CN117736691A - Photo-curing sealant and preparation method thereof - Google Patents
Photo-curing sealant and preparation method thereof Download PDFInfo
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- CN117736691A CN117736691A CN202311750490.2A CN202311750490A CN117736691A CN 117736691 A CN117736691 A CN 117736691A CN 202311750490 A CN202311750490 A CN 202311750490A CN 117736691 A CN117736691 A CN 117736691A
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- 239000000565 sealant Substances 0.000 title claims abstract description 50
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 31
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 229920005601 base polymer Polymers 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 150000002923 oximes Chemical class 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical group C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 238000001723 curing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
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- 230000005855 radiation Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
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- 239000000499 gel Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Sealing Material Composition (AREA)
Abstract
The invention discloses a photo-curing sealant and a preparation method thereof, and relates to the technical field of photo-curing sealants, wherein the photo-curing sealant comprises the following raw materials in parts by weight: 15-70 parts of base polymer, 5-45 parts of active calcium carbonate, 5-10 parts of petroleum resin, 3-9 parts of silica micropowder, 0.5-2 parts of gas-phase white carbon black, 1-10 parts of cross-linking agent, 0.1-1 part of coupling agent, 0.1-2 parts of catalyst, 4-7 parts of bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, 6-10 parts of photo-curing prepolymer, 2-4.5 parts of active diluent, 6-20 parts of acrylate type active monomer and 1.5-4 parts of hydroquinone. According to the invention, a sufficient amount of active calcium carbonate, petroleum resin and silicon micropowder are added into a base polymer to obtain a colloid substance, and bisphenol A epoxy monoacrylate, acrylate monomer photoinitiator and 2-methylimidazole are added into the colloid substance, so that the model performance of a subsequent finished sealant on a cured product is obviously improved, and the sealant also has good adhesion performance under a metal base.
Description
Technical Field
The invention relates to the technical field of photo-curing sealants, in particular to a photo-curing sealant and a preparation method thereof.
Background
Ultraviolet light curing is a type of radiation curing, and uses Ultraviolet (UV) to irradiate a coating, so that reactions such as radiation polymerization, radiation crosslinking, radiation grafting and the like are generated, low-molecular-weight substances are quickly converted into high-molecular-weight products, the curing is directly performed on unheated substrates, the system contains no solvent or a very small amount of solvent, and a liquid film is almost 100% cured after irradiation, so that the emission of VOC (volatile organic compounds) is very low. Therefore, since the end of 60 s, this technology has been rapidly developed internationally, and its products are widely used in many industries. UV curing to prepare adhesives are favored in the market for their unique advantages,
at present, silicone rubber is generally used as an assembly bonding sealant of a solar module, and the performance requirements of the silicone rubber for the solar module are different from those of the common silicone rubber due to the special use environment and the use requirements of the industry on the battery module. Solar modules are used under strong sunlight conditions, are outdoor, and are required to have excellent ultraviolet radiation resistance, excellent high and low temperature resistance, and water and dust resistance. In addition, the lifetime of the solar module is 20 to 30 years, so the service time of the silica gel must be longer than this time, and therefore, it is urgent to develop a weather-resistant anti-yellowing silicone sealant for the solar module.
As disclosed in chinese patent publication No. CN101914364a, the ultraviolet curing silicone sealant is prepared by ultraviolet curing technology, and the curing effect accords with national standard.
The following problems exist in the prior art:
however, the above-mentioned photo-curable sealants are often suitable for thinner coatings in use because the depth of curing is limited in the actual adhesion process, and the cured products have insufficient mechanical properties and the adhesion properties to the substrates such as the metal of the photo-curable sealants produced are general,
disclosure of Invention
The invention provides a photo-curing sealant and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention adopts the following technical scheme:
a photo-curing sealant and a preparation method thereof comprise the following raw materials in parts by weight:
15-70 parts of base polymer, 5-45 parts of active calcium carbonate, 5-10 parts of petroleum resin, 3-9 parts of silica micropowder, 0.5-2 parts of gas-phase white carbon black, 1-10 parts of cross-linking agent, 0.1-1 part of coupling agent, 0.1-2 parts of catalyst, 4-7 parts of bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, 6-10 parts of photo-curing prepolymer, 2-4.5 parts of active diluent, 6-20 parts of acrylate type active monomer and 1.5-4 parts of hydroquinone.
