CN114773379A - Modified siloxane, heat-resistant silicone structural sealant and preparation method thereof - Google Patents
Modified siloxane, heat-resistant silicone structural sealant and preparation method thereof Download PDFInfo
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- CN114773379A CN114773379A CN202210505682.6A CN202210505682A CN114773379A CN 114773379 A CN114773379 A CN 114773379A CN 202210505682 A CN202210505682 A CN 202210505682A CN 114773379 A CN114773379 A CN 114773379A
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 45
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000565 sealant Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 22
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- 229920002545 silicone oil Polymers 0.000 claims description 20
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000006229 carbon black Substances 0.000 claims description 17
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- -1 polydimethylsiloxanes Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- 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 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004590 silicone sealant Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- PXGZUMCOTGAVEC-UHFFFAOYSA-N 3-[dimethoxy(penta-1,4-dien-3-yloxy)silyl]propane-1,1,1-triamine Chemical compound C(=C)C(O[Si](OC)(OC)CCC(N)(N)N)C=C PXGZUMCOTGAVEC-UHFFFAOYSA-N 0.000 claims description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 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 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 4
- MGOBEGBHSBJTJR-UHFFFAOYSA-N ethyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](CC)C1=CC=CC=C1 MGOBEGBHSBJTJR-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229920006389 polyphenyl polymer Polymers 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 32
- 238000012360 testing method Methods 0.000 description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229940008099 dimethicone Drugs 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 4
- 239000013464 silicone adhesive Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- 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
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified siloxane and heat-resistant silicone structural sealant and a preparation method thereof. The modified siloxane has the following structure. The invention modifies the vinyl trimethoxy silane by the ethyl diphenyl silane, namely the ethyl diphenyl silane and the vinyl trimethoxy silane are used as raw materials, and the modified siloxane with the side groups of the polyphenyl rings is synthesized by hydrosilylation reaction under the action of a catalyst. And then the modified siloxane with the side groups of the multiple benzene rings is used as a coupling agent to prepare the sealant with the silicone structure, and because a heat-resistant large-volume chain segment is introduced into the main chain of the modified siloxane during crosslinking and curing, the thermal stability of the sealant with the silicone structure is greatly improved.
Description
Technical Field
The invention relates to the field of sealants, in particular to a modified siloxane and heat-resistant silicone structural sealant and a preparation method thereof.
Background
The application and development of the silicone sealant in China have been in history for decades, the whole-mounted aluminum doors and windows and building curtain walls in China are increased year by year at present, the introduction and application of a large amount of silicone structural adhesive are promoted, and the excellent application performance of the silicone structural adhesive is gradually recognized and accepted by the market. Meanwhile, a great number of problems are accumulated in the long-term rapid and extensive development, the problems of low efficiency, quality and the like are increasingly highlighted along with the lapse of time, and therefore, scientific research personnel always strive to prepare a structural adhesive with excellent performance.
The condensed type bi-component room temperature vulcanizing (RTV-2) silicone structural adhesive is an elastomer prepared by mixing a base material component A prepared from hydroxyl-terminated polydimethylsiloxane serving as a base adhesive, a filler and an additive, and a vulcanizing system component B prepared from a cross-linking agent, a coupling agent, a catalyst and the additive according to a certain proportion when in use. Because the crosslinking curing reaction can be carried out under the room temperature condition, the use is very convenient, and the crosslinking curing agent is widely applied to the fields of aerospace, electric and electronic, automobiles, machinery, buildings and the like. However, the service life of the structural silicone adhesive is shortened under severe environment, particularly under high temperature conditions, the structural silicone adhesive is aged according to two modes of methyl oxidation and main chain degradation, the mechanical property of the structural silicone adhesive is rapidly reduced, and the potential safety hazard of the structural silicone adhesive in use is increased.
Silazane was added into raw silicon rubber in the literature (polymer science, 2002 (05): 623-. In patent CN106833505B, α, ω -dihydroxy polysiloxane, a cross-linking agent, a reinforcing filler, a high temperature resistant filler (metal oxide), an organotin catalyst, and a coupling agent are used as raw materials to prepare a high temperature resistant single component room temperature vulcanized silicone sealant, which is mainly characterized in that the high temperature resistant metal oxide filler is used to improve the high temperature performance of the sealant, but the metal oxide has poor dispersibility in a sealing colloid system and is expensive.
