CN115386333A - Low-compression permanent-deformation single-component heat-cured organosilicon sealant and preparation method thereof - Google Patents
Low-compression permanent-deformation single-component heat-cured organosilicon sealant and preparation method thereof Download PDFInfo
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- CN115386333A CN115386333A CN202211110986.9A CN202211110986A CN115386333A CN 115386333 A CN115386333 A CN 115386333A CN 202211110986 A CN202211110986 A CN 202211110986A CN 115386333 A CN115386333 A CN 115386333A
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- 238000007906 compression Methods 0.000 title claims abstract description 46
- 239000000565 sealant Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 75
- 239000001257 hydrogen Substances 0.000 claims abstract description 75
- 229920002545 silicone oil Polymers 0.000 claims abstract description 69
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 69
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000004590 silicone sealant Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229920002050 silicone resin Polymers 0.000 claims abstract description 18
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002516 radical scavenger Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 230000006835 compression Effects 0.000 claims description 31
- -1 vinyl siloxane Chemical class 0.000 claims description 26
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 16
- 238000013007 heat curing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- OWRXWSVBJIIORE-UHFFFAOYSA-N 3,7,11-trimethyldodec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)(O)C#C OWRXWSVBJIIORE-UHFFFAOYSA-N 0.000 claims description 5
- INASARODRJUTTN-UHFFFAOYSA-N 3-methyldodec-1-yn-3-ol Chemical compound CCCCCCCCCC(C)(O)C#C INASARODRJUTTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 3
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 2
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims 4
- 239000002318 adhesion promoter Substances 0.000 claims 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 229920002379 silicone rubber Polymers 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 13
- 239000004945 silicone rubber Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000037303 wrinkles Effects 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-compression permanent deformation single-component thermosetting silicone sealant and a preparation method thereof, wherein high-viscosity vinyl silicone oil, low-viscosity vinyl silicone oil, fumed silica, a hydroxyl scavenging agent and water are used for preparing a base material, high-hydrogen-containing silicone oil and low-hydrogen-containing silicone oil are compounded to form a cross-linking agent, and the base material, the vinyl silicone resin, the high-hydrogen-containing silicone oil, the low-hydrogen-containing silicone oil, a tackifier, an inhibitor and a catalyst are prepared into the sealant according to a proportion.
Description
Technical Field
The invention relates to a low-compression permanent deformation single-component thermosetting organosilicon sealant, belonging to the technical field of liquid silicone rubber.
Background
The silicon rubber has excellent high and low temperature resistance, excellent weather aging resistance, good hydrophobic property, electrical insulation, high air permeability, physiological inertia and the like, and is widely applied to the fields of photovoltaics, new energy, electronic and electric appliances, automobiles, household appliances and the like.
With the progress of science and technology and the rapid development of society, people have more and more strong protection consciousness on environmental protection and renewable resources, and due to the use of renewable solar energy and no pollution, photovoltaic power generation is considered to be one of the most promising power generation fields, and now enters the industrial and residential power utilization fields and is visible everywhere; photovoltaic power generation is a technology for directly converting light energy into electric energy by utilizing the photovoltaic effect of a semiconductor interface, mainly comprises a solar panel (assembly), a controller and an inverter, most photovoltaic inverters are installed outdoors, and particularly, working environments of large photovoltaic power station inverters are outdoors, and the inverters are examined in the face of severe environments such as temperature difference change, humidity, storm and the like, so that protection of internal components of the photovoltaic inverters is particularly important. At present, the photovoltaic inverter shell is mostly subjected to waterproof sealing by using the mixing type silicon rubber sealing strip, the sealing strip does not have adhesiveness to a base material, a double-sided adhesive tape needs to be manually pasted for fixing, other adhesives need to be used for sealing in a closed position, the production efficiency is low, and the labor cost is high. The temperature of the photovoltaic inverter can reach 110 ℃ at most when the photovoltaic inverter works outdoors, the temperature resistance of the double-sided tape is poor, the sealing strip can be fused and broken through long-term aging, the sealing strip is slipped and dislocated, the sealing performance is obviously reduced, and the risk of water leakage is caused.
