradiation at room temperature without inert gas protection, and has low stripping force and good adhesion to a base material after curing.
The invention further aims to provide application of the ultraviolet curing organic silicon release agent.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an ultraviolet curing organic silicon release agent comprises the following steps: uniformly mixing and stirring epoxy organosilicon oligomer, reactive diluent and photoinitiator to obtain the ultraviolet curing organosilicon release agent;
the epoxy organic silicon oligomer is generated by carrying out hydrosilylation reaction on an epoxy monomer containing a six-membered ring and lateral hydrogen silicone oil;
the mass ratio of the organic silicon oligomer to the reactive diluent to the photoinitiator is as follows: 100: (10-30): (1-4).
Preferably, the preparation method of the epoxy-based silicone oligomer is as follows:
uniformly mixing lateral hydrogen silicone oil, epoxy monomer containing six-membered ring, catalyst and polymerization inhibitor, and heating to 80-110 ℃ for reaction for 4-8 hours;
the mole ratio of the lateral hydrogen silicone oil to the epoxy monomer containing the six-membered ring is 1: 2-1: 2.5;
the concentration of the catalyst in the whole reaction system is 4-20 ppm;
the mass of the polymerization inhibitor is 0.01-0.1% of the total weight of the reactants.
Preferably, the six-membered ring containing epoxy monomer is 4-vinyl-1-cyclohexene-1, 2 epoxy or limonene 1, 2-epoxide.
Preferably, the catalyst is at least one of a Karstedt catalyst or a Spiecer catalyst.
Preferably, the polymerization inhibitor is at least one of p-methoxyphenol, p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-p-cresol and p-benzoquinone.
The preparation method of the ultraviolet curing organosilicon release agent comprises the following step of preparing the active diluent, wherein the active diluent is at least one of 1, 2 epoxy-5-hexene, 1, 2 epoxy-7-octene, 1, 2 epoxy-9-decene, allyl glycidyl ether, methyl methacrylate (GMA), 4-vinyl-1-cyclohexene-1, 2 epoxy, limonene-1, 2 epoxide, butyl glycidyl ether, 1, 7-octadiene diepoxide, glycidyl propargyl ether, vinylcyclohexene dioxide, allyl glycidyl ether, glycidyl phenyl ether, tert-butyl glycidyl ether, 2-toluene glycidyl ether, octyl glycidyl ether and 1, 4-butanediol diglycidyl ether.
Preferably, the photoinitiator is at least one of triarylsulfonium salt cationic photoinitiators, 4-isobutylphenyl-4 '-methylphenyliodihexafluorophosphate, diphenyliodonium hexafluorophosphate, 4' -dimethyldiphenyliodonium hexafluorophosphate and triarylsulfonium hexafluoroantimonate liquid photoinitiators.
An ultraviolet light curing organic silicon release agent comprises epoxy organic silicon oligomer, reactive diluent and photoinitiator;
the mass ratio of the organic silicon oligomer to the reactive diluent to the photoinitiator is as follows: 100: (10-30): (1-4);
the epoxy organic silicon oligomer is generated by carrying out hydrosilylation reaction on an epoxy monomer containing a six-membered ring and lateral hydrogen silicone oil.
Preferably, the six-membered ring containing epoxy monomer is 4-vinyl-1-cyclohexene-1, 2 epoxy or limonene 1, 2-epoxide.
The application of the ultraviolet curing organic silicon release agent is used for forming a cured release agent coating on the surface of a material in an ultraviolet irradiation mode under the condition of no inert gas protection.
