CN114574155A - Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof - Google Patents
Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof Download PDFInfo
- Publication number
- CN114574155A CN114574155A CN202111566474.9A CN202111566474A CN114574155A CN 114574155 A CN114574155 A CN 114574155A CN 202111566474 A CN202111566474 A CN 202111566474A CN 114574155 A CN114574155 A CN 114574155A
- Authority
- CN
- China
- Prior art keywords
- triethoxysilane
- sealant
- parts
- reinforcing filler
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004590 silicone sealant Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000565 sealant Substances 0.000 claims abstract description 45
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000012767 functional filler Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 60
- 238000004898 kneading Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- -1 polydimethylsiloxane Polymers 0.000 claims description 12
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 11
- 229910021485 fumed silica Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 7
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 3
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 claims description 3
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 3
- PZTZFOWXGZSKPV-UHFFFAOYSA-N CN=C=O.CCO[SiH](OCC)OCC Chemical compound CN=C=O.CCO[SiH](OCC)OCC PZTZFOWXGZSKPV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- 239000003973 paint Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- BOTMPGMIDPRZGP-UHFFFAOYSA-N triethoxy(isocyanatomethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN=C=O BOTMPGMIDPRZGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 238000004026 adhesive bonding Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000012855 volatile organic compound Substances 0.000 description 16
- 239000004005 microsphere Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000013464 silicone adhesive Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000004579 marble Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- 239000004526 silane-modified polyether Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- ARGICNMLPHJXTP-UHFFFAOYSA-N [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].C(=C)C(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O ARGICNMLPHJXTP-UHFFFAOYSA-N 0.000 description 2
- OUGKFJZADGTJRG-UHFFFAOYSA-N [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O Chemical compound [SiH4].CC(OC(CCC)=NO)C(COC(CCC)=O)OC(CCC)=O OUGKFJZADGTJRG-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000003386 deoximation reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- BODAWKLCLUZBEZ-UHFFFAOYSA-N diethoxy(phenyl)silicon Chemical compound CCO[Si](OCC)C1=CC=CC=C1 BODAWKLCLUZBEZ-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007675 toxicity by organ Effects 0.000 description 1
- 231100000155 toxicity by organ Toxicity 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004078 waterproofing Methods 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
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- 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
Abstract
The invention relates to the field of adhesives, and discloses a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof, wherein the sealant comprises the following components: 30-60 parts of base resin, 3-15 parts of reinforcing filler, 30-60 parts of semi-reinforcing filler, 0-15 parts of functional filler, 1-5 parts of cross-linking agent and 1-5 parts of tackifier. The base resin is an alkoxy-terminated polymer. The sealant disclosed by the invention has the following characteristics: (1) the adhesive is plasticine-shaped, can be molded at will before solidification, has long operation time, and does not need auxiliary tools in the gluing process; (2) the coating can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance; (3) low VOC, no heavy metal catalyst, high safety and environmental protection.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof.
Background
With the modernization of production and life style, a large proportion of work and entertainment activities can be carried out indoors, and according to incomplete statistics, more than 80% of modern urban people spend indoors every day, so that the relation of indoor air quality to human health is more important. The result of authoritative investigation issued by the United states Environmental Protection Agency (EPA) shows that the indoor pollution degree of most buildings is several times or even tens of times of outdoor pollution, and 2400 thousands of people die in the world every year from diseases caused by indoor pollution such as overproof VOC (volatile organic Compounds), breeding of mildew microorganisms and the like. More than 90% of indoor pollution sources come from basic sealing, coating and bonding materials, and although the use amount of the materials is not large, the materials play a key role in water proofing, sealing and bonding.
The indoor bonding sealing adhesive mainly takes fluid and paste as main materials, is packaged in a rubber bottle or a hose, and is subjected to gluing and repairing operations by an auxiliary tool; the adhesive is divided into silicone adhesive, polyurethane adhesive, silane modified polyether adhesive and the like according to types, wherein acetic acid released after the deacidified and deoximated silicone adhesive is vulcanized is strong in corrosivity and pungent in smell, and butanone oxime is listed in a list of potential carcinogens by the European Union; the polyurethane adhesive contains free isocyanate monomer and has high toxicity; other types suffer more or less from problems with mechanical properties, adhesive properties, VOC, pollution, odour etc. The dealcoholized silicone sealant and the silane modified polyether sealant are dealcoholized products, have relatively low VOC and wide bonding range, and are more suitable for indoor use compared with other types.
