CN115010903B - 基于巯基点击反应的硅烷封端树脂及其合成方法 - Google Patents
基于巯基点击反应的硅烷封端树脂及其合成方法 Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000011347 resin Substances 0.000 title claims abstract description 57
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 41
- 238000012650 click reaction Methods 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960003151 mercaptamine Drugs 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyoxypropylene Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-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
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 3
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- CGQIJXYITMTOBI-UHFFFAOYSA-N hex-5-enyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCC=C CGQIJXYITMTOBI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 3
- JHYKJJIJPWNOME-UHFFFAOYSA-N 1,4a,8-triazido-2,3,4,5,6,7-hexahydro-1H-naphthalene Chemical compound N(=[N+]=[N-])C12CCCC(=C2C(CCC1)N=[N+]=[N-])N=[N+]=[N-] JHYKJJIJPWNOME-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
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- 230000009471 action Effects 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 2
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
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- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 2
- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 claims description 2
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 5
- HJXABDHMKBUSNG-UHFFFAOYSA-N but-1-ene triethoxysilane Chemical compound C(C)O[SiH](OCC)OCC.CCC=C HJXABDHMKBUSNG-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000000565 sealant Substances 0.000 abstract description 5
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- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
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- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- LUZRKMGMNFOSFZ-UHFFFAOYSA-N but-3-enyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCC=C LUZRKMGMNFOSFZ-UHFFFAOYSA-N 0.000 description 2