The mechanism of the invention is as follows: the epoxy silicone oligomer with photosensitivity is obtained by carrying out a hydrosilylation reaction on an epoxy monomer with photocuring capability and containing a six-membered ring and lateral hydrogen silicone oil (PHMS-PDMS), and then a photoinitiator is added to enable the epoxy silicone oligomer to be cured at room temperature under the irradiation of ultraviolet light without the protection of inert gas. The epoxy monomer containing the six-membered ring is selected, and the epoxy monomer containing the high-tension epoxy cyclohexane has high reactivity, so that the copolymerization with the silicone oil can remarkably accelerate the polymerization reaction; in addition, the six-membered ring epoxy monomer is selected, so that the mold release agent has more excellent heat resistance due to the rigidity of the six-membered ring, and can adapt to higher temperature environment in the storage process. TG tests of the release agent show that the corresponding temperatures of two maximum decomposition rates in an air atmosphere are 437.6 and 511.3 ℃, the corresponding temperature can reach 366.5 ℃ when the weight loss is 5 percent, and the corresponding temperature can reach 480 ℃ when the weight loss is 30 percent. Meanwhile, the epoxy organosilicon oligomer has a large number of photocurable epoxy groups, so that the organosilicon release agent can be cured at room temperature in air.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the ultraviolet curing organosilicon release agent is obtained by a one-step method of hydrosilylation reaction, and has high reaction speed.
(2) The preparation method of the ultraviolet curing organosilicon release agent does not need a solvent in the synthesis process, avoids using a toxic solvent and greatly saves the cost.
(3) The ultraviolet curing organic silicon release agent can be cured at room temperature in air, and a coating obtained after curing can generate a good release effect, and is low in stripping force, good in adhesive force and good in heat resistance.
(4) The ultraviolet curing organic silicon release agent has wide application range and can be applied to the outer surface layers of metal, glass, paper, plastic and the like.
Drawings
Fig. 1 is an infrared spectrum of the epoxy-based silicone oligomer obtained in example 1.
Fig. 2 is an infrared spectrum of the epoxy-based silicone oligomer obtained in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The side hydrogen silicone oils (PHMS-PDMS) with different hydrogen contents (0.06%, 0.09%, 0.12%) described in the examples were obtained from the new zhejiang rude silicone materials co.
The Karstedt catalyst used in the examples was formulated as follows: 0.0998g of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and 50.00g of toluene are accurately weighed and placed in a beaker to be stirred for 1 hour, and then the Karstedt catalyst with the concentration of 1000ppm is filled in a 100mL brown bottle to be stored.
In the examples, the method for testing the release force at normal temperature and the method for testing the residual adhesion rate of the release agent are respectively as follows:
a method for testing the normal-temperature release force of a release agent comprises the following steps: the TESA 7475 adhesive tape is stuck on the tested silicon-coated release paper according to the standard method, cut into strips according to the shape of the adhesive tape, and then pressed back and forth three times by a 2kg rubber compression roller. The treated adhesive tape was used at 20g/cm2The standard stainless steel strip is pressed for 20 hours at normal temperature, and is placed for 4 hours at room temperature, and then is tested by a release force tester, the stretching speed is 30cm/min, and the tensile force at the stretching angle of 180 degrees is the normal-temperature release force.
Secondly, a residual adhesion rate test method of the release agent:
(1) the Nitto31B tape was attached to the silicon-coated release paper to be tested by a standard method, cut into long strips in the shape of the tape, and then pressed back and forth three times with a 2kg rubber press roll. The treated adhesive tape was used at 20g/cm2The standard stainless steel strip was placed in an oven at 70 ℃ under internal pressure for 20 hours, and then taken out and left to stand for 1 hour.