However, although the VOC of the common dealcoholized sealant is low, the main component of the sealant is methanol, and the methanol can cause damage to human nervous and blood systems; meanwhile, a part of alcohol type sealant such as silane modified polyether sealant, dealcoholized silicone adhesive and the like can use trace heavy metal tin as a catalyst, and the tin is harmful to reproductive toxicity and specific target organ toxicity; meanwhile, the alcohol-type sealant mainly exists in a viscous paste form, is stored in a rubber bottle or a hose, needs auxiliary tools such as a rubber gun during use, cannot be molded randomly before curing, is troublesome to repair, and is not convenient enough when used in a small amount indoors.
When the sealant is prepared into a self-supporting plasticine shape, a consumer can be allowed to directly perform manual molding without using tools such as a glue gun and the like to perform personalized application, the use is convenient, and meanwhile, the manual direct contact also puts higher requirements on the environmental protection of the glue.
Plasticine-like silicone rubber products are currently known. CN201510106411.3 and CN110183854A disclose that the two-component putty-containing plasticine product prepared by adopting organic silicon polymer as a base material has high safety, does not seep oil or pollute the environment, can be used as a toy when being used alone, and can be used for molding when being mixed with two components. WO2012058953a1 discloses a silicone putty for sealing doors, windows and architectural joints, which has the advantage of using the form of the putty to be embedded in the joint to seal. Although the putty or plasticine silicone rubber products of these patents provide good hand and ease of use, they do not adhere to the substrate. CN112409795A adopts filler, polysiloxane, coupling agent and activating agent to mix and react according to a certain proportion to obtain a printing mud product which is light in weight, smooth and easy to mould, but is mainly used for moulding without curing and bonding; CN111548764B discloses that alpha, omega-dihydroxy polydimethylsiloxane, filler and the like are adopted to prepare a deoximation type plasticine sealant product which has good initial adhesion and strength and can be molded manually, but an organic tin catalyst is used, so that butanone oxime which is possibly carcinogenic is generated during curing, the operation time is short, and the direct contact with the skin is not environment-friendly.
Disclosure of Invention
In order to solve the technical problems, the invention provides a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof. The sealant disclosed by the invention has the following characteristics: (1) the adhesive is plasticine-shaped, can be molded at will before solidification, has long operation time, and does not need auxiliary tools in the gluing process; (2) the coating can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance; (3) low VOC, no heavy metal catalyst, high safety and environmental protection.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature, which comprises the following components in parts by weight:
30-60 parts of base resin,
3-15 parts of a reinforcing filler,
30-60 parts of semi-reinforcing filler,
0-15 parts of functional filler,
1-5 parts of a cross-linking agent,
1-5 parts of a tackifier.
The base resin is an ethoxy-terminated polymer and is one or more of the following structures:
R：-CH2CH3
structure (1): n is 500-
R：-CH2CH3
Structure (2): n is 100-500, R is-CH2CH3
R：-CH2CH3 
Structure (3): n is 20-500, m is 1-10
The sealant is a single-component dealcoholized silicone sealant which can be cured at room temperature. Wherein: the base resin adopts the three polymers, the two ends of the base resin are blocked by methyl isocyanate and triethoxysilane, and the alkoxysilane is connected with the carbamate through only one methylene group, so that the base resin has extremely high hydrolysis reaction activity and can have a sufficiently high curing rate without an organic tin heavy metal catalyst. The alpha, omega-dihydroxy polydimethylsiloxane of the base resin in CN111548764 needs to be fully cured in the presence of an organic tin heavy metal catalyst.
