CN108752578A - A kind of preparation method of polyether-based organic silicon surfactant - Google Patents
A kind of preparation method of polyether-based organic silicon surfactant Download PDFInfo
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- 229920000570 polyether Polymers 0.000 title claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract 3
- 229910052710 silicon Inorganic materials 0.000 title claims abstract 3
- 239000010703 silicon Substances 0.000 title claims abstract 3
- -1 mercaptopropylsiloxane Chemical class 0.000 claims abstract description 43
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 33
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 24
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 244000028419 Styrax benzoin Species 0.000 claims abstract description 12
- 235000000126 Styrax benzoin Nutrition 0.000 claims abstract description 12
- 235000008411 Sumatra benzointree Nutrition 0.000 claims abstract description 12
- 229960002130 benzoin Drugs 0.000 claims abstract description 12
- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- XJYOKAGZKHRYDJ-UHFFFAOYSA-N SCCC[SiH2]C(O[Si](C)(C)C)O[Si](C)(C)C Chemical compound SCCC[SiH2]C(O[Si](C)(C)C)O[Si](C)(C)C XJYOKAGZKHRYDJ-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- HCZBMENVWKFZDJ-UHFFFAOYSA-N 3-trimethylsilylpropane-1-thiol Chemical group C[Si](C)(C)CCCS HCZBMENVWKFZDJ-UHFFFAOYSA-N 0.000 claims description 4
- WMTHOCDKBFTQDR-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropane-1-thiol Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)CCCS WMTHOCDKBFTQDR-UHFFFAOYSA-N 0.000 claims description 4
- FKPFKJPGENKTQL-UHFFFAOYSA-N 1-[dimethyl(trimethylsilyloxy)silyl]propane-1-thiol Chemical compound SC(CC)[Si](O[Si](C)(C)C)(C)C FKPFKJPGENKTQL-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- DWUCCPNOMFYDOL-UHFFFAOYSA-N propyl(sulfanyl)silicon Chemical compound CCC[Si]S DWUCCPNOMFYDOL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006596 Alder-ene reaction Methods 0.000 abstract 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- HLPWCQDWRYCGLK-UHFFFAOYSA-N ethyl-methyl-bis(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](C)(CC)O[Si](C)(C)C HLPWCQDWRYCGLK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004754 hydrosilicons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
一种聚醚基有机硅表面活性剂的制备方法，该制备方法包括如下步骤：（1）将巯丙基硅氧烷、不饱和聚醚、溶剂和安息香二甲醚加入单口烧瓶中，进行巯烯反应，反应时间为30min~4小时；（2）反应结束后将未反应完单体、溶剂和残留引发剂除去，得聚醚基有机硅表面活性剂。本发明通过巰丙基硅烷与不饱和聚醚反应制备的具有优良表面活性的聚醚基有机硅表面活性剂，该方法具有原料便宜易得、操作简单、后处理简单的优点，避免使用价格昂贵的催化剂，有利于聚醚基有机硅表面活性剂的工业化生产及应用推广。
A preparation method of a polyether-based silicone surfactant, the preparation method comprising the following steps: (1) adding mercaptopropylsiloxane, unsaturated polyether, solvent and benzoin dimethyl ether into a single-necked flask, and carrying out mercaptopropylsiloxane ene reaction, the reaction time is 30min~4 hours; (2) After the reaction, the unreacted monomer, solvent and residual initiator are removed to obtain a polyether-based silicone surfactant. The polyether-based organic silicon surfactant with excellent surface activity prepared by the reaction of mercaptopropylsilane and unsaturated polyether in the present invention has the advantages of cheap and easy-to-obtain raw materials, simple operation and simple post-treatment, and avoids expensive use The catalyst is beneficial to the industrial production and application promotion of the polyether-based silicone surfactant.
Description
技术领域technical field
本发明涉及一种聚醚基有机硅表面活性剂的制备方法。The invention relates to a preparation method of a polyether-based silicone surfactant.