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- UVDDHYAAWVNATK-VGKOASNMSA-L (z)-4-[dibutyl-[(z)-4-oxopent-2-en-2-yl]oxystannyl]oxypent-3-en-2-one Chemical compound CC(=O)\C=C(C)/O[Sn](CCCC)(CCCC)O\C(C)=C/C(C)=O UVDDHYAAWVNATK-VGKOASNMSA-L 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08G18/83—Chemically modified polymers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
本发明属于高分子材料领域,具体涉及一种基于巯基点击反应的硅烷封端树脂及其合成方法。合成方法如下:将1.00当量份大分子二元醇和0.10~0.40当量份大分子三元醇通过升温和真空除水,投入2.30~3.20当量份液态二异氰酸酯,控制R值等于2,在70~80℃下反应得到异氰酸酯基封端树脂,20~35℃下与半胱胺反应得到巯基封端树脂,在40~60℃与端烯基或环氧基硅烷,通过巯‑烯点击反应或巯基‑环氧点击反应制得硅烷封端树脂。该合成路线工艺简便、条件温和、原料廉价易得,硅烷封端树脂具有高度支化的拓扑结构,比线型结构具有更为丰富的硅烷基团,能大幅提升树脂对基材的粘接能力,赋予更快的反应速率,用于密封剂或胶粘剂可显著缩短固化时间、提升施工效率。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种基于巯基点击反应的硅烷封端树脂及其合成方法。
背景技术
硅烷封端树脂具有聚醚的柔顺性和耐低温性,硅烷封端基良好的湿气固化性、粘结性,是胶粘剂和密封剂的主体原料。近年来,硅烷封端聚醚的研究工作进展迅速,由于其具有优异的粘结性能和加工性能,被广泛应用在超高层建筑、轨道交通、无痕组装领域。
研究硅烷封端树脂的重点在于硅烷改性技术,制备硅烷改性聚醚密封剂用的基础树脂-硅烷封端聚醚树脂是重要的原料,目前主要有日本Kaneka、德国瓦克等推出了相关成熟的产品。国内对于硅烷改性密封剂的制备和性能研究处于起步阶段,对于硅烷封端树脂合成技术的研究则较少,且研究方向主要集中于聚氨酯预聚体法和烯丙基-硅氢加成法。这两种方法都是以较低分子量的聚丙二醇为起始原料,合成过程中都需要进一步扩链增大聚醚树脂的分子量,以获得高弹性和良好的机械性能,但这也增加了合成步骤,使得合成和处理过程繁琐,尤其是后一种方法,涉及到除盐、除杂等纯化过程,增加了工业化生产的技术难点。另外,聚氨酯预聚体法合成得到的树脂含有较多的氨基甲酸酯极性基团,增大了基础树脂黏度,继而影响密封剂的制备和性能。
本发明开发出新的合成路线,即先用大分子二元醇、大分子三元醇、液态二异氰酸酯和半胱胺合成巯基封端树脂,再通过巯基封端树脂与端烯基或环氧基硅烷的点击反应合成出硅烷封端树脂,且该合成路线工艺简便、条件温和、原料廉价易得,适合工业化生产。将该硅烷封端树脂用于密封剂或胶粘剂可显著缩短固化时间、提升施工效率。
发明内容
为解决上述问题,本发明提供了一种基于巯基点击反应的硅烷封端树脂及其合成方法。
本发明涉及的基于巯基点击反应的硅烷封端树脂,由以下摩尔当量份的原料制得:
大分子二元醇1.00份;
大分子三元醇0.10~0.40份
液态二异氰酸酯2.30~3.20份
半胱胺2.30~3.20份
端烯基或环氧基硅烷2.30~3.20份。
所述基于巯基点击反应的硅烷封端树脂的合成方法,包括如下步骤:
(1)往反应釜中投入配方量的大分子二元醇和大分子三元醇,升温至105~120℃,控制真空度不大于-0.095MPa,在该条件下除水1~2小时;
(2)降温至70~80℃,投入配方量的液态二异氰酸酯,使异氰酸酯与羟基官能团的比值(R值)等于2,投入0.05%质量分数的二月桂酸二丁基锡,氮气保护下搅拌2~4小时,得到异氰酸酯基封端树脂;
(3)降温至20~35℃,投入配方量的半胱胺,氮气保护下搅拌2~4小时,得到巯基封端树脂;
(4)升温至40~60℃,投入配方量的端烯基或环氧基硅烷,并投入0.05%质量分数的相应催化剂,氮气保护下搅拌2~4小时,得到硅烷封端树脂,计量出料,密封包装得产品。
所述基于巯基点击反应的硅烷封端树脂,通过巯基封端树脂在催化剂作用下与端烯基或环氧基硅烷的点击反应来合成;
其中,与端烯基硅烷反应的催化剂为偶氮化合物或有机过氧化物,优选为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化苯甲酰、过氧化苯甲酰叔丁酯和过氧化甲乙酮中的一种或多种混合物;
