WO2024027006A1 - Low-toxicity single-component silicone sealant for photovoltaic frame and preparation method therefor - Google Patents
Low-toxicity single-component silicone sealant for photovoltaic frame and preparation method therefor Download PDFInfo
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- WO2024027006A1 WO2024027006A1 PCT/CN2022/123002 CN2022123002W WO2024027006A1 WO 2024027006 A1 WO2024027006 A1 WO 2024027006A1 CN 2022123002 W CN2022123002 W CN 2022123002W WO 2024027006 A1 WO2024027006 A1 WO 2024027006A1
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- Prior art keywords
- silicone sealant
- cross
- parts
- linking agent
- low
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- 239000004590 silicone sealant Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 231100000053 low toxicity Toxicity 0.000 title claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 34
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 32
- 230000003014 reinforcing effect Effects 0.000 claims description 28
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 25
- -1 N-(2-aminoethyl)-3-aminopropyl Chemical group 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 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 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- FWSXGNXGAJUIPS-UHFFFAOYSA-N n-pentan-2-ylidenehydroxylamine Chemical group CCCC(C)=NO FWSXGNXGAJUIPS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012808 vapor phase Substances 0.000 claims description 14
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- 229950002372 aminopropylone Drugs 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 15
- 238000004132 cross linking Methods 0.000 abstract description 9
- 230000000711 cancerogenic effect Effects 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 231100000315 carcinogenic Toxicity 0.000 abstract 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 239000000565 sealant Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 231100000357 carcinogen Toxicity 0.000 description 6
- 239000003183 carcinogenic agent Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 150000002923 oximes Chemical class 0.000 description 6
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 229910000085 borane Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XBIKWYOQJVTUEC-UHFFFAOYSA-N phosphorosomethanetriol Chemical compound OC(O)(O)P=O XBIKWYOQJVTUEC-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FWSXGNXGAJUIPS-WAYWQWQTSA-N (nz)-n-pentan-2-ylidenehydroxylamine Chemical compound CCC\C(C)=N/O FWSXGNXGAJUIPS-WAYWQWQTSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0892—Compounds with a Si-O-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the invention relates to the field of silicone sealant, and in particular to a low-toxic single-component photovoltaic frame silicone sealant and a preparation method thereof.
- the cross-linking agents used in solar photovoltaic module sealants are mainly methyltributylketoneoxime-based silane, vinyltributylketoneoxime-based silane or tetrabutylketoneoxime-based silane.
- patent application publication number CN104277759A discloses an aging-resistant solar photovoltaic module sealing material and its preparation method.
- the cross-linking agent used is methyltributyloxime-based silane, vinyl Tributanone oxime silane or tetrabutanone oxime silane, the reaction will release butanone oxime.
- application publication numbers CN102181264A, CN105062078A, CN108624281A, CN112694864A, etc. also have the same problem.
- the application publication numbers are CN113337245A, CN113337245B, CN109957357A, CN104194712B, CN109666448A, CN102816553A, CN102618209B, CN102618209A, CN104194712A, CN105062411A , CN102382615B and other related photovoltaic sealant patents use methyltriethoxysilane or methyltrimethoxy as the cross-linking agent Silane is a cross-linking agent and does not generate butanone oxime, which can avoid the generation of carcinogens. However, it does not belong to the ketoxime type sealant, but to the dealcoholization type. Due to the storage stability, the dealcoholization type photovoltaic sealant has a negative impact on the backplane. Due to its own shortcomings such as adhesion, it is currently unable to replace the mainstream ketoxime-based photovoltaic sealant.
- the application publication number CN103342979A mentions the cross-linking agent system involved in the present invention, but CN103342979A is mainly to solve the storage stability of the sealant rather than to prepare the photovoltaic module sealant.
- the present invention is to overcome the shortcomings of the prior art ketoxime-type photovoltaic sealant, which releases butanone oxime during use and has low adhesion, mechanical properties and aging resistance, and provides a low-toxicity monomer.
- the present invention first provides a low-toxic single-component silicone sealant for photovoltaic frames.
- the cross-linking agent contains linear or branched reinforcing segments
- the side group or terminal group of the reinforcing segment includes an acetone oxime group or a pentanone oxime group.
- the silicone sealant in the present invention uses a cross-linking agent containing an acetone oxime group or a pentanone oxime group during the curing process, which reacts with ⁇ , ⁇ -dihydroxypolydimethylsiloxane during the curing and cross-linking process.
- the hydroxyl group in the alkane reacts to release acetone oxime or pentanone oxime, ultimately achieving the purpose of cross-linking and curing.
- it will not release the carcinogen butanone oxime when reacting with moisture in the air. Since the released acetone oxime or pentanone oxime is not a carcinogen, it will not cause any harmful effects.
- the export and domestic production and use of deoxime type room temperature silica gel will have an impact.
- cross-linking agents commonly used in the prior art are all small molecule cross-linking agents (such as methyltributylketoneoximinosilane, vinyltributylketoneoximesilane or tetrabutylketoneoximylsilane).
- the small molecule cross-linking agent will form cross-linking nodes in the silicone gel for connecting ⁇ , ⁇ -dihydroxypolydimethylsiloxane.
- the long distance between adjacent cross-linking nodes Far away, resulting in smaller interactions between adjacent cross-linked nodes, making it difficult to continue to improve the mechanical properties of the silicone sealant.
- the cross-linking agent in the present invention has a linear or branched reinforcing segment in its structure. Since the acetone oxime group or the pentanone oxime group is grafted to the side group or terminal position of the reinforcing segment, in the present invention
- the cross-linking agent removes acetone oxime or pentanone oxime to form cross-link nodes, due to the traction and stretching effect of the enhanced chain segments between adjacent cross-link nodes, the tension between adjacent cross-link nodes is The interaction force is effectively increased, which is equivalent to increasing the cross-linking density.
- the preparation method of the cross-linking agent is as follows:
- the cross-linking agent in the present invention can be prepared through various reactions during the preparation process. The following is a further description of the preparation method of the cross-linking agent.
- the reactive groups during the preparation of the intermediate product can be silyloxy (-Si-OR), silylhydrogen (-Si-H), silicon chloride (-Si-Cl), silyl hydroxyl (-Si- OH), the above reactive groups can react with the hydroxyl group in acetone oxime or pentanone oxime, so that the acetone oxime group or pentanone oxime group can be grafted to the intermediate product.
- the reinforcing chain segment of the cross-linking agent is also doped with a phosphorus-containing element [0017] Due to the low polarity of the silicon-oxygen bond in the silicone sealant in the prior art, there is a gap between the silicone sealant and the photovoltaic module. The bonding stability of the photovoltaic modules is poor, which leads to the degradation of the bonding performance of the photovoltaic modules during long-term sunlight exposure, leading to the problem of decomposition and detachment. Therefore, in this preferred technical solution, the cross-linking agent is creatively doped with phosphorus-containing elements, which can effectively improve the polarity of the silicone sealant. Compared with the silicone sealant without phosphorus elements in the prior art, It can further improve the adhesion, mechanical properties and aging resistance of silicone sealants.
- the viscosity of the ⁇ , ⁇ -dihydroxypolydimethylsiloxane is between 5 and 100 Pa.S.