The technical scheme of the invention is further improved as follows: the photo-curing prepolymer is epoxy acrylate, specifically bisphenol A diacrylate with molecular weight 484.54 and refractive index of 1.549, and the boiling point of the bisphenol A diacrylate is 654.1 +/-55.0 ℃ and 1.2+/-0.1 g/cm < 3 >.
The technical scheme of the invention is further improved as follows: the reactive diluent adopts N-butyl glycidyl ether with colorless to pale yellow appearance, the epoxy value of the N-butyl glycidyl ether is more than or equal to 0.5, the organic chlorine value is less than or equal to 0.002, and the inorganic chlorine value is less than or equal to 0.005.
The technical scheme of the invention is further improved as follows: the cross-linking agent is methyl tributyl ketoxime silane or vinyl triisobutanone oxime silane, the base polymer is alpha, omega-dihydroxypolydimethylsiloxane, the gas-phase white carbon black is gas-phase white carbon black after drying and dehydration, the coupling agent is general silane coupling agent KH-550 or KH-560, the catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, and the plasticizer is conventional plasticizer methyl silicone oil or industrial grade mineral oil.
The technical scheme of the invention is further improved as follows: the method comprises the following steps:
s1: weighing quantitative base polymer according to a proportion, adding enough active calcium carbonate, petroleum resin and silicon micropowder into the base polymer, heating after stirring, adding bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, and standing at 50 ℃ after viscous transparent colloid substances appear in a reaction vessel.
S2: weighing enough commodity epoxy resin and acrylic acid liquid according to a proportion, taking a round bottom flask with reflux condensation, stirring and constant temperature, adding equal proportion of water into the round bottom flask, adding the commodity epoxy resin liquid while stirring, adding the re-steamed acrylic acid and a metered catalyst after the commodity epoxy resin liquid is segmented uniformly, and finally preparing the photo-curing prepolymer,
S3: and (3) placing the product obtained in the step (S1) in a mixing kettle, weighing the gas-phase white carbon black, the cross-linking agent, the coupling agent and the catalyst according to a proportion, uniformly stirring after the addition, and maintaining the temperature at 35 ℃ in the stirring process.
S4: and (2) adding an acrylic active monomer and bisphenol A epoxy monoacrylate+acrylic monomer photoinitiator+2-methylimidazole into the photo-curing prepolymer obtained in the step (S2), placing the photo-curing prepolymer into a reaction kettle, slowly adding an acid catalyst and deionized water, and keeping the reaction kettle in a sealed state all the time in the reaction process.
S5: and (3) placing the mixture obtained in the step (S3) and the mixture obtained in the step (S4) in a vacuum kneader, adding a trace amount of hydroquinone and a reactive diluent in the adding process, setting the operation temperature to be maintained at 150 ℃, setting the mixing time to be 60-150 min, placing the obtained mixture under ultraviolet light of 30-80 mW/cm < 2 >, irradiating for 10-40S, and curing to obtain the photo-curing sealant.
The technical scheme of the invention is further improved as follows: and adding a sufficient amount of active calcium carbonate, petroleum resin and silicon micropowder into the S1, dissolving by an organic solvent, stirring for 2 hours at 50 ℃, raising the temperature to 120 ℃, adding the subsequent substances, and heating for 30 minutes at the final temperature of 120 ℃.
The technical scheme of the invention is further improved as follows: the dome flask in S2 was maintained at a temperature stable to 150 ℃ for a reaction time of 2h.
The technical scheme of the invention is further improved as follows: and in the step S3, the heat preservation temperature of the reaction kettle is 50 ℃, the reaction time is 2 hours, and the boiling phenomenon occurs in the reaction kettle at 100 ℃.
By adopting the technical scheme, compared with the prior art, the invention has the following technical progress:
1. the invention provides a photo-curing sealant and a preparation method thereof, wherein a sufficient amount of active calcium carbonate, petroleum resin and colloidal substances obtained by mixing silicon micropowder are added into a base polymer, and bisphenol A epoxy monoacrylate + acrylate monomer photoinitiator + 2-methylimidazole is added, so that the model performance of a subsequent finished product sealant on a cured product is obviously improved, the curing operation can be completed after the sealant is placed for 2 hours after the sealant is exposed to ultraviolet light in a short time, and the sealant also has good adhesion performance under a metal base.