背景技术Background technique
有机硅表面活性剂是以硅氧/碳烷为疏水链节，连接一个或多个亲水基团组成的一类新型高效的表面活性剂。不但具有比烷烃类表面活性剂更优良的表面活性和“超铺展”性，而且具备有机硅材料的耐高低温、耐气候老化、无毒生理惰性等优异的性能。该类有机硅表面活性剂以其优异的性能广泛应用于聚氨酯泡沫、农药、纺织助剂、日用助剂、油田化学品等领域。随着有机硅材料进一步发展和对有机硅下游产品深入的开发，有机硅表面活性剂的品种以及制备方法也将不断的增加，应用领域也会不断扩大，这都是表面活性剂的发展方向与研究热点。Silicone surfactants are a new type of high-efficiency surfactants, which are composed of siloxane/carbonane as hydrophobic chain links and one or more hydrophilic groups. Not only has better surface activity and "super-spreading" properties than alkane surfactants, but also has excellent properties such as high and low temperature resistance, weather aging resistance, non-toxic and physiological inertia of silicone materials. This type of silicone surfactant is widely used in polyurethane foam, pesticides, textile auxiliaries, daily auxiliaries, oilfield chemicals and other fields due to its excellent performance. With the further development of silicone materials and the in-depth development of silicone downstream products, the varieties and preparation methods of silicone surfactants will also continue to increase, and the application fields will continue to expand. This is the development direction of surfactants and Research hotspots.
聚醚型有机硅表面活性剂是目前应用最多的品种，如Silwet系列等，其主要是含氢硅烷或硅油与不饱和聚醚在贵金属催化剂作用下进行硅氢加成制备而成。如中国专利CN107759792 A用多甲基硅氧烷和烯丙基聚醚采用硅氢加成反应制备农用有机硅表面活性剂。该制备方法反应时间长且需以铂等贵金属为催化剂的条件下方可进行。文献（OrganicLetters,2011,13 (22) :6006-6009）采用巯烯反应高效的制备聚醚型有机硅表面活性剂，但是需要制备含巯基聚醚，不太适合工业化生产。故，开发高效、高产率有机硅表面活性的合成方法十分必要。Polyether-type silicone surfactants are currently the most widely used varieties, such as Silwet series, etc., which are mainly prepared by hydrosilylation of hydrosilane or silicone oil and unsaturated polyether under the action of a noble metal catalyst. For example, Chinese patent CN107759792 A uses polymethylsiloxane and allyl polyether to prepare agricultural silicone surfactant by hydrosilylation reaction. The preparation method has a long reaction time and can be carried out under the condition that platinum and other precious metals are used as catalysts. The literature (Organic Letters, 2011, 13 (22): 6006-6009) uses mercaptoene reaction to efficiently prepare polyether-type silicone surfactants, but it needs to prepare mercapto-containing polyethers, which is not suitable for industrial production. Therefore, it is necessary to develop an efficient and high-yield synthetic method for silicone surface activity.
发明内容Contents of the invention
本发明其目的就在于提供一种聚醚基有机硅表面活性剂的制备方法，本发明通过巰丙基硅烷与不饱和聚醚反应制备的具有优良表面活性的聚醚基有机硅表面活性剂，该方法具有原料便宜易得、操作简单、后处理简单的优点，避免使用价格昂贵的催化剂，有利于聚醚基有机硅表面活性剂的工业化生产及应用推广。Its purpose of the present invention is just to provide a kind of preparation method of polyether-based silicone surfactant, the polyether-based silicone surfactant with excellent surface activity prepared by the reaction of mercaptopropylsilane and unsaturated polyether in the present invention, The method has the advantages of cheap and easy-to-obtain raw materials, simple operation and simple post-treatment, avoids the use of expensive catalysts, and is beneficial to the industrialized production and application of polyether-based silicone surfactants.
为实现上述目的而采取的技术方案是，一种聚醚基有机硅表面活性剂的制备方法，该制备方法包括如下步骤：The technical solution adopted for achieving the above object is a preparation method of a polyether-based silicone surfactant, the preparation method comprising the following steps:
（1）将巯丙基硅氧烷、不饱和聚醚、溶剂和安息香二甲醚加入单口烧瓶中，进行巯烯反应，反应时间为30min~4小时；(1) Add mercaptopropylsiloxane, unsaturated polyether, solvent and benzoin dimethyl ether into a single-necked flask to carry out mercaptoene reaction, and the reaction time is 30 minutes to 4 hours;
（2）反应结束后将未反应完单体、溶剂和残留引发剂除去，得聚醚基有机硅表面活性剂。(2) After the reaction, unreacted monomers, solvents and residual initiators are removed to obtain a polyether-based silicone surfactant.