(2) The adhesive tape of Nitto31B was peeled from the release paper and adhered to a clean PET film by a standard method, after 1.5 hours, the film was tested by a release force tester, the tensile force was measured at a tensile speed of 30cm/min and at a tensile angle of 180 degrees, and the obtained release force value was recorded. After repeating the experiment for a plurality of times, the average value of the release force values is calculated and recorded as F2。
(3) Directly sticking the adhesive tape of Nitto31B on a clean PET film according to a standard method, and testing the release force after 1.5 hoursAnd (4) testing by a machine, wherein the tensile force is measured when the tensile speed is 30cm/min and the tensile angle is 180 degrees, and the obtained release force value is recorded. After repeating the experiment for a plurality of times, the average value of the release force values is calculated and recorded as F1。
(4) Residual adhesion rate ═ F2/F1×100％。
Example 1
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 15 parts of 4-vinyl-1-cyclohexene-1, 2-epoxy and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the epoxy group organic silicon oligomer comprises the following steps: adding 10.00g of hydrogen-terminated silicone oil (PHMS-PDMS) (with the hydrogen content of 0.06 percent and purchased from New Zhejiang Runzao Silicone Material Co., Ltd.) and 1.48g of 4-vinyl-1-cyclohexene-1, 2-epoxy (the mass ratio of the substances is 1:2), 0.20g of Karstedt catalyst, 0.03g of p-methoxyphenol and 10.00g of toluene into a reaction vessel, stirring uniformly, heating to 100 ℃ for reaction for 6 hours, and obtaining epoxy silicone oligomer after the reaction is finished, wherein the reaction formula is as follows:
100 parts of the obtained epoxy organosilicon oligomer, 20 parts of 4-vinyl-1-cyclohexene-1, 2-epoxy and 4 parts of Easepi1176 (cationic photoinitiator) are stirred and mixed uniformly to obtain the ultraviolet curing organosilicon release agent of the embodiment.
The infrared spectrum of the epoxy-based silicone oligomer obtained in example 1 is shown in fig. 1, and it can be seen that the epoxy-based silicone oligomer was successfully synthesized in this example.
The TG test of the epoxy-based silicone oligomer obtained in this example shows that the temperatures corresponding to the two maximum decomposition rates under an air atmosphere are 437.6 and 511.3 ℃, the temperature corresponding to 5% weight loss can reach 366.5 ℃, and the temperature corresponding to 30% weight loss can reach 480 ℃. Meanwhile, the epoxy silicone oligomer obtained in the embodiment has a large number of light-curable epoxy groups, so that the silicone release agent can be cured at room temperature in air.
And (3) coating the ultraviolet curing organosilicon release agent on a PET film by using a 2-micron wire bar in a scraping manner, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in table 1 below. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 1 release performance test results of the uv-curable silicone release agent prepared in example 1
| Serial number | Normal temperature release force (g/25mm) | Residual adhesion (%) |
| 1 | 4.66 | 89.74 |
| 2 | 4.86 | 90.56 |
| 3 | 5.15 | 91.93 |
| Mean value of | 4.89 | 90.74 |
Example 2
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 20 parts of 4-vinyl-1-cyclohexene-1, 2 epoxy and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the epoxy group organic silicon oligomer comprises the following steps: 10.00g of lateral hydrogen silicone oil (PHMS-PDMS) (with the hydrogen content of 0.09% and purchased from New Zhejiang Runzao organosilicon Material Co., Ltd.), 2.24g of 4-vinyl-1-cyclohexene-1, 2-epoxy (the mass ratio of the substances is 1:2), 0.20g of Karstedt catalyst, 0.03g of p-methoxyphenol and 10.00g of toluene are added into a reaction vessel, the mixture is stirred uniformly and heated to 100 ℃ for reaction for 6 hours, and epoxy group organosilicon oligomer is obtained after the reaction is finished.
100 parts of the obtained epoxy organosilicon oligomer, 20 parts of 4-vinyl-1-cyclohexene-1, 2-epoxy and 4 parts of Easepi1176 (cationic photoinitiator) are stirred and mixed uniformly to obtain the ultraviolet curing organosilicon release agent of the embodiment.