Disclosure of Invention
Based on the preparation method, the modified siloxane with the multi-benzene-ring side group is prepared, and the heat resistance of the modified siloxane can be greatly improved when the modified siloxane is used for preparing the silicone structural adhesive.
Specifically, the present invention includes the following technical solutions.
A modified siloxane having the structure:
a modified siloxane consisting of2H5Ph2SiH vinyl trimethoxy silane is subjected to hydrosilylation reaction under the action of a catalyst to obtain,
said C is2H5Ph2The SiH has the following structural formula:
in some of these embodiments, the catalyst is a Pt catalyst.
In some of these embodiments, C2H5Ph2The reaction molar ratio of SiH to vinyltrimethoxysilane is 3-5: 1.
a preparation method of the modified siloxane comprises the following steps:
under the protection of nitrogen or inert gas, the vinyltrimethoxysilane and C2H5Ph2SiH reacts in the presence of the catalyst to obtain the modified siloxane;
the reaction temperature is 90-110 ℃.
In some of these embodiments, the reaction time is from 8h to 12 h.
In some of the examples, the reaction temperature is 95 ℃ to 105 ℃ and the reaction time is 9h to 11 h.
The invention also provides a silicone structural sealant which has good heat resistance. The technical scheme is as follows.
The coupling agent of the silicone structural sealant contains the modified siloxane.
In some of these embodiments, the silicone structural sealant comprises an A component and a B component,
the component A is prepared from the following raw materials in parts by weight:
100 parts of organopolysiloxane polymer
60-150 parts of filler
5-25 parts of a plasticizer;
the component B is prepared from the following raw materials in parts by weight:
100 parts of dimethyl silicone oil
50-150 parts of carbon black
15-60 parts of cross-linking agent
15-60 parts of coupling agent
0.1-1.5 parts of catalyst.
In some embodiments, the component A is prepared from the following raw materials in parts by weight:
100 parts of organopolysiloxane polymer
90-110 parts of filler
8-12 parts of a plasticizer;
the component B is prepared from the following raw materials in parts by weight:
100 parts of dimethyl silicone oil
90-110 parts of carbon black
45-55 parts of cross-linking agent
45-55 parts of coupling agent
0.8-1.2 parts of catalyst.
In some of these embodiments, the mixing volume ratio of the A component and the B component is 8-14:1 when used.
In some of these embodiments, the coupling agent is a modified siloxane as described above.
In some of these embodiments, the coupling agent consists of a first coupling agent and a second coupling agent, the first coupling agent being the modified siloxane described above; the second coupling agent is selected from gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, epoxycyclohexylmethyldimethoxysilane, epoxycyclohexylmethyldiethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidylmethyldimethoxysilane, gamma-glycidylmethyldiethoxysilane, gamma-glycidylmethoxysilane, gamma-glycidyloxypropyltriethoxysilane, gamma-dimethoxysilane, gamma-2-glycidylmethoxysilane, gamma-ethylenecarbonate, and a-ethylenecarbonate, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, epoxypropyltrimethoxysilane and divinyltriaminopropyltrimethoxysilane.
In some of these embodiments, the mass ratio of the first coupling agent to the second coupling agent is 1: 0-4.
In some of these embodiments, the mass ratio of the first coupling agent to the second coupling agent is 1: 0.2-1.5.
In some of these embodiments, the mass ratio of the first coupling agent to the second coupling agent is 1: 0.6-0.8.
In some of these embodiments, the coupling agent is formed from a mixture of, by mass, 1: 0.65-0.7 of the modified siloxane and gamma-glycidoxypropyltrimethoxysilane.
In some of these embodiments, the organopolysiloxane polymer is selected from at least one of hydroxyl terminated polydimethylsiloxanes, alkoxy terminated polydimethylsiloxanes, alkyl terminated polydimethylsiloxanes.
In some of these embodiments, the organopolysiloxane polymer has a viscosity at 25 ℃ of 10000 to 50000 mPas.
In some of these embodiments, the organopolysiloxane polymer has a viscosity at 25 ℃ of from 15000 mPas to 25000 mPas.
In some of these embodiments, the filler is nano-activated calcium carbonate.
In some embodiments, the nano active calcium carbonate has a particle size of 20 to 200 nm.
In some embodiments, the nano active calcium carbonate has a particle size of 40-80 nm.