Chinese patent No. CN112852167A discloses a low-hardness transparent liquid silicone rubber composition with low compression deformation, which improves the compression deformation performance by adding side vinyl silicone oil and vinyl MQ silicone resin, but is A and B two components which need to be mixed before use. Chinese patent CN101983939A discloses a liquid silicone rubber composition, which is characterized in that foaming agent and heat-resistant agent are added to enable silicone rubber to foam after curing to form a sponge shape to improve the compression permanent deformation performance, but the foaming agent and the heat-resistant agent need to be mixed before the A and B components are used, the mechanical property of the foamed and cured silicone rubber is poor, and the foaming agent does not have adhesive force to a base material. Chinese patent CN101665623A discloses a two-component addition type self-adhesive silicone rubber, which is characterized in that the ratio of vinyl group and silicon hydrogen group in the product is controlled to make the vinyl group excessive, and the unreacted vinyl group after curing makes the surface of the vulcanized silicone rubber have good adhesion, but the excessive vinyl group can cause incomplete vulcanization, and further affects the strength and compression permanent deformation performance of the silicone rubber. Chinese patent CN 114752345A discloses a double-component self-adhesive liquid silicone rubber and a preparation method thereof, wherein special tackifier is adopted for compounding, and hydrogen-containing cross-linking agents are adopted for compounding on the end and the side of the silicon rubber, so that the adhesion and the compression permanent deformation of a base material are improved, but the double components A and B need to be mixed before use, the tensile strength is only 3.5Mpa, and the maximum shear strength is only 2.6Mpa. Chinese patent CN 110669344A discloses a single-component addition type liquid silicone rubber, which is prepared by processing fumed silica with hexamethyldisilazane and high vinyl silicone oil to obtain a base material, and matching with alkynol inhibitor and platinum complex to obtain the single-component addition type liquid silicone rubber with better mechanical property, wherein the tensile strength can reach 9Mpa, the elongation is 400%, although the mechanical property is better, the surface energy of the cured liquid silicone rubber without tackifier is lower, the adhesion to the base material is poor, and the storage period at 25 ℃ is only 3 months.
In the prior patent and literature, the addition type liquid silicone rubber or the single-component system has poor adhesion with a base material after vulcanization and short storage time at room temperature, which causes great inconvenience for practical application. Or a bi-component system, the bi-component addition type liquid silicone rubber can be used only after the two components are metered according to the proportion by equipment and are uniformly mixed, and the phenomena of uneven metering and uneven mixing of the two components exist in the metering and mixing processes, so that the stability of the product performance is seriously influenced, and the mechanical property and the compression permanent deformation performance are influenced. Therefore, the development of a low compression set single-component heat-curing silicone sealant which has a long shelf life at room temperature, is rapidly cured at high temperature and has excellent adhesion to a base material becomes a future trend to replace the traditional sealing strip.
Disclosure of Invention
The invention aims to provide a low-compression permanent deformation single-component heat-curing organic silicon sealant and a preparation method thereof, and the sealant is characterized by having excellent compression permanent deformation performance, excellent bonding performance on stainless steel, aluminum materials, glass, unsaturated polyester coatings, temperature-resistant plastics (such as pc) and the like, can be stored for 9 months at 25 ℃, keeps the consistency unchanged within 9 months, and can be completely cured within 5min at 150 ℃; the tensile strength is more than 5Mpa, the elongation at break is more than 350 percent, and the hardness is 20-60 Shore A. The CIPG technology can be used for waterproof sealing of shells of photovoltaic radiators, new energy electric vehicles, household appliances and the like.
In order to achieve the above object, the present invention provides the following technical measures, wherein the raw materials are all in parts by weight.
The invention provides a low-compression permanent deformation single-component thermosetting organosilicon sealant which is prepared from the following raw materials:
wherein the base material is:
the high-viscosity vinyl silicone oil is added when the base material is prepared, so that the dispersion effect of the white carbon black can be improved, and the cross-linked and cured silicone rubber has more excellent mechanical properties; because the molecular weight is larger, the molecular chain is softer, the vinyl content is lower, and the proper amount of low-viscosity vinyl silicone oil is matched, the crosslinking points can be dispersed during crosslinking and curing, and the cured silicone rubber not only has better compressibility, but also has better rebound resilience. The common bi-component liquid silicone rubber needs to be mixed when in use, has higher requirement on consistency, and needs to add more fumed silica when preparing a base material in order to obtain better mechanical property, so that vinyl silicone oil with higher viscosity cannot be selected; in order to obtain better thixotropy, most of single-component liquid silicone rubber is added with more fumed silica, but the single-component liquid silicone rubber is limited by extrudability, and the vinyl silicone oil with higher viscosity cannot be used; in the invention, vinyl silicone oil with higher viscosity is added when the base material is prepared, in order to give consideration to the extrudability and the mechanical property and properly reduce the addition amount of the fumed silica, the surface treatment is carried out on the white carbon black by using the hydroxyl scavenging agent containing vinyl, and the vinyl carried on the white carbon black can react and crosslink with the hydrogen-containing silicone oil when the silicone rubber is cured, so that better mechanical property can also be obtained; active groups carried in the tackifier can form hydrogen bonds with hydroxyl groups on the white carbon black, so that excellent thixotropy is endowed to the silicone rubber.
Preferably, the vinyl silicone resin is vinyl MQ silicone resin, the vinyl content is 1.9% -3.8%, and the structural formula is as follows:
in the formula:
Z 2 and Z 3 Are respectively-CH 3 or-CH = CH 2 X = (2 to 100). The vinyl silicone resin is of a three-dimensional network structure, and the vinyl carried by the vinyl can participate in a crosslinking reaction, so that the vinyl has a good reinforcing effect; the compression permanent deformation performance of the cured silicone rubber is obviously improved due to the steric hindrance effect by introducing the phenyl or the ring-shaped epoxy group; the cyclic epoxy has a carbon functional group that improves adhesion to the substrate.