- the gas phase silica is gas phase silica treated with hexamethyldisilazane
- the silane coupling agent is ⁇ -[2,3-glycidoxy]propyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, ⁇ -amine Propyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane amino oligomer One or several combinations of things.
- the catalyst is any one or a combination of dibutyltin diacetate, dibutyltin dilaurate, and chelated tin.
- the present invention provides a method for preparing the low-toxic single-component photovoltaic frame silicone sealant, which includes the following steps:
- the stirring temperature in step (1) is 120 ⁇ 170°C
- the vacuum degree during the stirring process is ⁇ -0.095MPa
- the dehydration time is 120 ⁇ 240min
- step (2) a powered planetary mixer is used during the mixing process.
- the vacuum degree is ⁇ -0.095MPa
- the rotation speed is 600 ⁇ 1500rpm
- the mixing time is 100 ⁇ 180min.
- the present invention has the following beneficial effects:
- the silicone sealant in the present invention will not release the carcinogen methylethylketoxime when reacting with moisture in the air. Under the premise that the application of debutylketoxime-type RTV silicone rubber products is limited, the above-mentioned cross-linking agent The prepared silicone rubber has good applicability;
- the present invention contains linear or branched reinforcing segments in the cross-linking agent, which can effectively increase the interaction force between adjacent cross-linking nodes in the silicone sealant and increase the cross-linking density. Moreover, due to the existence of the reinforcing segment, there is a physical entanglement between the reinforcing segment and the main chain segment of ⁇ , ⁇ -dihydroxypolydimethylsiloxane, which can further improve the bonding of the silicone sealant. properties and mechanical properties;
- the cross-linking agent is creatively doped with structural units containing phosphorus elements, which can effectively improve the polarity of the silicone sealant.
- Sealant which can further improve the adhesion, mechanical properties and aging resistance of silicone sealant.
- Cross-linking agent (B) Under nitrogen protection, mix 10g of hydrogen-containing silicone oil (hydrogen value (wt %) is 1.5%, viscosity at 25°C is 20-30 mm2/s) and 10mg tris(pentafluorobenzene)borane Dissolve in 100 ml of toluene, stir evenly and add dropwise a mixture of 12g (165 mmol) acetone oxime and 30 ml toluene. Stir and react at room temperature for 5 hours until no bubbles are generated. Remove toluene and unreacted acetone oxime under reduced pressure to obtain the next step. Cross-linking agent (B) with acetone oxime groups.
- Cross-linking agent (C) Under nitrogen protection, mix 10g of hydrogen-containing silicone oil (hydrogen value (wt %) is 1.5%, viscosity at 25°C is 20-30 mm2/s) and 10mg tris(pentafluorobenzene)borane Dissolve in 100 ml of toluene, stir evenly and add dropwise a mixture of 16.68 g (165 mmol) 2-pentanone oxime and 30 ml of toluene. Stir and react at room temperature for 5 hours until no bubbles are generated. Remove toluene and unreacted 2 under reduced pressure. -pentanone oxime to obtain a cross-linking agent (C) grafted with a pentanone oxime group.
- Cross-linking agent (D) (1) Under nitrogen protection, mix 1.48g (10mmol) vinyltrimethoxysilane, 3g (32mmol) dimethylchlorosilane, 100ml tetrahydrofuran and 2g ferric chloride at 45°C. Stir the reaction for 3 hours, then lower the temperature to room temperature, add 5 parts of activated carbon, stir for 30 minutes, filter, evaporate tetrahydrofuran, and then distill to obtain the intermediate product (D-1).
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- a low-toxic one-component silicone sealant for photovoltaic frames specifically prepared according to the following steps:
- Extrusion performance reflects the construction performance of sealant extrusion, expressed by the volume (capacity) of sealant extruded per unit time.
- Tack drying time The time for the surface of the reaction sealant to lose its viscosity. It is carried out in accordance with Method B specified in GB/T 13477.5-2002.
- Elongation at break according to ISO 37 method.
- the present invention introduces structural units containing phosphorus elements into the cross-linking agent of the individually prepared ketone sealant (such as Example 5, Example 9 and Example 10).
- the creative step is in the cross-linking
- the agent is doped with structural units containing phosphorus elements, which can effectively improve the polarity of the silicone sealant. Compared with silicone sealants without phosphorus elements in the prior art, it can further improve the sealing performance of the silicone sealant. properties, mechanical properties and aging resistance.
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Abstract
The present invention relates to the field of silicone sealants, in particular to a low-toxicity single-component silicone sealant for a photovoltaic frame and a preparation method therefor. The silicone sealant is composed of raw materials comprising the following components: α,ω-dihydroxy-polydimethylsiloxane, a filler, a cross-linking agent, a silane coupling agent and a catalyst, wherein the cross-linking agent contains a linear or branched reinforced chain segment, and the side group or the end group of the reinforced chain segment contains an acetoximido group or a pentanoximido group. The silicone sealant in the present invention does not release diacetylmonoxime containing cancerogenic substances when reacting with moisture in the air, and has good applicability. In addition, the cross-linking agent of the present invention comprises a linear or branched reinforced chain segment, which can effectively improve the interaction force between adjacent cross-linking nodes in the silicone sealant, thereby effectively improving the cohesiveness and mechanical properties of the silicone sealant.
Description
本发明涉及硅酮密封胶领域，尤其涉及一种低毒单组份光伏边框硅酮密封胶及其制备方法。The invention relates to the field of silicone sealant, and in particular to a low-toxic single-component photovoltaic frame silicone sealant and a preparation method thereof.
已有技术中，太阳能光伏组件密封胶采用的交联剂主要是甲基三丁酮肟基硅烷、乙烯基三丁酮肟基硅烷或四丁酮肟基硅烷。In the prior art, the cross-linking agents used in solar photovoltaic module sealants are mainly methyltributylketoneoxime-based silane, vinyltributylketoneoxime-based silane or tetrabutylketoneoxime-based silane.
而这些交联剂与空气中的潮气反应，会释放出丁酮肟，欧盟委员会已经提议法规，将其丁酮肟列入致癌物，一旦法规生效，将对脱肟型室温硅胶出口产生巨大影响，同时，国内相关法规也可能会参照欧盟法规，如果确定了丁酮肟相关致癌性，以后在国内生产使用也将受限。These cross-linking agents react with moisture in the air to release butanone oxime. The European Commission has proposed regulations to list butanone oxime as a carcinogen. Once the regulations take effect, it will have a huge impact on the export of deoxime room temperature silica gel. , at the same time, relevant domestic regulations may also refer to EU regulations. If the carcinogenicity of butanone oxime is determined, domestic production and use will also be restricted in the future.
有关太阳能光伏密封胶的专利文献较多，例如申请公开号为CN104277759A的专利公开了耐老化型太阳能光伏组件密封材料及其制备方法采用的交联剂为甲基三丁酮肟基硅烷、乙烯基三丁酮肟基硅烷或四丁酮肟基硅烷，反应会释放出丁酮肟。例如申请公开号为CN102181264A、CN105062078A、CN108624281A、CN112694864A等也存在相同的问题。There are many patent documents related to solar photovoltaic sealants. For example, the patent application publication number CN104277759A discloses an aging-resistant solar photovoltaic module sealing material and its preparation method. The cross-linking agent used is methyltributyloxime-based silane, vinyl Tributanone oxime silane or tetrabutanone oxime silane, the reaction will release butanone oxime. For example, application publication numbers CN102181264A, CN105062078A, CN108624281A, CN112694864A, etc. also have the same problem.