In some embodiments, the plasticizer is selected from at least one of dimethicone, methylphenyl silicone oil, and hydroxy silicone oil.
In some of these embodiments, the plasticizer is a dimethicone having a viscosity of from 300 to 500mPa · s at 25 ℃.
In some of these embodiments, the viscosity of the dimethicone in the B component is from 5000mPa · s to 20000mPa · s at 25 ℃.
In some of these embodiments, the dimethicone of the B component has a viscosity of 8000 to 12000 mPa.s at 25 ℃.
In some of these embodiments, the cross-linking agent is selected from at least one of ethyl orthosilicate, propyl orthosilicate, ethyl polysilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, polymethyltriethoxysilane oligomer, phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.
In some of these embodiments, the catalyst is selected from at least one of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, isopropyl titanate, and n-butyl titanate.
The invention also provides a preparation method of the silicone structural sealant, which comprises the following technical scheme.
The preparation method of the silicone structural sealant comprises the following steps:
preparation of the component A: mixing the organopolysiloxane polymer, the filler and the plasticizer at the temperature of 60-120 ℃ for 10-200 min to obtain the composite material;
preparation of the component B: and (2) mixing the dimethyl silicone oil and the carbon black for 10-60 min at the temperature of 80-120 ℃, adding the cross-linking agent, the coupling agent and the catalyst, and continuously stirring for 10-100 min under the protection of nitrogen or inert gas to obtain the nano-silica/carbon black composite material.
In some embodiments, the method for preparing the silicone structural sealant comprises the following steps:
preparation of component A: mixing the organopolysiloxane polymer, the filler and the plasticizer at the temperature of 80-100 ℃ for 40-120 min to obtain the composite material;
preparation of the component B: and (2) mixing the dimethyl silicone oil and the carbon black for 20-40 min at the temperature of 90-110 ℃, cooling, adding the cross-linking agent, the coupling agent and the catalyst, and continuously stirring for 10-20 min under the protection of nitrogen or inert gas to obtain the nano-silica/carbon black composite material.
The invention modifies the vinyl trimethoxy silane through the ethyl diphenyl silane, namely, the ethyl diphenyl silane and the vinyl trimethoxy silane are used as raw materials, and the modified siloxane with the side groups of multiple benzene rings is synthesized through hydrosilylation under the action of a catalyst. And then the modified siloxane with the side groups of the benzene rings is used as a coupling agent to prepare the silicone structural sealant, and the heat stability of the obtained silicone structural sealant is greatly improved because a heat-resistant large-volume chain segment is introduced into the main chain of the modified siloxane during crosslinking and curing. And by controlling the addition amount of the modified siloxane with the multi-benzene ring side group in the coupling agent, the silicone structural sealant with excellent mechanical property and heat resistance can be obtained.
The synthetic process of the invention is simple, and the obtained silicone structural sealant can meet various requirements of special buildings, automobiles, electronic appliances and the like.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprises" and "comprising," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or apparatus that comprises a list of steps is not limited to only those steps or modules recited, but may alternatively include other steps not recited, or may alternatively include other steps inherent to such process, method, article, or apparatus.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
All viscosities stated herein are at 25 ℃.
The following are specific examples.
In the following examples, modified siloxanes with pendant polycyclic rings were prepared as follows:
in a three-mouth bottle drying system provided with a stirrer, a nitrogen inlet pipe and a reflux condenser pipe, 0.1mol of vinyltrimethoxysilane and 0.4mol of C are sequentially added under the protection of nitrogen2H5Ph2SiH, mass fraction 25X 10－6The Pt catalyst is slowly heated to 100 ℃ under the condition of mechanical stirring, stirred for 10 hours at constant temperature, then subjected to reduced pressure distillation to remove small molecules, and subjected to column chromatography to obtain the purified modified siloxane with the side groups of the polyphenyl rings, wherein the yield is 80%. The infrared spectrum of the obtained compound was measured at a wavelength of 950cm-1Characteristic peaks of Si-O were observed at the left and right sides, and the wavelength was 3100cm-1The characteristic peak of C-H stretching vibration is observed on the left and right, the same asAt a wavelength of 2180--1The range does not show a characteristic peak of an Si-H bond, and the wavelength is 1690-1500 cm-1The range also has no characteristic peak of C ═ C, which indicates C2H5Ph2Si-H in SiH and C ═ C in vinyltrimethoxysilane are subjected to addition reaction, and the target product modified siloxane after addition is successfully obtained.