Preferably, the high hydrogen-containing silicone oil is side hydrogen-containing silicone oil or end side hydrogen-containing silicone oil, the hydrogen content is 0.75-1.6%, the low hydrogen-containing silicone oil is side hydrogen-containing silicone oil, and the hydrogen content is 0.18-0.75%.
The side hydrogen-containing silicone oil or the end side hydrogen-containing silicone oil can adopt the hydrogen-containing silicone oil with the following structural formula, and is purchased and selected according to the requirement of hydrogen content:
a pendant hydrogen-containing polysiloxane,
n＝10～300，m＝1～100；
a hydrogen-containing polysiloxane on the end side,
n＝10～300，m＝1～100。
according to the invention, the high hydrogen-containing silicone oil and the low hydrogen-containing silicone oil are matched to be used as the cross-linking agent, so that the comprehensive properties of the tensile strength and the elongation at break of the silicone rubber can be considered.
The addition type liquid silicone rubber without the tackifier is in a highly saturated state due to the spiral curl of a molecular chain segment and the shielding of the polarity of a silicon-oxygen bond by a nonpolar side group, shows lower surface energy, has poor wettability to various substrates, lacks of groups with reactivity, has weak molecular acting force with the substrates, and has poor adhesive property. The addition of the tackifier with a specific structure can endow the silicone rubber with excellent adhesiveness, the tackifier introduces vinyl or hydrogen to participate in a crosslinking reaction, solves the problem of poor compatibility and exudation, introduces active groups such as alkoxy, epoxy, acryloxy and the like, and can react with hydroxyl on the surface of a base material to form a chemical bond or a hydrogen bond so as to realize firm adhesion.
Preferably, the tackifier is a cyclic or chain siloxane with the structural formula
Or is structured as
In the structural formula of the tackifier, R 1 And R 2 Is composed of
—CH 2 -CH 2 -CH 2 -Si-O-Si-H or-CH 2 -CH＝CH 2 Or
R 1 And R 2 May be the same or different;
R 3 is composed of
R 4 And R 5 Is composed of
The preparation method of the tackifier comprises the following steps:
1) Dispersing vinyl-containing or hydrogen-containing cyclic or chain siloxane in a solvent, adding a platinum catalyst, and slowly dropwise adding hydrogen-containing or vinyl siloxane to perform hydrosilylation reaction;
2) Adding active carbon for adsorption for 2-8 h, filtering, and distilling under reduced pressure to obtain the tackifier.
Preferably, the preparation method of the tackifier comprises the following steps:
1) Dispersing vinyl-containing or hydrogen-containing cyclic or chain siloxane in a solvent at the temperature of 20-60 ℃, adding a platinum catalyst, slowly dropwise adding hydrogen-containing or vinyl siloxane for hydrosilylation, heating to 50-100 ℃ and reacting for 2-5 h;
2) Adding active carbon for adsorption for 2-8 h, filtering, and distilling under reduced pressure to obtain the tackifier.
Preferably, the platinum catalyst is at least one of chloroplatinic acid and Karstedt platinum catalyst.
Further preferably, the platinum catalyst is at least one of octanol solution of chloroplatinic acid, isopropanol solution of chloroplatinic acid and Karstedt platinum catalyst, and the platinum content is 1000ppm to 3000ppm.
Preferably, the solvent is at least one of toluene, xylene, acetonitrile, cyclohexane, acetone, aromatic hydrocarbons, halogenated hydrocarbons, and cyclopentene hydrocarbons.
Preferably, the inhibitor is at least one of 3-methyl-1-dodecyn-3-ol, 3,7, 11-trimethyldodecyn-3-ol, 3-methyl-1-butyn-3-ol, 1-ethynylcyclohexanol, 3-phenyl-1-butyn-3-ol, bis [ (1, dimethyl-2-propynyl) oxy ] dimethylsilane, diallyl maleate and methyl fumarate.
The conventional alkyne compound can form a coordination bond with a platinum atom in a platinum catalyst molecule at room temperature, and can prevent Si-Vi group or Si-H group from simultaneously participating in coordination, so that the sealant is endowed with certain operation time, and the coordination bond between the inhibitor and the platinum atom is weakened because the low-molecular alkyne compound can volatilize at room temperature, and the Si-Vi group or Si-H group can quickly generate a crosslinking reaction; although the excessive low-molecular acetylene compounds can endow the sealant with better storage property at room temperature, the appearance of the sealant is influenced by the phenomenon of surface wrinkling during heating and curing, so that the addition amount of the sealant is limited; the long-chain or phenyl alkyne compound not only has good inhibition effect at room temperature, but also does not generate wrinkle phenomenon when being heated, so that the inhibitor is further preferably at least one of 3-methyl-1-dodecyn-3-ol, 3,7, 11-trimethyl dodecyn-3-ol and 3-phenyl-1-butyn-3-ol.