申请公开号为CN113337245A、CN113337245B、CN109957357A、CN104194712B、CN109666448A、CN102816553A、CN102618209B、CN102618209A、CN104194712A、CN105062411A、CN102382615B等相关光伏密封胶专利采用的交联剂为甲基三乙氧基硅烷或甲基三甲氧基硅烷为交联剂，不会生成丁酮肟，可以避免致癌物质的生成，但是不属于酮肟型密封胶，而属于脱醇型，脱醇型光伏密封胶由于贮存稳定性，对背板的粘接性等自身的缺陷，暂时还无法取代主流的酮肟型光伏密封胶。The application publication numbers are CN113337245A, CN113337245B, CN109957357A, CN104194712B, CN109666448A, CN102816553A, CN102618209B, CN102618209A, CN104194712A, CN105062411A , CN102382615B and other related photovoltaic sealant patents use methyltriethoxysilane or methyltrimethoxy as the cross-linking agent Silane is a cross-linking agent and does not generate butanone oxime, which can avoid the generation of carcinogens. However, it does not belong to the ketoxime type sealant, but to the dealcoholization type. Due to the storage stability, the dealcoholization type photovoltaic sealant has a negative impact on the backplane. Due to its own shortcomings such as adhesion, it is currently unable to replace the mainstream ketoxime-based photovoltaic sealant.
而申请公开号为CN103342979A提到本发明中涉及的交联剂体系，但CN103342979A主要是为了解决密封胶的贮存稳定性，而非制备光伏组件密封胶。The application publication number CN103342979A mentions the cross-linking agent system involved in the present invention, but CN103342979A is mainly to solve the storage stability of the sealant rather than to prepare the photovoltaic module sealant.
此外，除了考虑致癌物质的生成以及贮存稳定性，密封胶的粘结性、力学性能以及耐老化性能也是需要光伏密封胶重点关注的。然而，目前酮肟型光伏密封胶在这些方面仍需要较大的提升，以适应更为严苛的使用环境。In addition, in addition to considering the generation of carcinogens and storage stability, the adhesiveness, mechanical properties and aging resistance of the sealant also require focus on the photovoltaic sealant. However, the current ketoxime photovoltaic sealants still need to be greatly improved in these aspects to adapt to more stringent use environments.
本发明是为了克服现有技术中的酮肟型光伏密封胶在使用过程中会释放出丁酮肟，同时粘结性、力学性能以及耐老化性能较低的缺陷，提供了一种低毒单组份光伏边框硅酮密封胶及其制备方法。The present invention is to overcome the shortcomings of the prior art ketoxime-type photovoltaic sealant, which releases butanone oxime during use and has low adhesion, mechanical properties and aging resistance, and provides a low-toxicity monomer. Component photovoltaic frame silicone sealant and preparation method thereof.
为实现上述发明目的，本发明通过以下技术方案实现：In order to achieve the above-mentioned object of the invention, the present invention is implemented through the following technical solutions:
第一方面，本发明首先提供了一种低毒单组份光伏边框硅酮密封胶，In the first aspect, the present invention first provides a low-toxic single-component silicone sealant for photovoltaic frames.
其是由包括以下组分的原料构成：α，ω- 二羟基聚二甲基硅氧烷、填料、交联剂、硅烷偶联剂以及催化剂；其中：It is composed of raw materials including the following components: α,ω-dihydroxypolydimethylsiloxane, filler, cross-linking agent, silane coupling agent and catalyst; wherein:
所述交联剂中包含有线性或者支化的增强链段；The cross-linking agent contains linear or branched reinforcing segments;
所述增强链段的侧基或者端基包含有丙酮肟基或者戊酮肟基。The side group or terminal group of the reinforcing segment includes an acetone oxime group or a pentanone oxime group.
本发明中的硅酮密封胶其在固化过程中采用了含有丙酮肟基或者戊酮肟基的交联剂，其在固化交联的过程中与α，ω- 二羟基聚二甲基硅氧烷中的羟基反应，从而会释放出丙酮肟或者戊酮肟，最终达到交联固化的目的。相较于传统的丁酮肟型交联剂，与空气中的潮气反应不会释放出有致癌物质的丁酮肟，由于释放出的丙酮肟或者戊酮肟不属于致癌物质，因此不会对脱肟型室温硅胶的出口以及国内生产使用产生影响。The silicone sealant in the present invention uses a cross-linking agent containing an acetone oxime group or a pentanone oxime group during the curing process, which reacts with α, ω-dihydroxypolydimethylsiloxane during the curing and cross-linking process. The hydroxyl group in the alkane reacts to release acetone oxime or pentanone oxime, ultimately achieving the purpose of cross-linking and curing. Compared with the traditional butanone oxime-type cross-linking agent, it will not release the carcinogen butanone oxime when reacting with moisture in the air. Since the released acetone oxime or pentanone oxime is not a carcinogen, it will not cause any harmful effects. The export and domestic production and use of deoxime type room temperature silica gel will have an impact.
此外，现有技术中的常规使用的交联剂均为小分子型交联剂（例如甲基三丁酮肟基硅烷、乙烯基三丁酮肟基硅烷或四丁酮肟基硅烷），这些小分子型交联剂在反应后会在硅酮胶中形成用于连接α，ω- 二羟基聚二甲基硅氧烷的交联节点，然而由于相邻的交联节点之间的距离较远，导致相邻的交联节点之间的相互作用较小，因此导致硅酮密封胶的力学性能难以继续提升。In addition, the cross-linking agents commonly used in the prior art are all small molecule cross-linking agents (such as methyltributylketoneoximinosilane, vinyltributylketoneoximesilane or tetrabutylketoneoximylsilane). After the reaction, the small molecule cross-linking agent will form cross-linking nodes in the silicone gel for connecting α,ω-dihydroxypolydimethylsiloxane. However, due to the long distance between adjacent cross-linking nodes, Far away, resulting in smaller interactions between adjacent cross-linked nodes, making it difficult to continue to improve the mechanical properties of the silicone sealant.
本发明中的交联剂其在结构中存在线性或者支化的增强链段，由于丙酮肟基或者戊酮肟基接枝于增强链段的侧基或者端基位置处，因此在本发明中的交联剂在脱除丙酮肟或者戊酮肟形成交联节点的过程中，邻近的交联节点之间则由于存在增强链段的牵引拉伸作用，使得相邻的交联节点之间的相互作用力有效提升，相当于提升了交联密度。并且，由于增强链段的存在，使得增强链段与α，ω- 二羟基聚二甲基硅氧烷的主链链段之间存在物理缠结，从而能够进一步提升硅酮密封胶的粘结性能以及力学性能。The cross-linking agent in the present invention has a linear or branched reinforcing segment in its structure. Since the acetone oxime group or the pentanone oxime group is grafted to the side group or terminal position of the reinforcing segment, in the present invention When the cross-linking agent removes acetone oxime or pentanone oxime to form cross-link nodes, due to the traction and stretching effect of the enhanced chain segments between adjacent cross-link nodes, the tension between adjacent cross-link nodes is The interaction force is effectively increased, which is equivalent to increasing the cross-linking density. Moreover, due to the existence of the reinforcing segment, there is a physical entanglement between the reinforcing segment and the main chain segment of α,ω-dihydroxypolydimethylsiloxane, which can further improve the bonding of the silicone sealant. performance and mechanical properties.