The synthetic route is as follows:
example 1:
the preparation method of the heat-resistant silicone structural sealant provided by the embodiment is as follows:
the component A comprises the following components in parts by weight:
100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethyl silicone oil with the viscosity of 400 mPas are added into a kneader to be stirred and dispersed, after 5min, 100 parts of nano active calcium carbonate with the particle size of 60nm is added into the mixture in the stirring process to ensure that the glue completely covers the powder to form a self-leveling base material, the reaction temperature is controlled at 90 ℃, and the mixture is stirred and mixed for 1h to obtain a base material A (namely a component A), and the base material A is ground for later use.
The component B (in parts by weight) is as follows:
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min after the temperature is stabilized to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 50 parts of modified siloxane with a multi-benzene ring side group and 1 part of dibutyl tin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a planetary mixer according to the mixing volume ratio of 10:1, and then preparing an H-shaped test piece for detecting the tensile cohesiveness of the test sample.
Example 2:
the preparation method of the heat-resistant silicone structural sealant provided in this example is as follows:
the component A comprises the following components in parts by weight:
taking 100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethicone with the viscosity of 400 mPas, adding the mixture into a kneader, stirring and dispersing, adding 100 parts of nano active calcium carbonate with the particle size of 60nm into the mixture in the stirring process after 5min so that the glue completely covers the powder to form a self-leveling base material, controlling the reaction temperature to be 90 ℃, stirring and mixing for 1h to obtain a base material A (namely a component A), and grinding for later use.
The component B (parts by weight):
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 10 parts of gamma-glycidoxypropyltrimethoxysilane, 40 parts of modified siloxane with a multi-benzene ring side group and 1 part of dibutyl tin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a planetary mixer according to the mixing volume ratio of 10:1, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
Example 3:
the preparation method of the heat-resistant silicone structural sealant provided in this example is as follows:
the component A comprises the following components in parts by weight:
taking 100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethicone with the viscosity of 400 mPas, adding the mixture into a kneader, stirring and dispersing, adding 100 parts of nano active calcium carbonate with the particle size of 60nm into the mixture in the stirring process after 5min so that the glue completely covers the powder to form a self-leveling base material, controlling the reaction temperature to be 90 ℃, stirring and mixing for 1h to obtain a base material A (namely a component A), and grinding for later use.
The component B (in parts by weight) is as follows:
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min after the temperature is stabilized to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 20 parts of gamma-glycidyl ether oxypropyltrimethoxysilane, 30 parts of modified siloxane with a polycyclic side group and 1 part of dibutyltin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a mixing volume ratio of 10:1 in a planetary mixer, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
Example 4:
the preparation method of the heat-resistant silicone structural sealant provided in this example is as follows:
the component A comprises the following components in parts by weight:
taking 100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethicone with the viscosity of 400 mPas, adding the mixture into a kneader, stirring and dispersing, adding 100 parts of nano active calcium carbonate with the particle size of 60nm into the mixture in the stirring process after 5min so that the glue completely covers the powder to form a self-leveling base material, controlling the reaction temperature to be 90 ℃, stirring and mixing for 1h to obtain a base material A (namely a component A), and grinding for later use.
The component B (in parts by weight) is as follows:
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 30 parts of gamma-glycidoxypropyltrimethoxysilane, 20 parts of modified siloxane with a multi-benzene ring side group and 1 part of dibutyl tin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a planetary mixer according to the mixing volume ratio of 10:1, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
Example 5:
the preparation method of the heat-resistant silicone structural sealant provided in this example is as follows:
the component A comprises the following components in parts by weight:
taking 100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethicone with the viscosity of 400 mPas, adding the mixture into a kneader, stirring and dispersing, adding 100 parts of nano active calcium carbonate with the particle size of 60nm into the mixture in the stirring process after 5min so that the glue completely covers the powder to form a self-leveling base material, controlling the reaction temperature to be 90 ℃, stirring and mixing for 1h to obtain a base material A (namely a component A), and grinding for later use.