Preferably, the catalyst is one of platinum-divinyltetramethyldisiloxane complex and platinum-alkyne-based complex, namely at least one of bis (phenylacetylene) -cycloocta-1, 5-diene platinum complex, bis (phenylacetylene) -1, 5-dimethylcycloocta-1, 5-diene platinum complex, bis (1-ethynylcyclohexanol) -cycloocta-1, 5-diene platinum complex, bis (3-phenyl-1-butyn-3-ol) -cycloocta-1, 5-diene platinum complex and bis (3-methyl-1-butyn-3-ol) -cycloocta-1, 5-diene platinum complex, wherein the platinum content is 1000-3000 ppm.
Further preferably, the catalyst is a bis (phenylacetylene) -cycloocta-1, 5-diene platinum complex, a bis (phenylacetylene) -1, 5-dimethylcycloocta-1, 5-diene platinum complex or a bis (3-phenyl-1-butyn-3-ol) -cycloocta-1, 5-diene platinum complex.
Preferably, the high-viscosity vinyl silicone oil has a viscosity of 100000 to 200000mpa.s at a temperature of 25 ℃.
Preferably, the low-viscosity vinyl silicone oil has a viscosity of 1000 to 20000mpa.s at a temperature of 25 ℃.
Preferably, the fumed silica has a specific surface area of 150 to 400m 2 /g。
Preferably, the hydroxyl scavenger is at least one of hexamethyldisilazane, tetramethyldivinyldisilazane, vinyltrimethoxysilane, octyltrimethoxysilane, dimethyldimethoxysilane.
Further preferably, the hydroxyl scavenger is at least one of hexamethyldisilazane, tetramethyldivinyldisilazane, and vinyltrimethoxysilane.
The invention also provides a preparation method of the low compression permanent deformation single-component heat-curing organosilicon sealant, which comprises the following steps:
(1) Preparing a base material:
stirring 20-80 parts by mass of high-viscosity vinyl silicone oil, 20-80 parts by mass of low-viscosity vinyl silicone oil, 15-50 parts by mass of fumed silica, 2-15 parts by mass of hydroxyl scavenging agent and 2-10 parts by mass of water in a vacuum kneader for 60-120 min, heating to 120-200 ℃, stirring for 90-200 min, diluting, cooling and grinding to obtain a base material after the mixture is subjected to dehydration blending for 60-180 min under the vacuum degree of-0.08-0.1 MPa;
(2) Preparing the low compression permanent deformation single-component heat-curing organic silicon sealant:
adding 100 parts by mass of base material, 15-30 parts by mass of vinyl silicone resin, 2-5 parts by mass of high hydrogen silicone oil and 1-8 parts by mass of low hydrogen silicone oil into a planetary stirrer with a cooling and high-speed dispersing device, stirring for 10-20 min under the conditions of high-speed dispersion of 500-1000 r/min and low-speed stirring of 40-80 r/min, adding 1-5 parts by mass of tackifier and 0.1-1 part by mass of inhibitor, stirring for 15-20 min under the conditions of high-speed dispersion of 300-600 r/min, low-speed stirring of 30-60 r/min and vacuum degree of-0.08-0.1 MPa, adding 0.2-1 part by mass of catalyst, stirring for 5-15 min under the conditions of high-speed dispersion of 300-600 r/min, low-speed stirring of 30-60 r/min and vacuum degree of-0.08-0.1 MPa, discharging, sealing and storing to obtain the low-compression permanent deformation thermosetting silicone sealant.
The invention has the beneficial effects that:
(1) Compared with addition type silicon rubber, the condensed type single-component silicon rubber has the problems of long complete curing time, micromolecule release and the like. Therefore, the development of a low-compression permanent deformation single-component heat-curing silicone sealant which has a long storage period at room temperature, excellent adhesion to a base material and high-temperature quick curing is a trend in the future to replace the traditional mixing type silicone rubber sealing strip.
(2) The structural group of the tackifier has lower activity at normal temperature, part of the group can react with vinyl or hydrogen in the sealant during heating and curing, and part of the group can react with hydroxyl on the surface of a substrate (aluminum, stainless steel, plastic, epoxy or polyester coating material) to form chemical bonding, so that firm bonding is realized without pretreating the substrate.
(3) The invention uses the platinum complex and the inhibitor in combination, so that the low compression set single-component thermosetting organosilicon sealant can have a storage period of more than 9 months at 25 ℃, does not need low-temperature storage, has a longer storage period compared with the commercial single-component addition type organosilicon sealant, can be rapidly and completely cured at 150 ℃, and has a TC90 of 30-90 s.
(4) The low-compression permanent-deformation single-component thermosetting organosilicon sealant can be directly used, and the phenomenon of unstable product quality caused by uneven mixing can be avoided; the glue is applied manually or by equipment, the requirement on the accuracy of glue applying equipment is low, the number of mechanical equipment required in use is small, and the equipment cost is reduced.