作为优选，按照重量份数计，其是由以下按重量份数配比的原料构成 ：Preferably, in parts by weight, it is composed of the following raw materials in a proportion by weight:
α，ω- 二羟基聚二甲基硅氧烷
100 份α,ω-Dihydroxypolydimethylsiloxane
100 copies
碳酸钙
50～150份Calcium carbonate
50 to 150 servings
气相白炭黑
5～30 份Vapor phase silica
5 to 30 servings
交联剂
4～20份Cross-linking agent
4 to 20 servings
硅烷偶联剂
0.5～2 份A silane coupling agent
0.5～2 servings
催化剂
0.2～0.5份。Catalyst
0.2 ~ 0.5 parts.
作为优选，所述交联剂制备方法如下：Preferably, the preparation method of the cross-linking agent is as follows:
（1）制备侧基或者端基可反应基团的线性或者支化的中间产物；(1) Prepare linear or branched intermediates with side or terminal reactive groups;
（2）将中间产物中的可反应基团与丙酮肟或者戊酮肟反应，从而将丙酮肟基或者戊酮肟基接枝到中间产物上，得到所述交联剂。(2) React the reactive group in the intermediate product with acetone oxime or pentanone oxime, thereby grafting the acetone oxime group or pentanone oxime group to the intermediate product to obtain the cross-linking agent.
本发明中的交联剂在制备过程中可以通过多种反应制备得到，以下作为对交联剂的制备方法的进一步描述。The cross-linking agent in the present invention can be prepared through various reactions during the preparation process. The following is a further description of the preparation method of the cross-linking agent.
其中，在中间产物的制备过程中可反应基团可以为硅烷氧基（-Si-OR）、硅氢基（-Si-H）、硅氯（-Si-Cl）、硅羟基（-Si-OH），以上可反应基团均可以与丙酮肟或者戊酮肟中的羟基进行反应，从而即可将丙酮肟基或者戊酮肟基接枝到中间产物上。Among them, the reactive groups during the preparation of the intermediate product can be silyloxy (-Si-OR), silylhydrogen (-Si-H), silicon chloride (-Si-Cl), silyl hydroxyl (-Si- OH), the above reactive groups can react with the hydroxyl group in acetone oxime or pentanone oxime, so that the acetone oxime group or pentanone oxime group can be grafted to the intermediate product.
作为优选，所述交联剂的增强链段中还掺杂有含磷元素[0017] 现有技术中的硅酮密封胶由于硅氧键的极性较低，因此导致其与光伏组件之间的粘结稳定性较差，导致在长久的日晒过程中光伏组件存在粘结性能下降，导致分解脱离的问题。因此，本优选技术方案中创造性的在交联剂中掺杂有含磷元素，因而能够有效提升硅酮密封胶的极性，相较于现有技术中无磷元素的硅酮密封胶，从而能够进一步提升硅酮密封胶的粘结性、力学性能以及耐老化性能。Preferably, the reinforcing chain segment of the cross-linking agent is also doped with a phosphorus-containing element [0017] Due to the low polarity of the silicon-oxygen bond in the silicone sealant in the prior art, there is a gap between the silicone sealant and the photovoltaic module. The bonding stability of the photovoltaic modules is poor, which leads to the degradation of the bonding performance of the photovoltaic modules during long-term sunlight exposure, leading to the problem of decomposition and detachment. Therefore, in this preferred technical solution, the cross-linking agent is creatively doped with phosphorus-containing elements, which can effectively improve the polarity of the silicone sealant. Compared with the silicone sealant without phosphorus elements in the prior art, It can further improve the adhesion, mechanical properties and aging resistance of silicone sealants.
作为优选，所述α，ω-二羟基聚二甲基硅氧烷的粘度在5~100Pa.S。Preferably, the viscosity of the α,ω-dihydroxypolydimethylsiloxane is between 5 and 100 Pa.S.
作为优选，所述气相白炭黑为经六甲基二硅氮烷处理的气相法白炭黑；Preferably, the gas phase silica is gas phase silica treated with hexamethyldisilazane;
其比表面积为 100～600m
2/g。
Its specific surface area is 100~600m 2 /g.
作为优选，所述硅烷偶联剂为
γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、3-巯丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷氨基低聚物中的一种或几种组合。Preferably, the silane coupling agent is
γ-[2,3-glycidoxy]propyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-amine Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane amino oligomer One or several combinations of things.
作为优选，所述催化剂为二丁基二醋酸锡、二丁基二月桂酸锡、螯合锡中的任意一种或多种的组合。Preferably, the catalyst is any one or a combination of dibutyltin diacetate, dibutyltin dilaurate, and chelated tin.
第二方面，本发明其次提供了一种用于制备所述低毒单组份光伏边框硅酮密封胶的方法，包括以下步骤，In a second aspect, the present invention provides a method for preparing the low-toxic single-component photovoltaic frame silicone sealant, which includes the following steps:
(1) 将α，ω- 二羟基聚二甲基硅氧烷、填料混合搅拌并脱水，冷却得基料
；(1) Mix α,ω-dihydroxypolydimethylsiloxane and filler, stir and dehydrate, and cool to obtain the base material
;
(2) 将交联剂、硅烷偶联剂、催化剂分别加入到上述基料中，搅拌均匀后得到太阳能光伏组件用单组分硅酮密封胶。(2) Add the cross-linking agent, silane coupling agent, and catalyst to the above base material respectively, and stir evenly to obtain a one-component silicone sealant for solar photovoltaic modules.
作为优选，所述步骤（1）中搅拌温度为120~170℃，搅拌过程中真空度≤-0.095MPa，脱水时间为120 ~ 240min；Preferably, the stirring temperature in step (1) is 120~170°C, the vacuum degree during the stirring process is ≤-0.095MPa, and the dehydration time is 120~240min;
所述步骤（2）中搅拌过程中采用动力行星搅拌机，搅拌过程中真空度≤-0.095MPa，转速为 600～1500rpm ，搅拌时间为100
~180min。In step (2), a powered planetary mixer is used during the mixing process. During the mixing process, the vacuum degree is ≤-0.095MPa, the rotation speed is 600~1500rpm, and the mixing time is 100
~180min.