The sealant disclosed by the invention has the following characteristics:
(1) the putty is in a plasticine shape, can be freely shaped and trimmed before solidification, has good hand feeling and long operable time, and does not need auxiliary tools in the gluing process. Therefore, the adhesive can be used for filling, sealing and bonding positions of indoor doors and windows, joints, air-conditioning pores and the like, or used as a nail-free adhesive for bonding objects such as glass, metal, plastic, wood, stone and the like, or used as other adhesive seals, or used as a toy for personalized DIY manufacture, and the application is wider.
(2) The adhesive can be cured at room temperature, has high hardness and strength after curing, is waterproof and resistant to high and low temperatures, and achieves the effects of 0-level mildew resistance and V-0-level flame retardance after curing through the surface compactness of the adhesive and the interaction of the components in the formula.
(3) The VOC content is far lower than the requirement of the limit of volatile organic compounds of the adhesive of GB 33372-.
Further, the structure (1) is obtained by reacting alpha, omega-hydroxypropyl polydimethylsiloxane with methyl isocyanate triethoxysilane; the structure (2) and the structure (3) are obtained by reacting polypropylene glycol or hydroxyl-terminated polyurethane prepolymer with isocyanatomethyl triethoxysilane.
Preferably, the adhesion promoter may be used as a catalyst, and may be based on aminosilane, including one or more of γ -aminopropyltriethoxysilane, γ -aminopropylmethyldiethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldiethoxysilane, and the like.
More preferably, the tackifier further comprises a compound containing at least one of an epoxy group, an acrylic group, an alkoxysilyl group and a hydroxymethane group, wherein the compound is one or more of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma-methacryloxypropyltriethoxysilane, alkyltriethoxysilane and aryltriethoxysilane.
The tackifier of the sealant disclosed by the invention adopts aminosilane as a main material, and simultaneously takes a compound containing epoxy group, acrylic group, alkoxy silyl and hydroxymethyl group as an auxiliary material, wherein the two ends of the tackifier are blocked by methyl isocyanate trialkoxysilane, and the alkoxy silane is connected with carbamate only through one methylene group, so that the tackifier has extremely high hydrolysis reaction activity, and enough curing rate can be obtained by only adding aminosilane as the tackifier under the condition of no organic tin heavy metal catalyst; the compound containing an epoxy group, an acrylic group, an alkoxysilyl group, and a hydroxymethane group is used in combination with an amino silane coupling agent to improve adhesion, strength, and the like.
Preferably, the crosslinking agent comprises one or more of methyltriethoxysilane, n-ethyltriethoxysilane, isobutyltriethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, n-hexyltriethoxysilane, dodecyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, phenyldiethoxysilane, phenyltriethoxysilane, and ethyl orthosilicate, and condensates thereof. Further preferred is one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane and phenyltriethoxysilane.
The cross-linking agent of the sealant adopts the above materials, and the sealant has the advantages that the product is ethanol during curing, but not a possible carcinogenic butanone oxime generated during curing of an oxime type cross-linking agent, or corrosive and sharp acetic acid generated during curing of an acid type cross-linking agent, or methanol generated during curing of common alcohol type silicone adhesive or silane modified polyether sealant, and the sealant is green, environment-friendly and harmless to human bodies.
Preferably, the BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, being precipitated or fumed silica, silicon-aluminum mixed oxide, further preferably surface-modified hydrophobic fumed silica, commercially available as degusse R974, R106, R812, R972, Wacker's H20, H17, and the like.
Preferably, the particle size of the semi-reinforcing filler is 300-15000 mesh, more preferably 600-15000 mesh.
Preferably, the semi-reinforcing filler has an oil absorption value of 10 to 70g/100g, more preferably 10 to 40g/100 g.
Preferably, the semi-reinforcing filler is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate.
Further preferred are semi-reinforcing fillers subjected to surface modification treatment, such as aluminum hydroxide modified with silane, and vinyl-modified aluminum hydroxide (vinyl modification can lower the oil absorption value in the case where the semi-reinforcing filler is relatively small in particle diameter).
Preferably, the water content of the reinforcing filler and the semi-reinforcing filler is less than 1500ppm before use, and the water content can be controlled by adopting a drying treatment at 120 ℃ for 2 hours.