(5) Waterproof sealing for CIPG process, meeting requirement for H 2 O、O 2 The sealing requirements of (2).
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adjustments in the non-essential aspects according to the contents of the present invention.
The method for preparing the tackifier of embodiment 2 comprises the following steps:
1) Adding 63g of triallyl isocyanurate (TAIC) and 80g of toluene into a 250mL three-neck flask provided with a thermometer, a condenser tube and a mechanical stirring device, heating to 40 ℃, stirring and dispersing until the TAIC is completely dissolved, taking out for standby, and marking as a solution A
2) Adding 38g of hydrogen-containing double-head, 30g of toluene and 0.3g of Karstedt platinum catalyst of 3000ppm into a cleaned and dried three-neck flask, stirring and heating to 60 ℃, slowly dropwise adding 66g of 1, 2-epoxy-4-vinylcyclohexane under stirring at a low speed (dropwise adding is finished within 30 min), stirring and reacting for 2h, slowly dropwise adding the solution A under stirring at a low speed (dropwise adding is finished within 40 min), stirring and reacting for 3h, and then cooling to room temperature.
3) Adding active carbon for adsorption for 5h, filtering, and distilling under reduced pressure to obtain tackifier.
The method of making the tackifier of example 3, comprising the steps of:
1) 67g of 1-oxiranylmethyl-3, 5-diallyl isocyanurate (DA-MGIC) and 70g of xylene are added into a 250mL three-neck flask provided with a thermometer, a condenser and a mechanical stirring device, heated to 50 ℃, stirred and dispersed until the DA-MGIC is completely dissolved, taken out for later use, and marked as solution B.
2) And adding 37g of hydrogen-containing double end enclosure, 30g of dimethylbenzene and 0.5g of Karstedt platinum catalyst of 3000ppm into the cleaned and dried three-neck flask, stirring and heating to 65 ℃, slowly dropwise adding the solution B (dropwise adding is finished within 30 min) under stirring at a low rotating speed, stirring and reacting for 3.5h, and then cooling to room temperature.
3) Adding active carbon for adsorption for 3 hr, filtering, and distilling under reduced pressure to obtain tackifier.
Example 1
50 parts by mass of high-viscosity vinyl silicone oil with the viscosity of 120000mpa.s at the temperature of 25 ℃, 50 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 5000mpa.s at the temperature of 25 ℃ and the specific surface area of 350m 2 30 parts by mass of fumed silica per gram, 10 parts by mass of hexamethyldisilazane and 2 parts by mass of distilled water are added into a vacuum kneader and stirred for 70min, then heated to 130 ℃, stirred for 120min, vacuumized and stirred for 120min at 180 ℃, and then diluted, cooled and ground to obtain the base material. Structure of the will
Z 2 And Z 3 Are all-CH 3 X =80, 16 parts by mass of vinyl MQ silicone resin with 2% of vinyl content, 3 parts by mass of side hydrogen-containing silicone oil with 1.2% of hydrogen content, 5 parts by mass of side hydrogen-containing silicone oil with 0.6% of hydrogen content and 100 parts by mass of base material are mixed and stirred for 15min under high-speed dispersion of 800r/min and low-speed stirring of 60r/min (the stirring conditions of the following examples and comparative examples are the same as those of example 1), 1 part by mass of tetraisooctyl titanate, 1 part by mass of ethylene glycol diacrylate and 0.15 part by mass of 3-methyl-1-dodecyn-3-ol are added, after stirring and mixing for 15min under the vacuum degree of-0.08 MPa under high-speed dispersion of 450r/min and low-speed stirring of 45r/min, 0.2 part by mass of bis (phenylacetylene) -1, 5-dimethylcyclooctane-1, 5-diene platinum complex (with the platinum content of 3000 ppm) is stirred for 15min under the vacuum degree of-0.08 MPa, and after the vacuum degree of-0.099 MPa is kept for 10min, the result of low-compression sealing performance of the single-component silicone sealant is obtained, and the discharge heat curing is shown in the discharge table of the hot curing test.