And (3) coating the ultraviolet curing organosilicon release agent on a PET film by using a 2-micron wire bar in a scraping manner, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in table 2 below. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 2 release performance test results of the uv-curable silicone release agent prepared in example 2
| Serial number | Normal temperature release force (g/25mm) | Residual adhesion (%) |
| 1 | 5.11 | 91.32 |
| 2 | 5.23 | 90.54 |
| 3 | 5.37 | 92.78 |
| Mean value of | 5.24 | 91.54 |
Example 3
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 20 parts of 4-vinyl-1-cyclohexene-1, 2 epoxy and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the epoxy group organic silicon oligomer comprises the following steps: 10.00g of lateral hydrogen silicone oil (PHMS-PDMS) (with the hydrogen content of 0.12 percent and purchased from New Zhejiang Runzao organosilicon Material Co., Ltd.) and 2.98g of 4-vinyl-1-cyclohexene-1, 2-epoxy (the mass ratio of the substances is 1:2), 0.20g of Karstedt catalyst, 0.03g of p-methoxyphenol and 10.00g of toluene are added into a reaction vessel, the mixture is stirred uniformly and heated to 100 ℃ for reaction for 6 hours, and epoxy group organosilicon oligomer is obtained after the reaction is finished.
The IR spectrum of the epoxy-based silicone oligomer obtained in example 3 is shown in FIG. 2, from which it can be seen that the epoxy-based silicone oligomer was successfully synthesized.
100 parts of the obtained epoxy organosilicon oligomer, 20 parts of 4-vinyl-1-cyclohexene-1, 2-epoxy and 4 parts of Easepi1176 (cationic photoinitiator) are stirred and mixed uniformly to obtain the ultraviolet curing organosilicon release agent of the embodiment.
And (3) coating the ultraviolet curing organosilicon release agent on a PET film by using a 2-micron wire bar in a scraping manner, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in table 3 below. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 3 release performance test results of the uv-curable silicone release agent prepared in example 3
| Serial number | Normal temperature release force (g/25mm) | Residual adhesion (%) |
| 1 | 5.17 | 91.55 |
| 2 | 5.37 | 92.43 |
| 3 | 5.52 | 92.89 |
| Mean value of | 5.35 | 92.29 |
Example 4
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the organic silicon acrylate oligomer comprises the following steps: lateral hydrogen silicone oil (PHMS-PDMS) (hydrogen content 0.06%, purchased from Runzi Mitsuki Kaisha organic silicon New materials Co., Ltd.) 10.00g and limonene 1, 2-epoxide 1.82g (the ratio of the amount of the substances is 1:2), 0.20g Karstedt catalyst, 0.03g p-methoxyphenol, 10.00g toluene are added into a reaction vessel, the mixture is stirred uniformly and heated to 100 ℃ for reaction for 6 hours, and epoxy group organic silicon oligomer is obtained after the reaction is finished, wherein the reaction formula is as follows:
and stirring and uniformly mixing 100 parts of the obtained epoxy organosilicon oligomer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator) to obtain the ultraviolet curing organosilicon release agent of the embodiment.
And (3) coating the ultraviolet curing organosilicon release agent on a PET film by using a 2-micron wire bar in a scraping manner, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in table 4 below. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 4 release performance test results of the uv-curable silicone release agent prepared in example 4
| Serial number | Normal temperature release force (g/25mm) | Residue bondingPercentage (%) |
| 1 | 5.58 | 92.59 |
| 2 | 5.49 | 91.85 |
| 3 | 6.02 | 93.45 |
| Mean value of | 5.69 | 92.63 |
Example 5
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the epoxy group organic silicon oligomer comprises the following steps: 10.00g of lateral hydrogen silicone oil (PHMS-PDMS) (with the hydrogen content of 0.06 percent and purchased from New Zhejiang Runzao organosilicon Material Co., Ltd.) and 2.74g of limonene 1, 2-epoxide (the ratio of the amount of the substances is 1:2), 0.23g of Karstedt catalyst, 0.02g of p-methoxyphenol and 10.00g of toluene are added into a reaction vessel, the mixture is stirred uniformly and heated to 100 ℃ for reaction for 6 hours, and epoxy group organosilicon oligomer is obtained after the reaction is finished.
The IR spectrum of the silicone acrylate oligomer obtained in example 5 is shown in FIG. 2, from which it can be seen that the present invention successfully synthesized epoxy-based silicone oligomers.