Preferably, the functional filler is: the pigment for adjusting the color can be titanium dioxide, ferric oxide, chromium oxide, carbon black, pearl powder, noctilucent powder, various color pastes after grinding treatment and the like; density-adjusted, linearly-contracted microspheres such as hollow microspheres, glass microspheres, magnetized microspheres, etc.; additives for adjusting weather resistance and temperature resistance, such as benzotriazole and triazine ultraviolet absorbers, hindered amine light stabilizers, hindered phenol antioxidants and the like.
In a second aspect, the invention provides a preparation method of an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature, which comprises the following steps:
(1) mixing and stirring the base resin and part of the cross-linking agent at the temperature of between room temperature and 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and continuously kneading and stirring under a vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into balls, kneading and stirring under vacuum condition, and controlling the temperature below 60 ℃ during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest of the cross-linking agent and the tackifier, kneading and stirring under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
Preferably, in the step (1), the mixing and stirring time is 10-60 min; in the step (2), the mixing and stirring time is 30-60 min; in the step (3), kneading and stirring time is 15-30 min; in the step (4), the kneading and stirring time is 10-30 min.
Compared with the prior art, the invention has the following technical effects:
(1) the sealant is plasticine-shaped, can be freely shaped and moulded before curing, has long operable time, does not need auxiliary tools in the gluing process, and has wide application field in the aspect of use.
(2) The sealant can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance.
(3) The sealant disclosed by the invention is low in VOC (volatile organic compound), does not contain a heavy metal catalyst, is high in safety, and is green and environment-friendly.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
An environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature comprises the following components in parts by weight: 30-60 parts of base resin, 3-15 parts of reinforcing filler, 30-60 parts of semi-reinforcing filler, 0-15 parts of functional filler, 1-5 parts of cross-linking agent and 1-5 parts of tackifier.
The base resin is an ethoxy-terminated polymer and is one or more of the following structures:
R：-CH2CH3
structure (1) n is 500-
R：-CH2CH3
Structure (2) n is 100-2CH3
R：-CH2CH3 
Structure (3) n-20-500, m-1-10
The tackifier comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane and the like; and the compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxy methyl alkyl group is one or more of gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, alkyl triethoxysilane and aryl triethoxysilane.
The cross-linking agent comprises one or more of methyl triethoxysilane, n-ethyl triethoxysilane, isobutyl triethoxysilane, n-octyl triethoxysilane, isooctyl triethoxysilane, n-hexyl triethoxysilane, dodecyl triethoxysilane, dimethyl diethoxy silane, vinyl triethoxysilane, vinyl methyl diethoxy silane, phenyl triethoxysilane, ethyl orthosilicate and condensates thereof. Further preferred is one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane and phenyltriethoxysilane.
The BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, being precipitated or fumed silica, silicon-aluminum mixed oxide, further preferably surface-modified hydrophobic fumed silica, commercially available as degusse R974, R106, R812, R972, Wacker's H20, H17, and the like.
The particle size of the semi-reinforcing filler is 300-15000 meshes, and is more preferably 600-15000 meshes; the oil absorption value is 10 to 70g/100g, and more preferably 10 to 40g/100 g. Is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate; more preferably, the surface is modified, for example, with silane-modified aluminum hydroxide or vinyl-modified aluminum hydroxide.
Before the reinforcing filler and the semi-reinforcing filler are used, the water content is less than 1500ppm, and the water content can be controlled by adopting drying treatment at 120 ℃ for 2 hours.
The functional filler is: the pigment for adjusting the color can be titanium dioxide, ferric oxide, chromium oxide, carbon black, pearl powder, noctilucent powder, color paste of various colors after grinding treatment and the like; density-adjusted, linearly-contracted microspheres such as hollow microspheres, glass microspheres, magnetized microspheres, etc.; additives for adjusting weather resistance and temperature resistance, such as benzotriazole and triazine ultraviolet absorbers, hindered amine light stabilizers, hindered phenol antioxidants and the like.