The component B (parts by weight):
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 40 parts of gamma-glycidoxypropyltrimethoxysilane, 10 parts of modified siloxane with a multi-benzene ring side group and 1 part of dibutyl tin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a planetary mixer according to the mixing volume ratio of 10:1, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
Comparative example 1:
the preparation method of the heat-resistant silicone structural sealant provided by the comparative example is as follows:
the component A comprises the following components in parts by weight:
100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethyl silicone oil with the viscosity of 400 mPas are added into a kneader to be stirred and dispersed, after 5min, 100 parts of nano active calcium carbonate with the particle size of 60nm is added into the mixture in the stirring process to ensure that the glue completely covers the powder to form a self-leveling base material, the reaction temperature is controlled at 90 ℃, and the mixture is stirred and mixed for 1h to obtain a base material A (namely a component A), and the base material A is ground for later use.
The component B (parts by weight):
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 50 parts of gamma-glycidoxypropyltrimethoxysilane and 1 part of dibutyl tin dilaurate into the B base material, and stirring for 10min under the protection of nitrogen to obtain a component B;
and vacuumizing and uniformly mixing the component A and the component B in a mixing volume ratio of 10:1 in a planetary mixer, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
Comparative example 2
The preparation method of the heat-resistant silicone structural sealant provided by the comparative example comprises the following steps:
the component A comprises the following components in parts by weight:
100 parts of hydroxyl-terminated polydimethylsiloxane with the viscosity of 20000 mPas and 10 parts of dimethyl silicone oil with the viscosity of 400 mPas are added into a kneader to be stirred and dispersed, after 5min, 100 parts of nano active calcium carbonate with the particle size of 60nm is added into the mixture in the stirring process to ensure that the glue completely covers the powder to form a self-leveling base material, the reaction temperature is controlled at 90 ℃, and the mixture is stirred and mixed for 1h to obtain a base material A (namely a component A), and the base material A is ground for later use.
The component B (in parts by weight) is as follows:
adding 100 parts of 10000 mPa.s dimethyl silicone oil and 100 parts of carbon black into a planetary stirrer, stirring in vacuum, keeping the temperature at 100 ℃ for 30min to obtain a B base material, cooling to room temperature, adding 50 parts of methyltrimethoxysilane, 50 parts of vinyl trimethoxysilane and C into the B base material2H5Ph2SiH (vinyltrimethoxysilane and C)2H5Ph2The molar ratio of SiH is 1: 50 parts of total weight), and 1 part of dibutyl tin dilaurate is added, and stirred for 10min under the protection of nitrogen gas to obtain a component B;
wherein, C2H5Ph2The SiH has the following structural formula:
and vacuumizing and uniformly mixing the component A and the component B in a mixing volume ratio of 10:1 in a planetary mixer, and then preparing an H-shaped test piece for detecting the tensile adhesion of the test piece.
The H-type test pieces prepared in examples 1 to 5 and comparative examples 1 to 2 were cured for 14D under standard conditions, placed in an environment at a temperature of (90. + -. 2) ℃ for 1 hour, taken out, subjected to a tensile test at that temperature, and the tensile bonding strength of the test pieces was recorded. Tensile adhesion test the tensile adhesion test was performed according to GB/T13477.8-2003. The test results are shown in table 1.
TABLE 1 tensile adhesion test results of test pieces obtained in examples and comparative examples
From the experimental results of the above examples and comparative examples, it can be seen that: after the self-made modified siloxane coupling agent with the side groups of the multiple benzene rings is added, the tensile retention rate at 90 ℃ of the structural adhesive is improved by comparing the example 1 with the comparative examples 1-2, but the strength of the structural adhesive is slightly reduced by singly using the self-made coupling agent, which is probably because the aging of the structural adhesive is effectively reduced after a large-volume chain segment is introduced, but the molecular steric hindrance is larger when the addition amount is too much, and the formation of a cross-linked network structure of the structural adhesive is influenced. In order to balance the phenomenon, the comparative examples 2,3, 4 and 5 show that when the addition amount of the modified siloxane containing the multi-benzene ring side group is 30 parts, the comprehensive performance of the structural adhesive is better.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A modified siloxane characterized by the structure:
2. a modified siloxane is characterized by consisting of C2H5Ph2SiH and vinyl trimethoxy silane are subjected to hydrosilylation reaction under the action of a catalyst to obtain,
said C is2H5Ph2The SiH has the following structural formula:
3. the modified siloxane of claim 2, wherein the catalyst is a Pt catalyst; and/or the presence of a gas in the gas,
said C is2H5Ph2The reaction molar ratio of SiH to vinyltrimethoxysilane is 3-5: 1.