Example 2
Mixing high-viscosity vinyl silicone oil 70 with viscosity of 100000mpa.s at 25 deg.C30 parts of low-viscosity vinyl silicone oil with the viscosity of 5000mpa.s at the temperature of 25 ℃ and the specific surface area of 300m 2 35 parts by mass of fumed silica per gram, 8 parts by mass of hexamethyldisilazane, 2 parts by mass of tetramethyldivinyldisilazane and 3 parts by mass of distilled water, adding the materials into a vacuum kneader, stirring for 60min, heating to 150 ℃, stirring for 100min, vacuumizing and stirring for 120min at 170 ℃, wherein the vacuum degree is-0.08 MPa, diluting, cooling and grinding to obtain the base material. Will structure
Z 2 ＝—CH 3 ，Z 3 ＝—CH＝CH 2 X =50, 20 parts by mass of vinyl MQ silicone resin with 3.2% of vinyl content, 5 parts by mass of end-side hydrogen-containing silicone oil with 1.5% of hydrogen content, 8 parts by mass of end-side hydrogen-containing silicone oil with 0.55% of hydrogen content and 100 parts by mass of base material are mixed and stirred for 15min, and then the mixture is added with the structure
R 1 ＝—CH 2 -CH＝CH 2 ，R2＝
After 2.0 parts by mass of tackifier and 0.1 part by mass of 3,7, 11-trimethyldodecyne-3-ol are stirred and mixed for 16min under the vacuum degree of-0.08 Mpa, 0.3 part by mass of bis (phenylacetylene) -cyclooctane-1, 5-diene platinum complex (platinum content is 2000 ppm) is discharged, sealed and stored after the vacuum degree of-0.099 Mpa is kept and stirred for 12min to obtain the low-compression permanent deformation single-component thermosetting silicone sealant, and the detail of the test result of the product performance is shown in Table 2.
Example 3
40 parts by mass of high-viscosity vinyl silicone oil with the viscosity of 120000mpa.s at the temperature of 25 ℃, 60 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 10000mpa.s at the temperature of 25 ℃ and 400m of specific surface area 2 25 parts by mass of fumed silica per gram, 12 parts by mass of hexamethyldisilazane and 5 parts by mass of distilled water are added into a vacuum kneader and stirred for 80min, then heated to 140 ℃, stirred for 100min, vacuumized and stirred for 150min at 160 ℃, and then diluted, cooled and groundGrinding to obtain the base material. Will structure
Z 2 ＝CH 3 ，Z 3 ＝—CH＝CH 2 X =30, 16 parts by mass of vinyl MQ silicone resin having a vinyl content of 3.8%, 5 parts by mass of terminal-side hydrogen-containing silicone oil having a hydrogen content of 1.6%, 5 parts by mass of terminal-side hydrogen-containing silicone oil having a hydrogen content of 0.75%, and 100 parts by mass of a base material were mixed and stirred for 20min, and then a structure was added
R 1 Is composed of
R 2 is-CH 2 -CH 2 -CH 2 3.0 parts by mass of tackifier of-Si-O-Si-H and 0.1 part by mass of 3-phenyl-1-butyn-3-ol, stirring and mixing for 20min under the vacuum degree of-0.08 Mpa, then discharging and sealing for storage to obtain the low compression permanent deformation single-component heat-cured silicone sealant after 0.2 part by mass of bis (3-phenyl-1-butyn-3-ol) -cycloocta-1, 5-diene platinum complex (3000 ppm) is kept under the vacuum degree of-0.099 Mpa and stirred for 20min, and the test results of the product performance are shown in Table 2 in detail.
Example 4
30 parts by mass of high-viscosity vinyl silicone oil with the viscosity of 120000mpa.s at the temperature of 25 ℃, 70 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 10000mpa.s at the temperature of 25 ℃ and 300m of specific surface area 2 35 parts by mass of fumed silica per gram, 10 parts by mass of hexamethyldisilazane, 5 parts by mass of vinyltrimethoxysilane and 10 parts by mass of distilled water, adding the materials into a vacuum kneader, stirring for 90min, heating to 150 ℃, stirring for 90min, vacuumizing at 180 ℃, keeping the vacuum degree at-0.08 MPa, stirring for 180min, diluting, cooling and grinding to obtain the base material. Structure of the will
Z2 and Z3 are both-CH = CH 2 X =70, 18 parts by mass of vinyl MQ silicone resin having a vinyl content of 2.3%, 5 parts by mass of terminal-side hydrogen-containing silicone oil having a hydrogen content of 1.2%, the hydrogen content beingMixing 0.6% side hydrogen-containing silicone oil 5 parts by mass with base material 100 parts by mass, stirring for 15min, and adding structure
Example 5
The specific conditions and raw materials not described in this example were the same as in example 4, except that 5 parts by mass of the side hydrogen-containing silicone oil having a hydrogen content of 0.85% was used as the high hydrogen-containing silicone oil, 8 parts by mass of the side hydrogen-containing silicone oil having a hydrogen content of 0.6% was used as the low hydrogen-containing silicone oil, and the tackifier structure was changed
The catalyst is 0.4 part by mass of a bis (3-methyl-1-butyn-3-ol) -cycloocta-1, 5-diene platinum complex (platinum content is 1500 ppm), and the inhibitor is 0.2 part by mass of 3,7, 11-trimethyldodecyn-3-ol.