因此，本发明具有以下有益效果：Therefore, the present invention has the following beneficial effects:
（1）本发明中的硅酮密封胶与空气中的潮气反应不会释放出有致癌物质的丁酮肟，在脱丁酮肟型RTV硅橡胶产品应用受到限制的前提下，上述交联剂制备的硅橡胶具有良好适用性；(1) The silicone sealant in the present invention will not release the carcinogen methylethylketoxime when reacting with moisture in the air. Under the premise that the application of debutylketoxime-type RTV silicone rubber products is limited, the above-mentioned cross-linking agent The prepared silicone rubber has good applicability;
（2）本发明在交联剂中包含有线性或者支化的增强链段，其能够有效提升硅酮密封胶中相邻的交联节点之间的相互作用力，提升了交联密度。并且，由于增强链段的存在，使得增强链段与α，ω- 二羟基聚二甲基硅氧烷的主链链段之间存在物理缠结，从而能够进一步提升硅酮密封胶的粘结性以及力学性能；(2) The present invention contains linear or branched reinforcing segments in the cross-linking agent, which can effectively increase the interaction force between adjacent cross-linking nodes in the silicone sealant and increase the cross-linking density. Moreover, due to the existence of the reinforcing segment, there is a physical entanglement between the reinforcing segment and the main chain segment of α,ω-dihydroxypolydimethylsiloxane, which can further improve the bonding of the silicone sealant. properties and mechanical properties;
（3）本优选技术方案中创造性的在交联剂中掺杂有含磷元素的结构单元，因而能够有效提升硅酮密封胶的极性，相较于现有技术中无磷元素的硅酮密封胶，从而能够进一步提升硅酮密封胶的粘结性、力学性能以及耐老化性能。(3) In this preferred technical solution, the cross-linking agent is creatively doped with structural units containing phosphorus elements, which can effectively improve the polarity of the silicone sealant. Compared with silicones without phosphorus elements in the prior art, Sealant, which can further improve the adhesion, mechanical properties and aging resistance of silicone sealant.
下面结合具体实施例对本发明做进一步描述。本领域普通技术人员在基于这些说明的情况下将能够实现本发明。此外，下述说明中涉及到的本发明的实施例通常仅是本发明一部分的实施例，而不是全部的实施例。因此，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。The present invention will be further described below with reference to specific embodiments. A person of ordinary skill in the art will be able to implement the present invention based on these descriptions. In addition, the embodiments of the present invention mentioned in the following description are generally only some embodiments of the present invention, rather than all the embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts should fall within the scope of protection of the present invention.
【交联剂的制备】[Preparation of cross-linking agent]
交联剂（A）：氮气保护下，将10g端含氢硅油（含氢值（wt %）为0.1%）以及10mg三（五氟苯）硼烷溶于50ml甲苯中，搅拌均匀后向其中滴加0.88g（12mmol）丙酮肟与10ml甲苯的混合液，常温下搅拌反应2h，直至没有气泡生成，减压除去甲苯以及未反应的丙酮肟，得到接枝有丙酮肟基团的交联剂（A）。Cross-linking agent (A): Under nitrogen protection, dissolve 10g of hydrogen-containing silicone oil (hydrogen content (wt %) is 0.1%) and 10mg of tris(pentafluorobenzene)borane in 50ml of toluene, stir evenly and add Add dropwise a mixture of 0.88g (12mmol) acetone oxime and 10 ml toluene, stir and react at room temperature for 2 hours until no bubbles are generated, remove toluene and unreacted acetone oxime under reduced pressure, and obtain a cross-linking agent grafted with acetone oxime groups. (A).
其反应示意式如下式（一）所示：The reaction schematic formula is as shown in the following formula (1):
式（一）Formula (1)
交联剂（B）：氮气保护下，将10g含氢硅油（含氢值（wt %）为1.5%，,25℃粘度为20-30 mm2/s）以及10mg三（五氟苯）硼烷溶于100ml甲苯中，搅拌均匀后向其中滴加12g（165mmol）丙酮肟与30ml甲苯的混合液，常温下搅拌反应5h，直至没有气泡生成，减压除去甲苯以及未反应的丙酮肟，得到接枝有丙酮肟基团的交联剂（B）。Cross-linking agent (B): Under nitrogen protection, mix 10g of hydrogen-containing silicone oil (hydrogen value (wt %) is 1.5%, viscosity at 25°C is 20-30 mm2/s) and 10mg tris(pentafluorobenzene)borane Dissolve in 100 ml of toluene, stir evenly and add dropwise a mixture of 12g (165 mmol) acetone oxime and 30 ml toluene. Stir and react at room temperature for 5 hours until no bubbles are generated. Remove toluene and unreacted acetone oxime under reduced pressure to obtain the next step. Cross-linking agent (B) with acetone oxime groups.
其反应示意式如下式（二）所示：The reaction schematic formula is shown in the following formula (2):
式（二）Formula (2)
交联剂（C）：氮气保护下，将10g含氢硅油（含氢值（wt %）为1.5%，,25℃粘度为20-30 mm2/s）以及10mg三（五氟苯）硼烷溶于100ml甲苯中，搅拌均匀后向其中滴加16.68g（165mmol）2-戊酮肟与30ml甲苯的混合液，常温下搅拌反应5h，直至没有气泡生成，减压除去甲苯以及未反应的2-戊酮肟，得到接枝有戊酮肟基团的交联剂（C）。Cross-linking agent (C): Under nitrogen protection, mix 10g of hydrogen-containing silicone oil (hydrogen value (wt %) is 1.5%, viscosity at 25°C is 20-30 mm2/s) and 10mg tris(pentafluorobenzene)borane Dissolve in 100 ml of toluene, stir evenly and add dropwise a mixture of 16.68 g (165 mmol) 2-pentanone oxime and 30 ml of toluene. Stir and react at room temperature for 5 hours until no bubbles are generated. Remove toluene and unreacted 2 under reduced pressure. -pentanone oxime to obtain a cross-linking agent (C) grafted with a pentanone oxime group.
其反应示意式如下式（三）所示：The reaction schematic formula is shown in the following formula (3):
式（三）Formula (3)
交联剂（D）：(1)在氮气保护下，将1.48g（10mmol）乙烯基三甲氧基硅烷、3g（32mmol）二甲基氯硅烷、100ml四氢呋喃以及2g三氯化铁，45℃下搅拌反应3小时，然后降低温度至室温，加入5份活性炭，搅拌30分钟后过滤，蒸除四氢呋喃，然后进行蒸馏得到中间产物(D-1)。Cross-linking agent (D): (1) Under nitrogen protection, mix 1.48g (10mmol) vinyltrimethoxysilane, 3g (32mmol) dimethylchlorosilane, 100ml tetrahydrofuran and 2g ferric chloride at 45°C. Stir the reaction for 3 hours, then lower the temperature to room temperature, add 5 parts of activated carbon, stir for 30 minutes, filter, evaporate tetrahydrofuran, and then distill to obtain the intermediate product (D-1).
[0032] (2)取三口烧瓶，在氮气保护下，加入步骤(1)中得到的中间产物(D-1)14g（50mmol）以及甲苯50ml，然后加入0.2g卡斯特催化剂，升温至100℃，搅拌反应5小时，得到中间产物(D-2)。(2) Get a three-necked flask, under nitrogen protection, add 14g (50mmol) of the intermediate product (D-1) obtained in step (1) and 50ml of toluene, then add 0.2g Caster catalyst, and heat to 100 ℃, stir the reaction for 5 hours, and obtain the intermediate product (D-2).