A preparation method of an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature comprises the following steps:
(1) mixing and stirring the base resin and part of the cross-linking agent for 10-60min at the temperature of room temperature to 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and then continuously kneading and stirring for 30-60min under the vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into dough, kneading and stirring under vacuum condition for 15-30min, and controlling the temperature below 60 deg.C during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest of the cross-linking agent and the tackifier, kneading and stirring for 15-30min under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
Example 1
1500g of a base resin of structure (1) (n-1500, R-CH)2CH3) And 25g of vinyltriethoxysilane, at room temperature, 10rpm for 10 min;
1200g of 12500 mesh, 1200ppm of water content and 32g/100g of vinyl-modified aluminum hydroxide and 120g of vinyl-modified aluminum hydroxide having a specific surface area of 200m were added in portions2Kneading and stirring the Wake H20 hydrophobic fumed silica with the water content of 800ppm into a mass, starting vacuum, continuously stirring at 40rpm for 50min, introducing cooling water during stirring, and keeping the temperature below 60 ℃;
adding 300g of 600-mesh rare earth long-acting noctilucent powder and 8g of American 3M hollow glass microspheres S37, kneading into a mass at the rotating speed of 10rpm, and continuously mixing and stirring for 20min at the rotating speed of 10rpm under the vacuum condition;
and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, breaking the vacuum by nitrogen, adding 25g of methyltriethoxysilane and 80g of gamma-aminopropyltriethoxysilane, stirring for 20min in vacuum at 10rpm, breaking the vacuum by nitrogen, extruding into blocks, and sealing and packaging to obtain the food-grade plasticine-shaped sealant with the noctilucent effect.
Example 2
2000g of a triethoxy-terminated base resin of structure (1) (n ═ 1200, R ═ CH)2CH3) And 50g of dimethyldiethoxysilane, at 50 ℃ and 20rpm for 60 min;
adding 2500g of 1250-mesh sodium stearate modified high-white aluminum hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of sodium stearate modified high-white aluminum hydroxide with the specific surface area of 200m in batches2Kneading and stirring the degussa R974 hydrophobic fumed silica with the water content of 1000ppm into a mass, starting vacuum, stirring at 40rpm for 60min, introducing cooling water, and keeping the temperature below 60 ℃;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of methyl triethoxysilane, 50g of gamma-aminopropyltriethoxysilane and 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white food-grade plasticine-shaped sealant.
Example 3
3000g of a base resin of structure (2) (n-240, R-CH)2CH3) And 50g of vinyltriethoxysilane, at room temperature, at a rotation speed of 20rpm for 10 min;
adding 2500g of 600 mesh talcum powder with water content of 900ppm and oil absorption value of 26g/100g and 600g of 250m specific surface area in batches2Kneading and stirring the degussa R106 hydrophobic fumed silica with the water content of 800ppm into a mass, starting vacuum, stirring at 40rpm for 30min, introducing cooling water, and keeping the temperature below 50 ℃;
adding 150g of iron oxide red, 35g of Basff ultraviolet absorbent UV326 and 35g of antioxidant Irganox 245, kneading for 10min at the rotating speed of 20rpm, and stirring for 10min at the rotating speed of 20rpm under the vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of vinyltriethoxysilane, 50g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 50g of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane under the protection of nitrogen, rotating at 20rpm, stirring in vacuum for 20min, breaking the vacuum by nitrogen, extruding into blocks, and sealing and packaging to obtain the red food-grade plasticine-shaped sealant.
Example 4
2500g of a base resin of structure (3) (n-150, m-2, R-CH)2CH3R' is
) And 50g of vinyltriethoxysilane, and mixing for 30min at the rotation speed of 20rpm under the protection of dry nitrogen at room temperature;
adding 2500g of talcum powder with water content of 1200ppm and oil absorption value of 37g/100g and 250g of talcum powder with specific surface area of 250m in batches2The preparation method comprises the following steps of (1) kneading and stirring Degussa R106 hydrophobic fumed silica with the water content of 800ppm into a mass, then starting vacuum, stirring at 40rpm for 30min, introducing cooling water during stirring, and keeping the temperature below 50 ℃;
adding 37.5g of carbon black, 100g of medium steel group GS26 hollow glass microspheres, 50g of Pasteur ultraviolet absorbent UV326 and 30g of antioxidant Irganox 245, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under the vacuum condition; and (2) under the condition of no stirring in vacuum, reducing the temperature to be below 50 ℃, adding 50g of vinyltriethoxysilane, 100g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 50g of gamma-methacryloxypropyltriethoxysilane under the protection of nitrogen, rotating at 10rpm, stirring in vacuum for 20min, breaking the vacuum by nitrogen, extruding into blocks, sealing and packaging to obtain the black food-grade plasticine-shaped sealant.