Comparative example 1
50 parts by mass of high-viscosity vinyl silicone oil with the viscosity of 120000mpa.s at the temperature of 25 ℃, 50 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 5000mpa.s at the temperature of 25 ℃ and the specific surface area of 350m 2 30 parts by mass of fumed silica per gram, 10 parts by mass of hexamethyldisilazane and 2 parts by mass of distilled water are added into a vacuum kneader and stirred for 70min, and then addedHeating to 130 deg.C, stirring for 120min, vacuumizing at 180 deg.C under-0.08 MPa, stirring for 120min, diluting, cooling, and grinding to obtain base material. 16 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 10000mpa.s at the temperature of 25 ℃,3 parts by mass of lateral hydrogen-containing silicone oil with the hydrogen content of 1.2 percent, 5 parts by mass of lateral hydrogen-containing silicone oil with the hydrogen content of 0.6 percent and 100 parts by mass of base material are mixed and stirred for 15min, 0.15 part by mass of 3-methyl-1-dodecyn-3-ol, and after the mixture is stirred and mixed for 15min at the vacuum degree of-0.08 MPa, 0.2 part by mass of bis (phenylacetylene) -1, 5-dimethylcyclooctane-1, 5-diene platinum complex (3000 ppm) is discharged, sealed, stored and obtained after the stirring is carried out for 10min at the vacuum degree of-0.099 MPa, and the low-compression permanent deformation single-component heat-curing silicone sealant is obtained, wherein the test results of the product performance are shown in Table 2 in detail.
Comparative example 2
30 parts by mass of high-viscosity vinyl silicone oil with the viscosity of 120000mpa.s at the temperature of 25 ℃, 70 parts by mass of low-viscosity vinyl silicone oil with the viscosity of 10000mpa.s at the temperature of 25 ℃ and 300m of specific surface area 2 35 parts by mass of fumed silica per gram, 10 parts by mass of hexamethyldisilazane, 5 parts by mass of vinyltrimethoxysilane and 10 parts by mass of distilled water, adding the materials into a vacuum kneader, stirring for 90min, heating to 150 ℃, stirring for 90min, vacuumizing at 180 ℃, keeping the vacuum degree at-0.08 MPa, stirring for 180min, diluting, cooling and grinding to obtain the base material. Will structure
Z2 and Z3 are both-CH = CH 2 X =70, 18 parts by mass of vinyl MQ silicone resin having a vinyl content of 2.3%, 5 parts by mass of terminal-side hydrogen-containing silicone oil having a hydrogen content of 1.2%, 5 parts by mass of terminal-side hydrogen-containing silicone oil having a hydrogen content of 0.6%, and 100 parts by mass of a base material were mixed and stirred for 15min, and then a structure was added
The above examples and comparative examples were evaluated for properties according to the criteria of Table 1, and the results are shown in Table 2.
TABLE 1 Performance test standards
| Test items | Test standard |
| Vulcanization Properties | GB/T16584-1996 |
| Consistency of | GB/T1749-79 |
| Tensile strength | GB/T528-2009 |
| Elongation at break | GB/T528-2009 |
| Shear strength | GB/T7124-2008 |
| Compression set | GB/T7759.1-2015 |
TABLE 2 test results of product properties of each example and comparative example
As shown by the test data of the examples and the comparative examples, the addition of the vinyl MQ silicone resin containing benzene ring or epoxy to the sealant can provide excellent compression set performance due to the synergistic effect of the steric hindrance rigid effect of the benzene ring and the dense crosslinking points of the multi-vinyl functional groups of the silicone resin. The examples all used the vinyl MQ silicone resin containing benzene ring or epoxy, the comparative example 1 did not use the vinyl MQ silicone resin containing benzene ring or epoxy, and in addition, the comparative example 1 did not use the tackifier, and as can be seen from the compression set ratios of table 2, the compression set performance of each example was superior to that of the comparative example 1, that is, the compression set performance of the example 1 was significantly superior to that of the comparative example 1. The mechanical properties of example 1 are also clearly better than those of comparative example 1.
The vinyl, hydrogen, epoxy, acryloxy and alkoxy in the tackifier can generate stronger chemical bonding effect with the sealant and the base material, so that the adhesiveness of the sealant is obviously improved; the specially selected platinum-alkyne base compound (catalyst) is matched with long-chain alkynol or phenyl alkynol (inhibitor) for use, and the sealant has excellent storage performance at normal temperature. Each of examples and comparative example 1 used the platinum-alkyne base complex specifically selected in the present invention in combination with a long-chain alkynol or a phenylalkynol, but comparative example 2 used a common platinum catalyst in combination with a long-chain alkynol or a phenylalkynol, and each of examples and comparative example 1 was good in storage property and could be stably stored for 9 months with the viscosity kept substantially unchanged, but comparative example 2 was gradually reduced in consistency and poor in storage stability.
Claims (12)
1. The low compression permanent deformation single-component thermosetting organosilicon sealant is characterized by comprising the following raw material components in parts by mass:
the base material comprises the following raw material components in parts by mass:
2. the low compression set one-component heat-cure silicone sealant of claim 1, wherein the vinyl silicone resin is a vinyl MQ silicone resin, the vinyl content is 1.9% to 3.8%, and the structural formula is:
3. The low compression set one-component heat-curable silicone sealant according to claim 1, wherein the high hydrogen-containing silicone oil is side hydrogen-containing silicone oil or end side hydrogen-containing silicone oil, and the hydrogen content is 0.75% to 1.6%; the low-hydrogen silicone oil is side hydrogen silicone oil, and the hydrogen content is 0.18-0.75%.