所述巯丙基硅氧烷是巯丙基三甲基硅烷、巯丙基-三(三甲基硅氧基)硅烷、巯丙基-二(三甲基硅氧基)甲基硅烷、巯丙基-二(三甲基硅氧基)甲基硅烷、巯丙基-二(乙基二甲基硅氧基)甲基硅烷、巯丙基-二(丙基二甲基硅氧基)甲基硅烷、巯丙基-二(丁基二甲基硅氧基)甲基硅烷、巯丙基-二(苯基二甲基硅氧基)甲基硅烷、1-巯丙基五甲基二硅氧烷、1-巯丙基-3-乙基四甲基二硅氧烷、1-巯丙基-3-丙基四甲基二硅氧烷、1-巯丙基-3-丁基四甲基二硅氧烷、1-巯丙基 -3-苯基四甲基二硅氧烷中的一种。The mercaptopropylsiloxane is mercaptopropyltrimethylsilane, mercaptopropyl-tri(trimethylsiloxy)silane, mercaptopropyl-bis(trimethylsiloxy)methylsilane, mercaptopropyl Propyl-bis(trimethylsiloxy)methylsilane, Mercaptopropyl-bis(ethyldimethylsiloxy)methylsilane, Mercaptopropyl-bis(propyldimethylsiloxy) Methylsilane, Mercaptopropyl-bis(butyldimethylsiloxy)methylsilane, Mercaptopropyl-bis(phenyldimethylsiloxy)methylsilane, 1-mercaptopropylpentamethyl Disiloxane, 1-mercaptopropyl-3-ethyltetramethyldisiloxane, 1-mercaptopropyl-3-propyltetramethyldisiloxane, 1-mercaptopropyl-3-butyl One of tetramethyldisiloxane and 1-mercaptopropyl-3-phenyltetramethyldisiloxane.
所述不饱和聚醚为羟基封端不饱和聚醚和甲基封端不饱和聚醚，其中乙二醇链节数可为3~50，丙氧基链节数为0~20。The unsaturated polyether is a hydroxyl-terminated unsaturated polyether and a methyl-terminated unsaturated polyether, wherein the number of ethylene glycol chain members can be 3-50, and the number of propoxyl chain members is 0-20.
所述巯丙基硅氧烷与不饱和聚醚的摩尔比为1~1.3：1。The molar ratio of the mercaptopropylsiloxane to the unsaturated polyether is 1-1.3:1.
所述溶剂为甲醇、乙醇、四氢呋喃、异丙醇、丁醇、乙腈、N,N-二甲基甲酰胺中的一种或其混合溶剂。The solvent is one of methanol, ethanol, tetrahydrofuran, isopropanol, butanol, acetonitrile, N,N-dimethylformamide or a mixed solvent thereof.
所述安息香二甲醚用量为1%~5% 质量分数。The amount of benzoin dimethyl ether is 1% to 5% by mass fraction.
有益效果Beneficial effect
与现有技术相比本发明具有以下优点。Compared with the prior art, the present invention has the following advantages.
1.本发明制备的聚醚基有机硅表面活性剂γCMC小于28 mN/m，具有高表面活性，且不存在同分异构体对其表面活性的影响，可用于农药助剂、药物缓释、功能性纳米材料、纺织加工助剂等领域；1. The polyether-based organosilicon surfactant γ CMC prepared by the present invention is less than 28 mN/m, has high surface activity, and does not have the influence of isomers on its surface activity, and can be used for pesticide adjuvant, drug buffer Interpretation, functional nanomaterials, textile processing aids and other fields;
2.相比采用硅氢加成制备聚醚基有机硅表面活性剂，巯烯反应所需反应时间大幅度降低，且不采用贵金属催化剂、不需要加热，不存在同分异构体，而且更加的经济简单；2. Compared with the preparation of polyether-based silicone surfactants by hydrosilicon addition, the reaction time required for mercaptoene reaction is greatly reduced, and no precious metal catalyst is used, no heating is required, there are no isomers, and it is more The economy is simple;
3.本方法所用的聚醚原料为市场成熟产品，促使本发明的制备方法更加可行，易于操作，适合工业化生产应用。3. The polyether raw material used in the method is a mature product in the market, which makes the preparation method of the present invention more feasible, easy to operate, and suitable for industrial production and application.
附图说明Description of drawings
以下结合附图对本发明作进一步详述。The present invention will be described in further detail below in conjunction with the accompanying drawings.
图1为本发明方法所制得聚醚基有机硅表面活性剂的结构式的视图。Fig. 1 is a view of the structural formula of the polyether-based silicone surfactant prepared by the method of the present invention.
具体实施方式Detailed ways
一种聚醚基有机硅表面活性剂的制备方法，如图1所示，该制备方法包括如下步骤：A preparation method of polyether-based silicone surfactant, as shown in Figure 1, the preparation method comprises the steps:
（1）将巯丙基硅氧烷、不饱和聚醚、溶剂和安息香二甲醚加入单口烧瓶中，进行巯烯反应，反应时间为30min~4小时；(1) Add mercaptopropylsiloxane, unsaturated polyether, solvent and benzoin dimethyl ether into a single-necked flask to carry out mercaptoene reaction, and the reaction time is 30 minutes to 4 hours;
（2）反应结束后将未反应完单体、溶剂和残留引发剂除去，得聚醚基有机硅表面活性剂。(2) After the reaction, unreacted monomers, solvents and residual initiators are removed to obtain a polyether-based silicone surfactant.