4. a process for preparing a modified siloxane as claimed in any one of claims 1 to 3, comprising the steps of:
under the protection of nitrogen or inert gas, the vinyl trimethoxy silane and C2H5Ph2SiH reacts in the presence of the catalyst to obtain the modified siloxane;
the reaction temperature is 90-110 ℃.
5. The method for preparing modified siloxane as claimed in claim 4, wherein the reaction time is 8-12 h; preferably, the reaction temperature is 95-105 ℃, and the reaction time is 9-11 h.
6. A silicone sealant characterized in that a coupling agent comprises the modified siloxane according to any one of claims 1 to 3.
7. The silicone structural sealant according to claim 6, wherein said silicone structural sealant comprises an A-side and a B-side,
the component A is prepared from the following raw materials in parts by weight:
100 parts of organopolysiloxane polymer
60-150 parts of filler
5-25 parts of a plasticizer;
the component B is prepared from the following raw materials in parts by weight:
100 parts of dimethyl silicone oil
50-150 parts of carbon black
15-60 parts of cross-linking agent
15-60 parts of coupling agent
0.1-1.5 parts of a catalyst;
preferably, the component A is prepared from the following raw materials in parts by weight:
100 parts of organopolysiloxane polymer
90-110 parts of filler
8-12 parts of a plasticizer;
the component B is prepared from the following raw materials in parts by weight:
100 parts of dimethyl silicone oil
90-110 parts of carbon black
45-55 parts of cross-linking agent
45-55 parts of coupling agent
0.8-1.2 parts of a catalyst;
preferably, when used, the mixing volume ratio of the A component and the B component is 8-14: 1.
8. The silicone structural sealant according to claim 7, wherein the coupling agent is the modified siloxane according to any one of claims 1 to 3, or the coupling agent is composed of a first coupling agent and a second coupling agent, the first coupling agent is the modified siloxane according to any one of claims 1 to 3; the second coupling agent is selected from gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, epoxycyclohexylmethyldimethoxysilane, epoxycyclohexylmethyldiethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxyethyltriethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, chloropropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma-glycidyloxyethylsilane, gamma-glycidyloxypropyltriethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-methyl-ethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyl-methyl-ethyl ester, and a, At least one of N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, epoxypropyltrimethoxysilane, and divinyltriaminopropyltrimethoxysilane;
preferably, the mass ratio of the first coupling agent to the second coupling agent is 1: 0 to 4;
preferably, the mass ratio of the first coupling agent to the second coupling agent is 1: 0.2-1.5;
preferably, the mass ratio of the first coupling agent to the second coupling agent is 1: 0.6-0.8;
preferably, the coupling agent is prepared from a mixture of 1: 0.65-0.7 of the modified siloxane and gamma-glycidoxypropyltrimethoxysilane.
9. The silicone structural sealant according to claim 7 or 8, wherein the organopolysiloxane polymer is selected from at least one of hydroxyl terminated polydimethylsiloxanes, alkoxy terminated polydimethylsiloxanes, alkyl terminated polydimethylsiloxanes; and/or the presence of a gas in the gas,
the viscosity of the organopolysiloxane polymer at 25 ℃ is 10000mPa & s-50000 mPa & s; and/or the presence of a gas in the gas,
the filler is nano active calcium carbonate; and/or the presence of a gas in the atmosphere,
the plasticizer is selected from at least one of dimethyl silicone oil, methyl phenyl silicone oil and hydroxyl silicone oil; and/or the presence of a gas in the gas,
the cross-linking agent is selected from at least one of ethyl orthosilicate, propyl orthosilicate, polyethyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, polymethyltriethoxysilane oligomer, phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane; and/or the presence of a gas in the gas,
the catalyst is at least one selected from dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctoate, isopropyl titanate and n-butyl titanate.
10. A method for preparing a silicone structural sealant according to any one of claims 7 to 9, comprising the steps of:
preparation of the component A: mixing the organopolysiloxane polymer, the filler and the plasticizer at the temperature of 60-120 ℃ for 10-200 min to obtain the composite material;
preparation of the component B: and (2) mixing the dimethyl silicone oil and the carbon black for 10-60 min at the temperature of 80-120 ℃, cooling, adding the cross-linking agent, the coupling agent and the catalyst, and continuously stirring for 10-100 min under the protection of nitrogen or inert gas to obtain the nano-silica/carbon black composite material.
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