2. The invention provides a photo-curing sealant and a preparation method thereof, wherein the photo-curing polymer and acrylic active monomer generated by reaction are used for finishing the change of the characteristics, flexibility and hardness of a cured coating of the sealant, so that the sealant meets the construction adhesion requirement and the coating performance index, the ultraviolet curing speed is accelerated, the heat resistance and other properties of a cured product can be improved, and the increased hydroquinone before the completion of manufacture can reduce the occurrence of thermal polymerization during storage and improve the storage stability.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
a photo-curing sealant comprises the following raw materials in parts by weight:
25 parts of a base polymer, 15 parts of activated calcium carbonate, 5 parts of petroleum resin, 8 parts of silica micropowder, 2 parts of gas-phase white carbon black, 6 parts of a cross-linking agent, 0.5 part of a coupling agent, 0.5 part of a catalyst, 5 parts of bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, 8 parts of a photo-curing prepolymer, 3 parts of an active diluent, 10 parts of an acrylate type active monomer and 2 parts of hydroquinone.
The photo-curing prepolymer is epoxy acrylate, specifically bisphenol A diacrylate with molecular weight 484.54 and refractive index of 1.549, and the boiling point of the bisphenol A diacrylate is 654.1 +/-55.0 ℃ and 1.2+/-0.1 g/cm < 3 >.
The reactive diluent adopts N-butyl glycidyl ether with colorless to pale yellow appearance, the epoxy value of the N-butyl glycidyl ether is more than or equal to 0.5, the organic chlorine value is less than or equal to 0.002, and the inorganic chlorine value is less than or equal to 0.005.
The cross-linking agent of the catalyst is methyl tributyl ketoxime silane or vinyl triisobutanone oxime silane, the base polymer is alpha, omega-dihydroxypolydimethylsiloxane, the gas-phase white carbon black after drying and dehydration is gas-phase white carbon black, the coupling agent is general silane coupling agent KH-550 or KH-560, the catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, and the plasticizer is conventional plasticizer methyl silicone oil or industrial grade mineral oil.
A preparation method of a photo-curing sealant comprises the following steps:
s1: weighing quantitative base polymer according to a proportion, adding enough active calcium carbonate, petroleum resin and silicon micropowder into the base polymer, heating after stirring, adding bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, and standing at 50 ℃ after viscous transparent colloid substances appear in a reaction vessel.
S2: weighing enough commodity epoxy resin and acrylic acid liquid according to a proportion, taking a round bottom flask with reflux condensation, stirring and constant temperature, adding equal proportion of water into the round bottom flask, adding the commodity epoxy resin liquid while stirring, adding the re-steamed acrylic acid and a metered catalyst after the commodity epoxy resin liquid is segmented uniformly, and finally preparing the photo-curing prepolymer,
S3: and (3) placing the product obtained in the step (S1) in a mixing kettle, weighing the gas-phase white carbon black, the cross-linking agent, the coupling agent and the catalyst according to a proportion, uniformly stirring after the addition, and maintaining the temperature at 35 ℃ in the stirring process.
S4: and (2) adding an acrylic active monomer and bisphenol A epoxy monoacrylate+acrylic monomer photoinitiator+2-methylimidazole into the photo-curing prepolymer obtained in the step (S2), placing the photo-curing prepolymer into a reaction kettle, slowly adding an acid catalyst and deionized water, and keeping the reaction kettle in a sealed state all the time in the reaction process.
S5: and (3) placing the mixture obtained in the step (S3) and the mixture obtained in the step (S4) in a vacuum kneader, adding a trace amount of hydroquinone and a reactive diluent in the adding process, setting the operation temperature to be maintained at 150 ℃, setting the mixing time to be 60-150 min, placing the obtained mixture under ultraviolet light of 30-80 mW/cm < 2 >, irradiating for 10-40S, and curing to obtain the photo-curing sealant.
S1, adding enough active calcium carbonate, petroleum resin and silicon micropowder, dissolving by an organic solvent, stirring for 2 hours at 50 ℃, raising the temperature to 120 ℃ and then heating for 30 minutes at the final temperature of 120 ℃.