其反应示意式如下式（四）所示：The reaction schematic formula is shown in the following formula (4):
式（四）Formula (4)
（3）氮气保护下，将得到的中间产物(D-2)以及10mg三（五氟苯）硼烷溶于50ml甲苯中搅拌均匀后向其中滴加8g（110mmol）丙酮肟与30ml甲苯的混合液，常温下搅拌反应5h，直至没有气泡生成，减压除去甲苯以及未反应的丙酮肟，得到接枝有丙酮肟基团的交联剂（D）。(3) Under nitrogen protection, dissolve the obtained intermediate product (D-2) and 10 mg tris(pentafluorobenzene)borane in 50 ml toluene, stir evenly, and then add dropwise a mixture of 8 g (110 mmol) acetone oxime and 30 ml toluene. liquid, stir and react for 5 hours at room temperature until no bubbles are generated, remove toluene and unreacted acetone oxime under reduced pressure, and obtain a cross-linking agent (D) grafted with an acetone oxime group.
其反应示意式如下式（五）所示：The reaction schematic formula is shown in the following formula (5):
式（五）Formula (5)
交联剂（E）：Cross-linking agent (E):
（1）氮气保护下，14g（0.1mol）三羟甲基氧化磷以及30.3g（0.3mol）溶于500ml二氯甲烷中，然后在-10℃条件下，向其中滴加28.4g（0.3mol）二甲基氯硅烷与50ml二氯甲烷中的混合液，1小时内滴加完毕，然后升温至室温继续反应3h，过滤除去生成的盐酸三乙胺盐，有机相经过水洗后，蒸发去除二氯甲烷，得到中间产物（E-1）。(1) Under nitrogen protection, 14g (0.1mol) trihydroxymethylphosphorus oxide and 30.3g (0.3mol) were dissolved in 500ml methylene chloride, and then 28.4g (0.3mol) was added dropwise at -10°C. ) The mixture of dimethylsilyl chloride and 50 ml dichloromethane was added dropwise within 1 hour, then the temperature was raised to room temperature and the reaction continued for 3 hours. The generated triethylamine hydrochloride salt was removed by filtration. After the organic phase was washed with water, the dimethyl chloride was evaporated to remove Methyl chloride to obtain intermediate product (E-1).
其反应示意式如下式（六）所示：The reaction schematic formula is shown in the following formula (6):
式（六）Formula (6)
（2）氮气保护下，将得3.98g（10mmol）到的中间产物（E-1）以及10mg三（五氟苯）硼烷溶于50ml甲苯中搅拌均匀后向其中滴加2.56g（30mmol）丙酮肟与30ml甲苯的混合液，常温下搅拌反应5h，直至没有气泡生成，减压除去甲苯以及未反应的丙酮肟，得到接枝有丙酮肟基团的交联剂（E）。(2) Under nitrogen protection, dissolve 3.98g (10mmol) of the obtained intermediate product (E-1) and 10mg tris(pentafluorobenzene)borane in 50ml of toluene, stir evenly, and then add 2.56g (30mmol) dropwise thereto. A mixture of acetone oxime and 30 ml of toluene was stirred and reacted at room temperature for 5 hours until no bubbles were generated. Toluene and unreacted acetone oxime were removed under reduced pressure to obtain a cross-linking agent (E) grafted with an acetone oxime group.
其反应示意式如下式（七）所示：The reaction schematic formula is shown in the following formula (7):
式（七）Formula (7)
实施例1Example 1
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of gas-phase silica with a specific surface area of 200m2/g treated with hexamethyldisilazane, were added to the mixer and heated to a temperature of 150 ℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（A）8份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm 搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 8 parts of cross-linking agent (A), 1 part of γ-[2,3-epoxypropoxy]propyltrimethoxysilane, and 0.1 part of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1Pa. Add 3 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 800rpm for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例2Example 2
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（B）8份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm 搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 8 parts of cross-linking agent (B), 1 part of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.1 part of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1Pa. Add 3 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 800rpm for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例3Example 3
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（C）8份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm 搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 8 parts of cross-linking agent (C), 1 part of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.1 part of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1Pa. Add 3 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 800rpm for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例4Example 4
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（D）8份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm 搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 8 parts of cross-linking agent (D), 1 part of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.1 part of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1Pa. Add 3 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 800rpm for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例5Example 5
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（E）8份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm 搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 8 parts of cross-linking agent (E), 1 part of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.1 part of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1Pa. Add 3 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 800rpm for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例6Example 6
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙50份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑30份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 50 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 30 parts of vapor phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, were added to the mixer and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（A）17份，交联剂（D）3份,γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 0.5份, 二丁基二月桂酸锡0.2份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 17 parts of cross-linking agent (A), 3 parts of cross-linking agent (D), 0.5 parts of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate. , 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C, added to a power vacuum planetary mixer equipped with the above base material, vacuum degree -0.095Mpa, rotation speed 800rpm
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例7Example 7
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙150份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑5份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 150 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 5 parts of gas-phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（D）4份, N-(2-氨乙基)-3-氨丙基三甲氧基硅烷氨基低聚物2份, 二丁基二月桂酸锡0.5份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。Mix 4 parts of cross-linking agent (D), 2 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane amino oligomer, and 0.5 parts of dibutyltin dilaurate at room temperature at 25°C. Add 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S into a power vacuum planetary mixer equipped with the above base material. The vacuum degree is -0.095Mpa and the rotation speed is 800rpm.
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例8Example 8
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙100份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑20份，加入搅拌机中，于温度120℃、真空度为-0.095MPa，脱水共混捏合240分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 100 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 20 parts of vapor phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 120℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 240 minutes, cool to obtain base gum;
室温将交联剂（B）3份, 交联剂（D）2份, N-(2-氨乙基)-3-氨丙基三甲氧基硅烷2份, 二丁基二月桂酸锡0.5份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 3 parts of cross-linking agent (B), 2 parts of cross-linking agent (D), 2 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 0.5 dibutyltin dilaurate. 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C are added to a power vacuum planetary mixer equipped with the above base material. The vacuum degree is -0.095Mpa and the rotation speed is 800rpm.
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例9Example 9
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙100份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑20份，加入搅拌机中，于温度120℃、真空度为-0.095MPa，脱水共混捏合240分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 100 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 20 parts of vapor phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 120℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 240 minutes, cool to obtain base gum;
室温将交联剂（B）3份, 交联剂（E）2份, N-(2-氨乙基)-3-氨丙基三甲氧基硅烷2份, 二丁基二月桂酸锡0.5份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 3 parts of cross-linking agent (B), 2 parts of cross-linking agent (E), 2 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 0.5 dibutyltin dilaurate. 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C are added to a power vacuum planetary mixer equipped with the above base material. The vacuum degree is -0.095Mpa and the rotation speed is 800rpm.