4. The low compression set one-component heat-curable silicone sealant as claimed in claim 1, wherein the tackifier is a cyclic or chain siloxane of the formula
Or structural formula
Or the tackifier is a mixture of tetraisooctyl titanate and hexanediol diacrylate.
5. The low compression set, one-part, heat-curable silicone sealant as claimed in claim 4, wherein said adhesion promoter has the formula wherein R 1 And R 2 is-CH 2 -CH 2 -CH 2 -Si-O-Si-H or-CH 2 -CH＝CH 2 Or
R 3 is composed of
R 4 And R 5 Is composed of
6. The low compression set, one-part, heat-curable silicone sealant of claim 5 wherein said adhesion promoter is prepared by a process comprising the steps of:
1) Dispersing vinyl-containing or hydrogen-containing cyclic or chain siloxane in a solvent, adding a platinum catalyst, and slowly dropwise adding hydrogen-containing or vinyl siloxane to perform hydrosilylation reaction;
2) Adding active carbon for adsorption for 2-8 h, filtering, and distilling under reduced pressure to obtain the tackifier.
7. The low compression set one-part, heat curable silicone sealant according to claim 1, wherein said inhibitor is at least one of 3-methyl-1-dodecyn-3-ol, 3,7,11-trimethyldodecyn-3-ol, 3-methyl-1-butyn-3-ol, 1-ethynylcyclohexanol, 3-phenyl-1-butyn-3-ol, bis [ (1, dimethyl-2-propynyl) oxy ] dimethylsilane, diallyl maleate, methyl fumarate.
8. The low compression set one-component, heat-curable silicone sealant according to claim 1, wherein the catalyst is at least one of a platinum-divinyltetramethyldisiloxane complex, a platinum-alkyne based complex, namely a bis (phenylacetylene) -cycloocta-1, 5-dienoplatin complex, a bis (phenylacetylene) -1, 5-dimethylcycloocta-1, 5-dienoplatin complex, a bis (1-ethynylcyclohexanol) -cycloocta-1, 5-dienoplatin complex, a bis (3-phenyl-1-butyn-3-ol) -cycloocta-1, 5-dienoplatin complex, a bis (3-methyl-1-butyn-3-ol) -cycloocta-1, 5-dienoplatin complex, wherein the platinum content is 1000 to 3000ppm.
9. The low compression set one-component heat-cure silicone sealant of claim 1, wherein the viscosity of the high viscosity vinyl silicone oil is 100000-200000 mpa.s at 25 ℃.
10. The low compression set one-component heat-curable silicone sealant according to claim 1, wherein the fumed silica has a specific surface area of 150-400 m 2 /g。
11. The low compression set one-component heat cure silicone sealant of claim 1, wherein the hydroxyl scavenger is at least one of hexamethyldisilazane, tetramethyldivinyldisilazane, vinyltrimethoxysilane, octyltrimethoxysilane, dimethyldimethoxysilane.
12. The method of preparing a low compression set one-part heat-curable silicone sealant according to any one of claims 1 to 11, characterized in that the method comprises the steps of:
(1) Preparing a base material:
stirring 20-80 parts by mass of high-viscosity vinyl silicone oil, 20-80 parts by mass of low-viscosity vinyl silicone oil, 15-50 parts by mass of fumed silica, 2-15 parts by mass of hydroxyl scavenging agent and 2-10 parts by mass of water in a vacuum kneader for 60-120 min, heating to 120-200 ℃, stirring for 90-200 min, then diluting, cooling and grinding to obtain a base material after the mixture is subjected to dehydration and blending for 60-180 min at the vacuum degree of-0.08-0.1 MPa;
(2) Preparing the low compression permanent deformation single-component heat-curing organic silicon sealant:
adding 100 mass parts of base material, 15-30 mass parts of vinyl silicone resin, 2-5 mass parts of high hydrogen silicone oil and 1-8 mass parts of low hydrogen silicone oil into a planetary stirrer with a cooling and high-speed dispersing device, stirring for 10-20 min under high-speed dispersion of 500-1000 r/min and low-speed stirring of 40-80 r/min, adding 1-5 mass parts of tackifier and 0.1-1 mass part of inhibitor, stirring for 15-20 min under high-speed dispersion of 300-600 r/min, low-speed stirring of 30-60 r/min and vacuum degree of-0.08-0.1 MPa, adding 0.2-1 mass part of catalyst, stirring for 5-15 min under high-speed dispersion of 300-600 r/min, low-speed stirring of 30-60 r/min and vacuum degree of-0.08-0.1 MPa, discharging, sealing and storing to obtain the low-compression permanent deformation single-component thermosetting silicone sealant.
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