The dome flask was maintained at a temperature stable at 150℃for a reaction time of 2h in S2. And S3, the heat preservation temperature of the reaction kettle is 50 ℃, the reaction time is 2 hours, and the boiling phenomenon occurs in the reaction kettle at 100 ℃.
Embodiment two:
a photo-curing sealant comprises the following raw materials in parts by weight:
35 parts of base polymer, 17 parts of activated calcium carbonate, 8 parts of petroleum resin, 7 parts of silica micropowder, 1 part of gas-phase white carbon black, 4 parts of cross-linking agent, 1 part of coupling agent, 1 part of catalyst, 7 parts of photo-curing prepolymer, 4 parts of reactive diluent, 12 parts of acrylic ester type active monomer and 3 parts of hydroquinone.
The photo-curing prepolymer is epoxy acrylate, specifically bisphenol A diacrylate with molecular weight 484.54 and refractive index of 1.549, and the boiling point of the bisphenol A diacrylate is 654.1 +/-55.0 ℃ and 1.2+/-0.1 g/cm < 3 >.
The reactive diluent adopts N-butyl glycidyl ether with colorless to pale yellow appearance, the epoxy value of the N-butyl glycidyl ether is more than or equal to 0.5, the organic chlorine value is less than or equal to 0.002, and the inorganic chlorine value is less than or equal to 0.005.
The cross-linking agent of the catalyst is methyl tributyl ketoxime silane or vinyl triisobutanone oxime silane, the base polymer is alpha, omega-dihydroxypolydimethylsiloxane, the gas-phase white carbon black after drying and dehydration is gas-phase white carbon black, the coupling agent is general silane coupling agent KH-550 or KH-560, the catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, and the plasticizer is conventional plasticizer methyl silicone oil or industrial grade mineral oil.
A preparation method of a photo-curing sealant comprises the following steps:
s1: weighing quantitative base polymer according to a proportion, adding enough active calcium carbonate, petroleum resin and silicon micropowder into the base polymer, heating after stirring, adding bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, and standing at 50 ℃ after viscous transparent colloid substances appear in a reaction vessel.
S2: weighing enough commodity epoxy resin and acrylic acid liquid according to a proportion, taking a round bottom flask with reflux condensation, stirring and constant temperature, adding equal proportion of water into the round bottom flask, adding the commodity epoxy resin liquid while stirring, adding the re-steamed acrylic acid and a metered catalyst after the commodity epoxy resin liquid is segmented uniformly, and finally preparing the photo-curing prepolymer,
S3: and (3) placing the product obtained in the step (S1) in a mixing kettle, weighing the gas-phase white carbon black, the cross-linking agent, the coupling agent and the catalyst according to a proportion, uniformly stirring after the addition, and maintaining the temperature at 35 ℃ in the stirring process.
S4: and (3) placing the photo-curing prepolymer obtained in the step (S2) added with the acrylic active monomer in a reaction kettle, slowly adding an acid catalyst and deionized water, and keeping the reaction kettle in a sealed state all the time in the reaction process.
S5: and (3) placing the mixture obtained in the step (S3) and the mixture obtained in the step (S4) in a vacuum kneader, adding a trace amount of hydroquinone and a reactive diluent in the adding process, setting the operation temperature to be maintained at 150 ℃, setting the mixing time to be 60-150 min, placing the obtained mixture under ultraviolet light of 30-80 mW/cm < 2 >, irradiating for 10-40S, and curing to obtain the photo-curing sealant.
S1, adding enough active calcium carbonate, petroleum resin and silicon micropowder, dissolving by an organic solvent, and stirring for 2 hours at 50 ℃.
The dome flask was maintained at a temperature stable at 150℃for a reaction time of 2h in S2. And S3, the heat preservation temperature of the reaction kettle is 50 ℃, the reaction time is 2 hours, and the boiling phenomenon occurs in the reaction kettle at 100 ℃.