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例10Example 10
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷94份，粘度为80Pa.S的α，ω-二羟基聚二甲基硅氧烷6份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙50份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑30份，加入搅拌机中，于温度 150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 94 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 6 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 80Pa.S, and the water content. 50 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 30 parts of vapor phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, were added to the mixer and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将交联剂（E）5份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 0.8份, 二丁基二月桂酸锡0.3份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷5份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速1500rpm 搅拌100min制得太阳能光伏组件用单组分硅酮密封胶。Mix 5 parts of cross-linking agent (E), 0.8 parts of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.3 parts of dibutyltin dilaurate at room temperature. The viscosity at 25°C is 0.1 Pa. Add 5 parts of S polydimethylsiloxane into a power vacuum planetary mixer equipped with the above base material, stir at a vacuum degree of -0.095Mpa and a rotation speed of 1500rpm for 100 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例11Example 11
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷100份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑8份，加入搅拌机中，于温度 170℃、真空度为-0.095MPa，脱水共混捏合120分钟，冷却得基胶；
25℃, mix 100 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 8 parts of gas-phase silica with a specific surface area of 200 m 2 /g treated with hexamethyldisilazane, were added to the mixer and brought to a temperature of 170℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 120 minutes, cool to obtain base gum;
室温将交联剂（B）3份、交联剂（D）1份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 0.8份, 二丁基二月桂酸锡0.3份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷5份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速600rpm 搅拌180min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 3 parts of cross-linking agent (B), 1 part of cross-linking agent (D), 0.8 parts of γ-[2,3-glycidoxy]propyltrimethoxysilane, and 0.3 parts of dibutyltin dilaurate. , 5 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C, was added to a power vacuum planetary mixer equipped with the above base material, the vacuum degree was -0.095Mpa, the rotation speed was 600rpm, and stirred for 180 minutes to obtain a monomer for solar photovoltaic modules. Component silicone sealant.
对比例1Comparative example 1
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将甲基三丙酮肟基硅烷6份、乙烯基三丙酮肟基硅烷2份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 6 parts of methyltriacetoneoximesilane, 2 parts of vinyltriacetoneoximesilane, 1 part of γ-[2,3-glycidoxy]propyltrimethoxysilane, and dibutyltin dilaurate 0.1 part, 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C, added to the power vacuum planetary mixer equipped with the above base material, vacuum degree -0.095Mpa, rotation speed 800rpm
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
对比例2Comparative example 2
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um, less than 0.1%, and 15 parts of vapor phase silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, added to the mixer, and brought to a temperature of 150℃, vacuum degree is -0.095MPa, dehydrate, blend and knead for 180 minutes, cool to obtain base gum;
室温将甲基三戊酮肟基硅烷5份、乙烯基三戊酮肟基硅烷3份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 5 parts of methyl tripentyl ketone oxime silane, 3 parts of vinyl tripentyl ketone oxime silane, 1 part of γ-[2,3-glycidoxy]propyl trimethoxysilane, and dibutyl dilauryl silane. 0.1 part of tin acid, 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C, added to a power vacuum planetary mixer equipped with the above base material, vacuum degree -0.095Mpa, rotation speed 800rpm
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
对比例3Comparative example 3
一种低毒单组份光伏边框硅酮密封胶，具体按照以下方案步骤制备：A low-toxic one-component silicone sealant for photovoltaic frames, specifically prepared according to the following steps:
25℃,将粘度为20Pa.S的α，ω-二羟基聚二甲基硅氧烷90份，粘度为50Pa.S的α，ω-二羟基聚二甲基硅氧烷10份,含水量低于0.1%、粒径在0.1~5um的补强碳酸钙60份，六甲基二硅氮烷处理果的比表面积为200m
2/g的气相白炭黑15份以及三羟甲基氧化磷5份，加入搅拌机中，于温度150℃、真空度为-0.095MPa，脱水共混捏合180分钟，冷却得基胶；
At 25°C, mix 90 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 20 Pa.S, 10 parts of α,ω-dihydroxypolydimethylsiloxane with a viscosity of 50Pa.S, and the water content. 60 parts of reinforcing calcium carbonate with a particle size of 0.1~5um below 0.1%, 15 parts of fumed silica with a specific surface area of 200m 2 /g treated with hexamethyldisilazane, and trimethylol phosphorus oxide 5 parts, added to the mixer, at a temperature of 150°C and a vacuum of -0.095MPa, dehydrated, blended and kneaded for 180 minutes, and cooled to obtain a base gum;
室温将甲基三戊酮肟基硅烷5份、乙烯基三戊酮肟基硅烷3份，γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷 1份, 二丁基二月桂酸锡0.1份，25℃时粘度为0.1Pa.S聚二甲基硅氧烷3份，加入装有上述基料的动力真空行星搅拌机内，真空度-0.095Mpa、转速800rpm
搅拌120min制得太阳能光伏组件用单组分硅酮密封胶。At room temperature, mix 5 parts of methyl tripentyl ketone oxime silane, 3 parts of vinyl tripentyl ketone oxime silane, 1 part of γ-[2,3-glycidoxy]propyl trimethoxysilane, and dibutyl dilauryl silane. 0.1 part of tin acid, 3 parts of polydimethylsiloxane with a viscosity of 0.1Pa.S at 25°C, added to a power vacuum planetary mixer equipped with the above base material, vacuum degree -0.095Mpa, rotation speed 800rpm
Stir for 120 minutes to prepare a one-component silicone sealant for solar photovoltaic modules.
实施例1~11以及对比例1~3中的配方汇总如下表1~2所示。The formulas in Examples 1 to 11 and Comparative Examples 1 to 3 are summarized in Tables 1 to 2 below.
表一Table I
表二Table II
【性能测试】。【Performance Testing】.
挤出性能：反应密封胶挤出的施工性能，以密封胶在单位时间内挤出的体积（容量）表示。Extrusion performance: reflects the construction performance of sealant extrusion, expressed by the volume (capacity) of sealant extruded per unit time.
表干时间：反应密封胶表面失去黏性的时间，按照GB/T 13477.5-2002规定B法进行。Tack drying time: The time for the surface of the reaction sealant to lose its viscosity. It is carried out in accordance with Method B specified in GB/T 13477.5-2002.
拉伸强度：按照ISO 37方法进行。Tensile Strength: According to ISO 37 method.
断裂伸长率：按照ISO 37方法进行。Elongation at break: according to ISO 37 method.
剪切强度：按照ASTMD 3164方法进行。Shear Strength: According to ASTMD 3164 method.
【测试结果】【Test Results】
实施例1~11以及对比例1~3中的性能测试结果如下表3所示。The performance test results in Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Table 3 below.
表3table 3
从上表数据中可知，通过本发明中制备得到的酮密封胶（实施例1~11），其挤出性能、表干性能以及固化效时间与采用小分子交联剂的对（对比例1~2）性能较为接近。同时其具有更好的力学性能，表明由于交联剂中增强链段的加入能够有效提升整体的力学性能以及粘结性能。It can be seen from the data in the above table that the extrusion performance, surface drying performance and curing effect time of the ketone sealant prepared in the present invention (Examples 1 to 11) are comparable to those using a small molecule cross-linking agent (Comparative Example 1 ~2) The performance is relatively close. At the same time, it has better mechanical properties, indicating that the addition of reinforcing segments in the cross-linking agent can effectively improve the overall mechanical properties and bonding properties.
此外，本发明在个别制备得到的酮密封胶的交联剂中引入含有含磷元素的结构单元（例如实施例5、实施例9以及实施例10），本优选技术方案中创造性的在交联剂中掺杂有含磷元素的结构单元，因而能够有效提升硅酮密封胶的极性，相较于现有技术中无磷元素的硅酮密封胶，从而能够进一步提升硅酮密封胶的密封性、力学性能以及耐老化性能。In addition, the present invention introduces structural units containing phosphorus elements into the cross-linking agent of the individually prepared ketone sealant (such as Example 5, Example 9 and Example 10). In this preferred technical solution, the creative step is in the cross-linking The agent is doped with structural units containing phosphorus elements, which can effectively improve the polarity of the silicone sealant. Compared with silicone sealants without phosphorus elements in the prior art, it can further improve the sealing performance of the silicone sealant. properties, mechanical properties and aging resistance.