与环氧基硅烷反应的催化剂为无水氢氧化锂、无水碳酸钾、四丁基氟化铵、苄基三乙基氯化铵、四丁基溴化铵、四丁基硫酸氢铵、二氢三氟四丁基铵、1,5,7-三叠氮双环(4.4.0)癸-5-烯,二氮杂二环、二氮杂双环、三苯基膦、三正丁基膦、三异丙基磷、三苄基膦、三环戊基膦、三(二甲胺基)膦、三吡咯烷膦、三正辛基膦中的一种或多种混合物。
所述巯基封端树脂由大分子二元醇、大分子三元醇、液态二异氰酸酯和半胱胺合成。
优选地,所述大分子二元醇为端羟基聚丁二烯、氢化端羟基聚丁二烯、聚酯二元醇、聚乙二醇、聚氧化丙烯二醇、聚四亚甲基醚二醇中的一种或多种混合物,数均分子量500~8000g/mol。
优选地,所述大分子三元醇为聚氧化丙烯三醇,数均分子量500~3000g/mol。
优选地,所述液态二异氰酸酯为异佛尔酮二异氰酸酯IPDI、二环己基甲烷二异氰酸酯HMDI、1,6-己二异氰酸酯HDI、多亚甲基多苯基多异氰酸酯PAPI、二聚酸二异氰酸酯DDI中的一种或多种混合物。
优选地,所述端烯基硅烷为乙烯基三乙氧基硅烷(CAS号78-08-0)、乙烯基三甲氧基硅烷(CAS号2768-02-7)、乙烯基三异丙氧基硅烷(CAS号18023-33-1)、乙烯基三(2-甲氧基乙氧基)硅烷(CAS号1067-53-4)、烯丙基三甲氧基硅烷(CAS号2551-83-9)、烯丙基三乙氧基硅烷(CAS号2550-04-1)、甲基乙烯基二甲氧基硅烷(CAS号16753-62-1)、3-丁烯三乙氧基硅烷(CAS号57813-67-9)、二乙氧基甲基乙烯基硅烷(CAS号5507-44-8)、11-烯丙氧基十一烷基三甲氧基硅烷(CAS号1196453-35-6)、5-己烯基三乙氧基硅烷(CAS号52034-14-7)、5-己烯基三甲氧基硅烷(CAS号58751-56-7)中的一种或多种混合物。
优选地,所述环氧基硅烷为3-(2,3-环氧丙氧)丙基三甲氧基硅烷(CAS号2530-83-8)、3-缩水甘油醚氧基丙基三乙氧基硅烷(CAS号2602-34-8)、3-缩水甘油醚氧基丙基甲基二乙氧基硅烷(CAS号2897-60-1)、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷(CAS号65799-47-5)、2-(3,4-环氧环己烷)乙基三甲氧基硅烷(CAS号3388-04-3)、2-(3,4-环氧环己烷基)乙基三乙氧基硅烷(CAS号10217-34-2)中的一种或多种混合物。
与现有技术相比,本发明的有益效果是:
1.本发明的基于巯基点击反应的硅烷封端树脂,巧妙运用二官能度和三官能度大分子多元醇,获得高度支化结构,采用巯-烯或巯基-环氧点击反应实现端基转换,高度支化的拓扑结构比起线型结构,具有更为丰富的硅烷基团,能大幅提升树脂对基材的粘接能力,赋予更快的反应速率,用于密封剂或胶粘剂可显著缩短固化时间、提升施工效率。
2.本发明的基于巯基点击反应的硅烷封端树脂,合成路线工艺简便、条件温和、原料廉价易得,适合工业化生产。
具体实施实例
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
本发明实施例及对比例中实验所用的原料如下,但是不限于以下原料,本发明只是以下原料为具体例子来进一步具体说明本发明中所述基于巯基点击反应的硅烷封端树脂的效果:
聚氧化丙烯二醇:DL-2000,数均分子量2000g/mol,蓝星东大。
聚氧化丙烯三醇:C305,数均分子量500g/mol,一诺威。
液态二异氰酸酯:异佛尔酮二异氰酸酯IPDI,科思创。
端烯基硅烷:乙烯基三甲氧基硅烷,KH-171,南京经天纬。
环氧基硅烷:3-(2,3-环氧丙氧)丙基三甲氧基硅烷,KH-560,上海探圭。
催化剂:偶氮二异丁腈AIBN,山东旭晨化工;无水氢氧化锂LiOH,上海欧化。
半胱胺,湖北启牛;2-巯基乙醇,山东艾特,二月桂酸二丁基锡,阿拉丁。
本发明设置实施例1~6及对比例1~2,按照二/三官能度大分子多元醇搭配方式设计配方。
实施例和对比例按照相同方法合成,获得基于巯基点击反应的硅烷封端树脂,其合成方法如下:(1)往反应釜中投入0.100mol DL-2000和0.010~0.040mol C305,升温至110℃,控制真空度不大于-0.095MPa,在该条件下除水2小时;(2)降温至80℃,投入0.230~0.320mol IPDI,使异氰酸酯与羟基官能团的比值(R值)等于2,投入0.05%质量分数的二月桂酸二丁基锡,氮气保护下搅拌4小时;(3)降温至25℃,投入0.230~0.320mol半胱胺或2-巯基乙醇,氮气保护下搅拌4小时;(4)升温至60℃,投入0.230~0.320mol KH-171或KH-560,并投入0.05%质量分数的相应催化剂AIBN(针对KH-171)或LiOH(针对KH-560),氮气保护下搅拌4小时,得到硅烷封端树脂,计量出料,密封包装得产品。