Comparative example 1
2000g of alpha, omega-dihydroxypolydimethylsiloxane
200g of methyl tributyrinoxime silane and 80g of vinyl tributyrinoxime silane are mixed for 60min at the temperature of 60 ℃ and the rotating speed of 20 rpm;
2500g of 1250 mesh sodium stearate modified high-white aluminium hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of specific surface area of 200m are added in batches2(g) Degussa R974 hydrophobic fumed silica with water content of 1000ppm is kneaded, stirred and agglomerated, then vacuum is started, and stirring is carried out at 40rpmIntroducing cooling water for 60min, and keeping the temperature below 60 deg.C;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of methyl triethoxysilane, 50g of gamma-aminopropyl triethoxysilane and 50g N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white plasticine-shaped sealant.
Comparative example 2
2000g of alpha, omega-dihydroxypolydimethylsiloxane
And 200g of methyl tributyrinoxime silane and 80g of vinyl tributyrinoxime silane, at 60 ℃ and 20rpm for 60 min;
2500g of 1250 mesh sodium stearate modified high-white aluminium hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of specific surface area of 200m are added in batches2The preparation method comprises the following steps of (1) kneading and stirring Degussa R974 hydrophobic fumed silica with the water content of 1000ppm into a mass, starting vacuum, stirring at 40rpm for 60min, introducing cooling water, and keeping the temperature below 60 ℃;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to be below 50 ℃, adding 50g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 3g of dibutyltin dilaurate under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white plasticine-shaped sealant.
Performance test the operable time test: placing the 20mm by 20mm rubber block at 23 ℃ under the standard condition of 55% RH, kneading the rubber block every half hour, if the rubber block can be molded again by kneading, the rubber block is operable if the surface is smooth and has no particles, if the surface is skinned, cured and molded again, particles and blocks appear, the appearance is uneven, the rubber block is inoperable, the operable time is recorded as the time for last molding, and the precision is 0.5 h.
And (3) testing initial adhesion: two marble blocks with the mass of-2 kg are bonded together by 5g of plasticine-like silicone adhesive, after the marble blocks are placed for 5s, one marble block is placed at the edge of a table, the other marble block is suspended, whether the suspended marble slides downwards or not is observed in 5s, if the sliding downwards does not exceed 1cm, the initial adhesion is marked to be large, otherwise, the initial adhesion is small.
The plasticity before curing is measured with reference to GB/T12828-2006 "determination of plasticity and recovery values of crude and unvulcanized rubber mixes", the temperature during the test is controlled at 23 + -2 ℃ respectively, 2cm3 of silicone rubber is taken to be made into a cylinder with a diameter of 10mm, placed between parallel plates on an instrument, then a force of 49N is applied to the top plate to deform the sample for 90 seconds, the final gap between the plates is measured, and this value is multiplied by 100;
testing the hardness of the silicone adhesive by using GB/T531.2-2009 Experimental method for pressing hardness of vulcanized rubber or thermoplastic rubber;
the tensile strength and the elongation at break of the silicone rubber are detected by GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber;
the mildew resistance of the cured film is detected by GB-T1741-2020 paint film mildew resistance determination method;
the content of volatile organic compounds of the sealant is tested by GB 33372-2020 volatile organic compound Limit of adhesive, and the VOC of the home decoration silicone sealant and the VOC of the home decoration MS sealant are respectively less than 100g/kg and 50g/kg according to the standard;
and (3) detecting the flame retardant property of the sealant by adopting a vertical combustion test method according to UL 94V-0, V-1 and V-2 flammability standards.
The results of all the tests of examples 1 to 4 and comparative examples 1 to 2 are shown in the following table.