Embodiment III:
a photo-curing sealant comprises the following raw materials in parts by weight:
19 parts of a basic polymer, 20 parts of activated calcium carbonate, 8 parts of petroleum resin, 9 parts of silica powder, 2 parts of fumed silica, 6 parts of a cross-linking agent, 1 part of a coupling agent, 1 part of a catalyst, 4 parts of an active diluent, 16 parts of an acrylic ester type active monomer, 6 parts of bisphenol A epoxy monoacrylate+acrylic ester monomer photoinitiator+2-methylimidazole and 8 parts of a photo-curing prepolymer.
The reactive diluent adopts N-butyl glycidyl ether with colorless to pale yellow appearance, the epoxy value of the N-butyl glycidyl ether is more than or equal to 0.5, the organic chlorine value is less than or equal to 0.002, and the inorganic chlorine value is less than or equal to 0.005.
The cross-linking agent of the catalyst is methyl tributyl ketoxime silane or vinyl triisobutanone oxime silane, the base polymer is alpha, omega-dihydroxypolydimethylsiloxane, the gas-phase white carbon black after drying and dehydration is gas-phase white carbon black, the coupling agent is general silane coupling agent KH-550 or KH-560, the catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, and the plasticizer is conventional plasticizer methyl silicone oil or industrial grade mineral oil.
A preparation method of a photo-curing sealant comprises the following steps:
s1: weighing quantitative base polymer according to a proportion, adding enough active calcium carbonate, petroleum resin and silicon micropowder into the base polymer, heating after stirring, adding bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, and standing at 50 ℃ after viscous transparent colloid substances appear in a reaction vessel.
S2: and (3) placing the product obtained in the step (S1) in a mixing kettle, weighing the gas-phase white carbon black, the cross-linking agent, the coupling agent and the catalyst according to a proportion, uniformly stirring after the addition, and maintaining the temperature at 35 ℃ in the stirring process.
S3: and (3) placing the photo-curing prepolymer obtained in the step (S2) added with the acrylic active monomer in a reaction kettle, slowly adding an acid catalyst and deionized water, and keeping the reaction kettle in a sealed state all the time in the reaction process.
S4: and (3) placing the mixture obtained in the step (S3) and the mixture obtained in the step (S4) in a vacuum kneader, adding a micro-amount of reactive diluent in the adding process, setting the operation temperature to be maintained at 150 ℃, setting the mixing time to be 60-150 min, placing the obtained mixture under ultraviolet light of 30-80 mW/cm < 2 >, irradiating for 10-40S, and curing to obtain the photo-curing sealant.
S1, adding enough active calcium carbonate, petroleum resin and silicon micropowder, dissolving by an organic solvent, and stirring for 2 hours at 50 ℃.
The dome flask was maintained at a temperature stable at 150℃for a reaction time of 2h in S2. And S3, the heat preservation temperature of the reaction kettle is 50 ℃, the reaction time is 2 hours, and the boiling phenomenon occurs in the reaction kettle at 100 ℃.
Different experimental tests were performed on the photo-curing sealants prepared in the first, second and third embodiments, respectively.
The photo-curing sealant prepared in the first and second examples was tested for adhesion property by using a rotational viscometer at 25 deg. and 60 deg. per cps/C, and the adhesion property of the sealant prepared in the first example was stronger than that of the sealant prepared in the second example.
And (3) carrying out thermal stability detection on the photo-curing sealant prepared in the first embodiment and the third embodiment, setting the high-stability detection environment temperature to 120 ℃, setting the low-temperature detection environment temperature to-25 ℃, repeatedly carrying out high-low temperature cyclic impact test at-40-120 ℃ on the basis, and storing two parts of the obtained photo-curing sealant in a 60 ℃ oven for 2 weeks, and storing two parts of the obtained photo-curing sealant at room temperature for 6 months.
The result is that the sealant obtained in the third embodiment has micro-melting phenomenon under high temperature environment, and becomes solid state under low temperature detection environment, and is heated again to be liquid state, and has micro-gel phenomenon, aging phenomenon occurs in the oven at 60 ℃ for 1 week, and the sealant is stored at room temperature for 3 months and is gelled;
the sealant obtained in the first embodiment has no change under a high-temperature environment, has a microgel phenomenon under a low-temperature environment, has an aging phenomenon in a 60 ℃ oven for 2 weeks, and has no gel phenomenon after being stored at room temperature for 6 months, so that the thermal stability and the storage stability of the sealant obtained in the first embodiment are higher than those of the sealant obtained in the third embodiment.