And stirring and uniformly mixing 100 parts of the obtained epoxy organosilicon oligomer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator) to obtain the ultraviolet curing organosilicon release agent of the embodiment.
And (3) coating a 2-micron wire bar of the ultraviolet curing organosilicon release agent on a PET film by scraping, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in the following table 5. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 5 test results of release properties of uv-curable silicone release agent prepared in example 5
| Serial number | Normal temperature release force (g/25mm) | Residual adhesion (%) |
| 1 | 4.66 | 90.54 |
| 2 | 5.15 | 91.34 |
| 3 | 5.22 | 92.42 |
| Mean value of | 5.01 | 91.43 |
Example 6
An ultraviolet curing organosilicon release agent is prepared from the following raw materials in parts by weight: 100 parts of epoxy group organic silicon prepolymer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator).
The preparation method of the epoxy group organic silicon oligomer comprises the following steps: 10.00g of hydrogen side silicone oil (PHMS-PDMS) (with the hydrogen content of 0.06 percent and purchased from New Zhejiang Runzao organosilicon Material Co., Ltd.), 3.66g of limonene 1, 2-epoxide (the ratio of the amount of substances is 1:2), 0.22g of Karstedt catalyst, 0.02g of p-methoxyphenol and 10.00g of toluene are added into a reaction vessel, the mixture is stirred uniformly and heated to 100 ℃ for reaction for 6 hours, and epoxy group organosilicon oligomer is obtained after the reaction is finished.
And stirring and uniformly mixing 100 parts of the obtained epoxy organosilicon oligomer, 20 parts of limonene 1, 2-epoxide and 4 parts of Easepi1176 (cationic photoinitiator) to obtain the ultraviolet curing organosilicon release agent of the embodiment.
And (3) coating the ultraviolet curing organosilicon release agent on a PET film by using a 2-micron wire bar in a scraping manner, then putting the coated PET film into a CH-1022000W UV curing box, and curing for 30 seconds to obtain the cured organosilicon release coating. The results of the release property test are shown in table 6 below. Numbers 1, 2, 3 indicate that three replicates were made and then averaged.
Table 6 release performance test results of the uv-curable silicone release agent prepared in example 6
Reactive diluents in the above examples:
the reactive diluent of the present invention refers to a reactive monomer having at least one epoxy group, including but not limited to at least one of 1, 2 epoxy-5-hexene, 1, 2 epoxy-7-octene, 1, 2 epoxy-9-decene, allyl glycidyl ether, methyl methacrylate (GMA), 4-vinyl-1-cyclohexene-1, 2 epoxy, limonene-1, 2 epoxide, butyl glycidyl ether, 1, 7-octadiene diepoxide, glycidyl propargyl ether, vinylcyclohexene dioxide, allyl glycidyl ether, glycidyl phenyl ether, t-butyl glycidyl ether, 2-toluene glycidyl ether, octyl glycidyl ether, 1, 4-butanediol diglycidyl ether.
The photoinitiator in the above embodiments may also be:
the cationic photoinitiator is a compound with photoinitiation activity, and after absorbing light energy, the compound is in an excited state, molecules are subjected to photolysis reaction to generate super acid, namely super strong protonic acid or Lewis acid, so that cationic oligomer and reactive diluent are initiated to carry out cationic polymerization. May be at least one of triarylsulfonium salt cationic photoinitiator (Easepi1176), 4-isobutylphenyl-4 '-methylphenyliodihexafluorophosphate (cationic photoinitiator 250), diphenyliodonium hexafluorophosphate, 4' -dimethyldiphenyliodonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate liquid photoinitiator.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the ultraviolet curing organic silicon release agent is characterized by comprising the following steps: uniformly mixing and stirring epoxy organosilicon oligomer, reactive diluent and photoinitiator to obtain an ultraviolet curing organosilicon release agent;
the epoxy organic silicon oligomer is generated by carrying out hydrosilylation reaction on an epoxy monomer containing a six-membered ring and lateral hydrogen silicone oil;
the mass ratio of the organic silicon oligomer to the reactive diluent to the photoinitiator is as follows: 100: (10-30): (1-4).