所述巯丙基硅氧烷为巯丙基三甲基硅烷、巯丙基-三(三甲基硅氧基)硅烷、巯丙基-二(三甲基硅氧基)甲基硅烷、巯丙基-二(三甲基硅氧基)甲基硅烷、巯丙基-二(乙基二甲基硅氧基)甲基硅烷、巯丙基-二(丙基二甲基硅氧基)甲基硅烷、巯丙基-二(丁基二甲基硅氧基)甲基硅烷、巯丙基-二(苯基二甲基硅氧基)甲基硅烷、1-巯丙基五甲基二硅氧烷、1-巯丙基- 3-乙基四甲基二硅氧烷、1-巯丙基-3-丙基四甲基二硅氧烷、1-巯丙基-3-丁基四甲基二硅氧烷、1-巯丙基-3-苯基四甲基二硅氧烷中的一种。The mercaptopropylsiloxane is mercaptopropyltrimethylsilane, mercaptopropyl-tri(trimethylsiloxy)silane, mercaptopropyl-bis(trimethylsiloxy)methylsilane, mercaptopropyl Propyl-bis(trimethylsiloxy)methylsilane, Mercaptopropyl-bis(ethyldimethylsiloxy)methylsilane, Mercaptopropyl-bis(propyldimethylsiloxy) Methylsilane, Mercaptopropyl-bis(butyldimethylsiloxy)methylsilane, Mercaptopropyl-bis(phenyldimethylsiloxy)methylsilane, 1-mercaptopropylpentamethyl Disiloxane, 1-mercaptopropyl-3-ethyltetramethyldisiloxane, 1-mercaptopropyl-3-propyltetramethyldisiloxane, 1-mercaptopropyl-3-butyl One of tetramethyldisiloxane and 1-mercaptopropyl-3-phenyltetramethyldisiloxane.
所述不饱和聚醚为羟基封端不饱和聚醚和甲基封端不饱和聚醚，其中乙二醇链节数可为3~50，丙氧基链节数为0~20。The unsaturated polyether is a hydroxyl-terminated unsaturated polyether and a methyl-terminated unsaturated polyether, wherein the number of ethylene glycol chain members can be 3-50, and the number of propoxyl chain members is 0-20.
所述巯丙基硅氧烷与不饱和聚醚的摩尔比为1~1.3：1。The molar ratio of the mercaptopropylsiloxane to the unsaturated polyether is 1-1.3:1.
所述溶剂为甲醇、乙醇、四氢呋喃、异丙醇、丁醇、乙腈、N,N-二甲基甲酰胺中的一种或其混合溶剂。The solvent is one of methanol, ethanol, tetrahydrofuran, isopropanol, butanol, acetonitrile, N,N-dimethylformamide or a mixed solvent thereof.
所述安息香二甲醚用量为1%~5% 质量分数。The amount of benzoin dimethyl ether is 1% to 5% by mass fraction.
实施例1Example 1
（1）于100 ml单口瓶中加入14.8 g巯丙基-二(三甲基硅氧基)甲基硅烷、36.5g烯丙基聚乙二醇单甲醚（分子质量约为750 g/mol）、0.99 g 安息香二甲醚和30 ml 甲醇，室温搅拌进行巯烯反应；（2）40分钟后停止反应，减压出去未反应单体、溶剂、引发剂等，冷却即得三硅氧烷型非离子表面活性剂。(1) Add 14.8 g of mercaptopropyl-bis(trimethylsiloxy)methylsilane and 36.5 g of allyl polyethylene glycol monomethyl ether (molecular mass is about 750 g/mol) into a 100 ml single-necked bottle ), 0.99 g benzoin dimethyl ether and 30 ml methanol, stirred at room temperature for mercaptoene reaction; (2) stop the reaction after 40 minutes, remove unreacted monomers, solvents, initiators, etc. under reduced pressure, and cool to obtain trisiloxane type nonionic surfactants.
其产率为98%，密封干燥保存。该非离子型有机硅表面活性剂γCMC为 22.4 mN/m。Its yield rate is 98%, and it is stored in a sealed and dry place. The γ CMC of the nonionic silicone surfactant was 22.4 mN/m.