As can be seen from the comparative experiments: the sealant prepared in example one is the best in terms of adhesion, storage stability and thermal stability, and thus example one is the best example in this application.
The foregoing invention has been generally described in great detail, but it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, it is intended to cover modifications or improvements within the spirit of the inventive concepts.
Claims (5)
1. The photo-curing sealant is characterized by comprising the following raw materials in parts by weight: 15-70 parts of base polymer, 5-45 parts of active calcium carbonate, 5-10 parts of petroleum resin, 3-9 parts of silica micropowder, 0.5-2 parts of gas-phase white carbon black, 1-10 parts of cross-linking agent, 0.1-1 part of coupling agent, 0.1-2 parts of catalyst, 4-7 parts of bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, 6-10 parts of photo-curing prepolymer, 2-4.5 parts of active diluent, 6-20 parts of acrylate type active monomer and 1.5-4 parts of hydroquinone.
2. A photo-curable sealant according to claim 1, wherein: the photo-curing prepolymer is epoxy acrylate, specifically bisphenol A diacrylate with molecular weight 484.54 and refractive index of 1.549, and the boiling point of the bisphenol A diacrylate is 654.1 +/-55.0 ℃ and 1.2+/-0.1 g/cm < 3 >.
3. A photo-curable sealant according to claim 1, wherein: the reactive diluent adopts N-butyl glycidyl ether with colorless to pale yellow appearance, the epoxy value of the N-butyl glycidyl ether is more than or equal to 0.5, the organic chlorine value is less than or equal to 0.002, and the inorganic chlorine value is less than or equal to 0.005.
4. A photo-curable sealant according to claim 1, wherein: the cross-linking agent is methyl tributyl ketoxime silane or vinyl triisobutanone oxime silane, the base polymer is alpha, omega-dihydroxypolydimethylsiloxane, the gas-phase white carbon black is gas-phase white carbon black after drying and dehydration, the coupling agent is general silane coupling agent KH-550 or KH-560, the catalyst is dibutyl tin dilaurate or dibutyl tin diacetate, and the plasticizer is conventional plasticizer methyl silicone oil or industrial grade mineral oil.
5. The method for preparing the photo-curing sealant according to claims 1-4, comprising the following steps:
s1: weighing quantitative base polymer according to a proportion, adding enough active calcium carbonate, petroleum resin and silicon micropowder into the base polymer, heating after stirring, adding bisphenol A epoxy monoacrylate+acrylate monomer photoinitiator+2-methylimidazole, and standing at 50 ℃ after viscous transparent colloid substances appear in a reaction vessel.
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|---|---|---|---|---|
| US5432208A (en) * | 1992-02-25 | 1995-07-11 | Japan Institute Of Advanced Dentistry | Photocuring adhesive containing an oligo siloxanyl di(meth)acrylate |
| CN101914364A (en) * | 2010-08-12 | 2010-12-15 | 华南理工大学 | UV (ultraviolet) curing silicone sealant and preparation method thereof |
| CN103232829A (en) * | 2013-04-23 | 2013-08-07 | 广东信翼新材料股份有限公司 | Light-moisture dual-curing adhesive |
| CN112852379A (en) * | 2021-02-26 | 2021-05-28 | 烟台信友新材料有限公司 | High-toughness, heat and humidity resistant ultraviolet curing conductive adhesive and preparation method thereof |
-
2023
- 2023-12-19 CN CN202311750490.2A patent/CN117736691A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5432208A (en) * | 1992-02-25 | 1995-07-11 | Japan Institute Of Advanced Dentistry | Photocuring adhesive containing an oligo siloxanyl di(meth)acrylate |
| CN101914364A (en) * | 2010-08-12 | 2010-12-15 | 华南理工大学 | UV (ultraviolet) curing silicone sealant and preparation method thereof |
| CN103232829A (en) * | 2013-04-23 | 2013-08-07 | 广东信翼新材料股份有限公司 | Light-moisture dual-curing adhesive |
| CN112852379A (en) * | 2021-02-26 | 2021-05-28 | 烟台信友新材料有限公司 | High-toughness, heat and humidity resistant ultraviolet curing conductive adhesive and preparation method thereof |
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