2. The method for preparing the ultraviolet curing silicone release agent according to claim 1, characterized in that the epoxy-based silicone oligomer is prepared by the following steps:
uniformly mixing lateral hydrogen silicone oil, epoxy monomer containing six-membered ring, catalyst and polymerization inhibitor, and heating to 80-110 ℃ for reaction for 4-8 hours;
the mole ratio of the lateral hydrogen silicone oil to the epoxy monomer containing the six-membered ring is 1: 2-1: 2.5;
the concentration of the catalyst in the whole reaction system is 4-20 ppm;
the mass of the polymerization inhibitor is 0.01-0.1% of the total weight of the reactants.
3. The method for preparing the ultraviolet-curable silicone release agent according to claim 2, wherein the epoxy monomer containing a six-membered ring is 4-vinyl-1-cyclohexene-1, 2 epoxy or limonene 1, 2-epoxide.
4. The method for preparing the ultraviolet-curable silicone release agent according to claim 2, wherein the catalyst is at least one of Karstedt catalyst or Spiecer catalyst.
5. The method for preparing the ultraviolet-curable silicone release agent according to claim 2, wherein the polymerization inhibitor is at least one of p-methoxyphenol, p-hydroxyanisole, hydroquinone, 2, 6-di-tert-butyl-p-cresol, and p-benzoquinone.
6. The method for preparing the ultraviolet curing organosilicon release agent according to any one of claims 1 to 5, the reactive diluent is characterized by being at least one of 1, 2 epoxy-5-hexene, 1, 2 epoxy-7-octene, 1, 2 epoxy-9-decene, allyl glycidyl ether, methyl methacrylate (GMA), 4-vinyl-1-cyclohexene-1, 2 epoxy, limonene-1, 2 epoxide, butyl glycidyl ether, 1, 7-octadiene diepoxide, glycidyl propargyl ether, vinylcyclohexene dioxide, allyl glycidyl ether, glycidyl phenyl ether, tert-butyl glycidyl ether, 2-toluene glycidyl ether, octyl glycidyl ether and 1, 4-butanediol diglycidyl ether.
7. The method for preparing the ultraviolet curing organosilicon release agent according to any one of claims 1 to 5, wherein the photoinitiator is at least one of triarylsulfonium salt cationic photoinitiator, 4-isobutylphenyl-4 '-methylphenyliodihexafluorophosphate, diphenyliodonium hexafluorophosphate, 4' -dimethyldiphenyliodonium hexafluorophosphate and triarylsulfonium hexafluoroantimonate liquid photoinitiator.
8. An ultraviolet light curing organic silicon release agent is characterized by comprising an epoxy organic silicon oligomer, a reactive diluent and a photoinitiator;
the mass ratio of the organic silicon oligomer to the reactive diluent to the photoinitiator is as follows: 100: (10-30): (1-4);
the epoxy organic silicon oligomer is generated by carrying out hydrosilylation reaction on an epoxy monomer containing a six-membered ring and lateral hydrogen silicone oil.
9. The uv-curable silicone release agent according to claim 8, wherein the six-membered ring-containing epoxy monomer is 4-vinyl-1-cyclohexene-1, 2 epoxy or limonene 1, 2-epoxide.
10. The application of the ultraviolet curing organic silicon release agent as claimed in any one of claims 8 to 9, which is used for forming a cured release agent coating on the surface of a material by adopting an ultraviolet irradiation mode under the condition of no inert gas protection.
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| CN116063682A (en) * | 2022-12-07 | 2023-05-05 | 中科院广州化学有限公司 | UV/moisture dual-curing epoxy-based organic silicon resin and preparation method and application thereof |
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