As can be seen by comparing the data in the table above:
examples 1-4 all had operating times > 2h, large initial tack, grade 0 mildew resistance and V-0 flame retardancy, with low VOC's of less than 30 g/kg.
Comparative example 1 the resin of example 4 was changed to α, ω -dihydroxypolydimethylsiloxane of the same viscosity and the crosslinking agent was changed to a ketoxime type crosslinking agent, and the gum obtained was plasticine-like in appearance but did not cure after standing in air for 48 hours in the absence of a tin catalyst.
Comparative example 2 after a certain amount of organotin catalyst was added to the formulation of comparative example 1, the operation time was short, vulcanization and skinning started in more than half an hour, and molding could not be performed again, the VOC was slightly high, the butanone oxime smell was heavy during the operation, and environmental protection was not sufficient.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The safe and environment-friendly single-component plasticine-shaped silicone sealant is characterized in that: the paint comprises the following components in parts by weight:
30-60 parts of base resin,
3 to 15 parts of reinforcing filler,
30-60 parts of semi-reinforcing filler,
0-15 parts of functional filler,
1-5 parts of a cross-linking agent,
1-5 parts of a tackifier;
the base resin is an ethoxy-terminated polymer and is one or more of the following structures:
structure (1): n is 500-
Structure (2): n is 100-
Structure (3): n is 20-500, m is 1-10.
2. The sealant of claim 1, wherein:
the structure (1) is obtained by reacting alpha, omega-hydroxypropyl polydimethylsiloxane with methyl isocyanate triethoxysilane;
the structure (2) and the structure (3) are obtained by reacting polypropylene glycol or hydroxyl-terminated polyurethane prepolymer with isocyanatomethyl triethoxysilane.
3. The sealant of claim 1, wherein:
the tackifier comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane and the like; and/or
The cross-linking agent comprises one or more of methyl triethoxysilane, n-ethyl triethoxysilane, isobutyl triethoxysilane, n-octyl triethoxysilane, isooctyl triethoxysilane, n-hexyl triethoxysilane, dodecyl triethoxysilane, dimethyl diethoxy silane, vinyl triethoxysilane, vinyl methyl diethoxy silane, phenyl triethoxysilane, ethyl orthosilicate and condensates thereof.
4. A sealant according to claim 3, wherein:
the tackifier also comprises a compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxyl methyl alkyl group; and/or
The cross-linking agent comprises one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane.
5. The sealant of claim 4 wherein: the compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxyl methyl group is one or more of gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, alkyl triethoxysilane and aryl triethoxysilane.
6. The sealant of claim 1, wherein:
the BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, is silicon dioxide, silicon-aluminum mixed oxide by a precipitation method or a gas phase method;
the particle size of the semi-reinforcing filler is 300-15000 meshes, and the oil absorption value is 10-70g/100 g; is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate;
the water content of the reinforcing filler and the semi-reinforcing filler before use is less than 1500 ppm.
7. The sealant of claim 1, wherein:
the reinforcing filler is surface-modified hydrophobic fumed silica;
the semi-reinforcing filler has the particle size of 600-15000 meshes and the oil absorption value of 10-40g/100 g.
8. The sealant according to claim 1 or 7, wherein: the semi-reinforcing filler is subjected to surface modification treatment.
9. A process for preparing the sealant according to any one of claims 1 to 8, comprising the steps of:
(1) mixing and stirring the base resin and part of the cross-linking agent at the temperature of between room temperature and 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and continuously kneading and stirring under a vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into balls, kneading and stirring under vacuum condition, and controlling the temperature below 60 ℃ during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest crosslinking agent and the tackifier, kneading and stirring under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
10. The method of claim 9, wherein:
in the step (1), the mixing and stirring time is 10-60 min;
in the step (2), the mixing and stirring time is 30-60 min;
in the step (3), kneading and stirring time is 15-30 min;
in the step (4), the kneading and stirring time is 10-30 min.
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Cited By (1)
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| CN115093779A (en) * | 2022-06-24 | 2022-09-23 | 广州集泰化工股份有限公司 | Solvent-free transparent waterproof coating and preparation method thereof |
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Application publication date: 20220603 |