实施例2Example 2
（1）于100 ml单口瓶中加入19.3 g巯丙基-三(三甲基硅氧基)硅烷、50.0g烯丙基聚甲醚（分子质量约为1000 g/mol）、1.34 g 安息香二甲醚和50 ml 甲醇，室温搅拌进行巯烯反应；（2）1小时后停止反应，减压出去未反应单体、溶剂、引发剂等，冷却即得三硅氧烷型非离子表面活性剂。(1) Add 19.3 g of mercaptopropyl-tris(trimethylsiloxy)silane, 50.0 g of allyl polymethyl ether (molecular mass is about 1000 g/mol), and 1.34 g of benzoin into a 100 ml single-necked bottle Methyl ether and 50 ml of methanol, stirred at room temperature for mercaptoene reaction; (2) stop the reaction after 1 hour, remove unreacted monomers, solvents, initiators, etc. under reduced pressure, and cool to obtain trisiloxane nonionic surfactant .
其产率为97%，密封干燥保存。该非离子型有机硅表面活性剂γCMC为 21.6 mN/m。Its yield rate is 97%, and it is stored in a sealed and dry place. The γ CMC of the nonionic silicone surfactant was 21.6 mN/m.
实施例3Example 3
（1）于100 ml单口瓶中加入17.2 g巯丙基-二(乙基二甲基硅氧基)甲基硅烷、50.0g烯丙基聚醚（分子质量约为1000 g/mol）、1.21 g 安息香二甲醚和50 ml 甲醇，室温搅拌进行巯烯反应；（2）1小时后停止反应，减压出去未反应单体、溶剂、引发剂等，冷却即得含乙基三硅氧烷型非离子表面活性剂。(1) Add 17.2 g of mercaptopropyl-bis(ethyldimethylsiloxy)methylsilane, 50.0 g of allyl polyether (molecular mass about 1000 g/mol), 1.21 g benzoin dimethyl ether and 50 ml methanol, stirring at room temperature to react mercaptoene; (2) stop the reaction after 1 hour, remove unreacted monomers, solvents, initiators, etc. under reduced pressure, and cool to obtain ethyl trisiloxane type nonionic surfactants.
其产率为95%，密封干燥保存。该非离子型有机硅表面活性剂γCMC为 25.3 mN/m。Its yield rate is 95%, and it is stored in a sealed and dry place. The γ CMC of this nonionic silicone surfactant is 25.3 mN/m.
实施例4Example 4
（1）于100 ml单口瓶中加入17.2g巯丙基-二(苯基二甲基硅氧基)甲基硅烷、40.0g烯丙基聚甲醚（分子质量约为1000 g/mol）、1.42 g 安息香二甲醚和40 ml 四氢呋喃，室温搅拌进行巯烯反应；（2）1.5小时后停止反应，减压出去未反应单体、溶剂、引发剂等，冷却即得三硅氧烷型非离子表面活性剂。(1) Add 17.2g of mercaptopropyl-bis(phenyldimethylsiloxy)methylsilane, 40.0g of allyl polymethyl ether (molecular weight is about 1000 g/mol), 1.42 g benzoin dimethyl ether and 40 ml tetrahydrofuran, stirred at room temperature for mercaptoene reaction; (2) stop the reaction after 1.5 hours, remove unreacted monomers, solvents, initiators, etc. under reduced pressure, and cool to obtain trisiloxane non- ionic surfactant.
其产率为95%，密封干燥保存。该非离子型有机硅表面活性剂γCMC为 26.5 mN/m。Its yield rate is 95%, and it is stored in a sealed and dry place. The γ CMC of the nonionic silicone surfactant was 26.5 mN/m.
实施例5Example 5
（1）于100 ml单口瓶中加入7.9 g巯丙基三甲基硅烷、12.5g烯丙基聚乙二醇（分子质量约为270 g/mol）、0.31 g 安息香二甲醚和20 ml 甲醇，室温搅拌进行巯烯反应；（2）40分钟后停止反应，减压出去未反应单体、溶剂、引发剂等，冷却即得三硅氧烷型非离子表面活性剂。(1) Add 7.9 g of mercaptopropyltrimethylsilane, 12.5 g of allyl polyethylene glycol (molecular mass of about 270 g/mol), 0.31 g of benzoin dimethyl ether and 20 ml of methanol into a 100 ml single-necked bottle , Stir at room temperature for mercaptoene reaction; (2) Stop the reaction after 40 minutes, remove unreacted monomers, solvents, initiators, etc. under reduced pressure, and cool to obtain a trisiloxane-type nonionic surfactant.
其产率为99%，密封干燥保存。该非离子型有机硅表面活性剂γCMC为 21.5 mN/m。Its yield rate is 99%, and it is stored in a sealed and dry place. The γ CMC of this nonionic silicone surfactant is 21.5 mN/m.
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