而相较于单独额外添加三羟甲基氧化磷的对比例3，其虽然相较于对比例2而言，性能略微有所提升，但是与直接在交联剂中引入含有含磷元素的结构单元的实施例相比较（例如实施例5、实施例9以及实施例10），其性能则远远逊于这些实施例，表明单独额外添加三羟甲基氧化磷后其所携带的羟基也会对交联剂中的酮肟基进行反应，从而对α，ω-二羟基聚二甲基硅氧烷起到与交联剂中的酮肟基之间的反应起到竞争，从而降低了其整体性能。Compared with Comparative Example 3 in which trihydroxymethylphosphorus oxide is added separately, although its performance is slightly improved compared to Comparative Example 2, it is different from directly introducing a structure containing phosphorus elements into the cross-linking agent. Compared with the examples of the unit (such as Example 5, Example 9 and Example 10), its performance is far inferior to these examples, indicating that the hydroxyl groups carried by trihydroxymethylphosphorus oxide alone will also be React with the ketoxime group in the cross-linking agent, thereby competing with the reaction between α,ω-dihydroxypolydimethylsiloxane and the ketoxime group in the cross-linking agent, thus reducing its Overall performance.
Claims (10)
- 一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic one-component silicone sealant for photovoltaic frames, characterized by:其是由包括以下组分的原料构成：α，ω- 二羟基聚二甲基硅氧烷、填料、交联剂、硅烷偶联剂以及催化剂；其中：It is composed of raw materials including the following components: α,ω-dihydroxypolydimethylsiloxane, filler, cross-linking agent, silane coupling agent and catalyst; wherein:所述交联剂中包含有线性或者支化的增强链段；The cross-linking agent contains linear or branched reinforcing segments;所述增强链段的侧基或者端基包含有丙酮肟基或者戊酮肟基。The side group or terminal group of the reinforcing segment includes an acetone oxime group or a pentanone oxime group.
- 根据权利要求1所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic single-component silicone sealant for photovoltaic frames according to claim 1, characterized in that:按照重量份数计，其是由包括以下按重量份数配比的原料构成 ：In parts by weight, it consists of the following raw materials in proportion by weight:α，ω- 二羟基聚二甲基硅氧烷 100 份α,ω-Dihydroxypolydimethylsiloxane 100 copies碳酸钙 50～150份Calcium carbonate 50～150 servings气相白炭黑 5～30 份Vapor phase silica 5～30 servings交联剂 4～20份Cross-linking agent 4 to 20 parts硅烷偶联剂 0.5～2 份Silane coupling agent 0.5～2 parts催化剂 0.2～0.5份。Catalysts 0.2～0.5 parts.
- 根据权利要求1所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic single-component silicone sealant for photovoltaic frames according to claim 1, characterized in that:所述交联剂制备方法如下：The preparation method of the cross-linking agent is as follows:（1）制备侧基或者端基可反应基团的线性或者支化的中间产物；(1) Prepare linear or branched intermediates with side or terminal reactive groups;（2）将中间产物中的可反应基团与丙酮肟或者戊酮肟反应，从而将丙酮肟基或者戊酮肟基接枝到中间产物上，得到所述交联剂。(2) React the reactive group in the intermediate product with acetone oxime or pentanone oxime, thereby grafting the acetone oxime group or pentanone oxime group to the intermediate product to obtain the cross-linking agent.
- 根据权利要求1或3所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic single-component photovoltaic frame silicone sealant according to claim 1 or 3, characterized in that:所述交联剂的增强链段中还掺杂有含磷元素。The reinforcing chain segment of the cross-linking agent is also doped with phosphorus-containing elements.
- 根据权利要求1或2所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic one-component photovoltaic frame silicone sealant according to claim 1 or 2, characterized in that:所述α，ω-二羟基聚二甲基硅氧烷的粘度在5~100Pa.S。The viscosity of the α,ω-dihydroxypolydimethylsiloxane ranges from 5 to 100 Pa.S.
- 根据权利要求2所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic single-component silicone sealant for photovoltaic frames according to claim 2, characterized in that:所述气相白炭黑为经六甲基二硅氮烷处理的气相法白炭黑；The vapor phase silica is a vapor phase silica treated with hexamethyldisilazane;其比表面积为 100～600m 2/g。 Its specific surface area is 100~600m 2 /g.
- 据权利要求1或2所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic single-component silicone sealant for photovoltaic frames according to claim 1 or 2, characterized in that:所述硅烷偶联剂为 γ-〔2，3- 环氧丙氧〕丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、3-巯丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷氨基低聚物中的一种或几种组合。The silane coupling agent is γ-[2,3-glycidoxy]propyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethyl Oxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl One or several combinations of trimethoxysilyl amino oligomers.
- 根据权利要求1或2所述的一种低毒单组份光伏边框硅酮密封胶，其特征在于，A low-toxic one-component photovoltaic frame silicone sealant according to claim 1 or 2, characterized in that:所述催化剂为二丁基二醋酸锡、二丁基二月桂酸锡、螯合锡中的任意一种或多种的组合。The catalyst is any one or a combination of dibutyltin diacetate, dibutyltin dilaurate, and chelated tin.
- 一种用于制备如权利要求1~8中任意一项所述低毒单组份光伏边框硅酮密封胶的方法，其特征在于，A method for preparing low-toxicity single-component photovoltaic frame silicone sealant as described in any one of claims 1 to 8, characterized by:包括以下步骤，Includes the following steps,(1) 将α，ω- 二羟基聚二甲基硅氧烷、填料混合搅拌并脱水，冷却得基料 ；(1) Mix α,ω-dihydroxypolydimethylsiloxane and filler, stir and dehydrate, and cool to obtain the base material ;(2) 将交联剂、硅烷偶联剂、催化剂分别加入到上述基料中，搅拌均匀后得到太阳能光伏组件用单组分硅酮密封胶。(2) Add the cross-linking agent, silane coupling agent, and catalyst to the above base material respectively, and stir evenly to obtain a one-component silicone sealant for solar photovoltaic modules.
- 根据权利要求9所述的方法，其特征在于，The method according to claim 9, characterized in that:所述步骤（1）中搅拌温度为120~170℃，搅拌过程中真空度≤-0.095MPa，脱水时间为120 ~ 240min；In the step (1), the stirring temperature is 120~170°C, the vacuum degree during the stirring process is ≤-0.095MPa, and the dehydration time is 120~240min;所述步骤（2）中搅拌过程中采用动力行星搅拌机，搅拌过程中真空度≤-0.095MPa，转速为 600～1500rpm ，搅拌时间为100 ~180min。In step (2), a powered planetary mixer is used during the mixing process. The vacuum degree during the mixing process is ≤-0.095MPa, and the rotation speed is 600~1500rpm. , the stirring time is 100 ~180min.
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