实施例1~6及对比例1~2的基于巯基点击反应的硅烷封端树脂的配方如表1所示:
表1基于巯基点击反应的硅烷封端树脂的配方
将表1上述产物与0.005当量份(相对于基于巯基点击反应的硅烷封端树脂)N-(2-氨乙基)-3-氨丙基三甲氧基硅烷和0.00001当量份的双(乙酰丙酮酸)二丁基锡在动混机中搅拌混合15分钟,挤出制样,参考GB/T 13477.5-2002规定的A法进行测试表干时间,参考GB/T 32369-2015方法二规定的方法测试24小时的固化程度,以检验硅烷是否成功封端。
实施例1~6及对比例1~2的基于巯基点击反应的硅烷封端树脂的性能如表2所示:
表2基于巯基点击反应的硅烷封端树脂的性能
表2实施例1~6表明,无论大分子多元醇和液态二异氰酸酯的配比如何搭配,只要通过半胱胺将端基转换成巯基,其产物均能与硅烷进行点击反应,获得链末端为硅烷基团的高端支化树脂,最终产物均能表干和深层固化,说明该合成路线的关键在于获得巯基封端的树脂,然后再与端烯基或环氧基硅烷进行点击反应,将链末端基团转换成硅烷基团。相比之下,对比例1~2采用2-巯基乙醇,其羟基和巯基在室温下的活性相当但活性较低,都有可能与预聚体发生反应,巯基被消耗或未接枝于预聚体,因此获得巯基封端的高度支化树脂,最终不能将链末端转换成硅烷基团。
以上所述仅为本发明的实施例而已,并不用于限制本发明。本发明可以有各种合适的更改和变化。凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种基于巯基点击反应的硅烷封端树脂,其特征在于,由以下摩尔当量份的原料通过巯-烯点击反应或巯基-环氧点击反应制得:大分子二元醇1.00份、大分子三元醇0.10~0.40份、液态二异氰酸酯2.30~3.20份、半胱胺2.30~3.20份、端烯基或环氧基硅烷2.30~3.20份;
所述大分子二元醇为端羟基聚丁二烯、氢化端羟基聚丁二烯、聚酯二元醇、聚乙二醇、聚氧化丙烯二醇、聚四亚甲基醚二醇中的一种或多种混合物,数均分子量500~8000g/mol;
所述大分子三元醇为聚氧化丙烯三醇,数均分子量500~3000g/mol;
所述液态二异氰酸酯为异佛尔酮二异氰酸酯IPDI、二环己基甲烷二异氰酸酯HMDI、1,6-己二异氰酸酯HDI、多亚甲基多苯基多异氰酸酯PAPI、二聚酸二异氰酸酯DDI中的一种或多种混合物;
所述端烯基硅烷为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、烯丙基三甲氧基硅烷、烯丙基三乙氧基硅烷、甲基乙烯基二甲氧基硅烷、3-丁烯三乙氧基硅烷、二乙氧基甲基乙烯基硅烷、11-烯丙氧基十一烷基三甲氧基硅烷、5-己烯基三乙氧基硅烷、5-己烯基三甲氧基硅烷中的一种或多种混合物;
所述环氧基硅烷为3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅烷、3-[(2,3)-环氧丙氧]丙基甲基二甲氧基硅烷、2-(3,4-环氧环己烷)乙基三甲氧基硅烷、2-(3,4-环氧环己烷基)乙基三乙氧基硅烷中的一种或多种混合物;
所述基于巯基点击反应的硅烷封端树脂的合成方法,包括如下步骤:
(1)往反应釜中投入配方量的大分子二元醇和大分子三元醇,升温至105~120℃,控制真空度不大于-0.095MPa,在该条件下除水1~2小时;
(2)降温至70~80℃,投入配方量的液态二异氰酸酯,使异氰酸酯与羟基官能团的比值等于2,投入0.05%质量分数的二月桂酸二丁基锡,氮气保护下搅拌2~4小时,得到异氰酸酯基封端树脂;
(3)降温至20~35℃,投入配方量的半胱胺,氮气保护下搅拌2~4小时,得到巯基封端树脂;
(4)升温至40~60℃,投入配方量的端烯基或环氧基硅烷,并投入0.05%质量分数的相应催化剂,氮气保护下搅拌2~4小时,得到硅烷封端树脂,计量出料,密封包装得产品。
2.根据权利要求1所述的基于巯基点击反应的硅烷封端树脂,其特征在于,所述巯基封端树脂在催化剂作用下与端烯基或环氧基硅烷发生点击反应;
其中,与端烯基硅烷反应的催化剂为偶氮化合物或有机过氧化物;
与环氧基硅烷反应的催化剂为无水氢氧化锂、无水碳酸钾、四丁基氟化铵、苄基三乙基氯化铵、四丁基溴化铵、四丁基硫酸氢铵、二氢三氟四丁基铵、1,5,7-三叠氮双环(4.4.0)癸-5-烯,二氮杂二环、二氮杂双环、三苯基膦、三正丁基膦、三异丙基磷、三苄基膦、三环戊基膦、三(二甲胺基)膦、三吡咯烷膦、三正辛基膦中的一种或多种混合物。
3.根据权利要求2所述的基于巯基点击反应的硅烷封端树脂,其特征在于,所述偶氮化合物为偶氮二异丁腈、偶氮二异庚腈或偶氮二异丁酸二甲酯。
4.根据权利要求2所述的基于巯基点击反应的硅烷封端树脂,其特征在于,所述有机过氧化物为过氧化苯甲酰、过氧化苯甲酰叔丁酯或过氧化甲乙酮。
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