CN101560220A - Organosilicone gemini quaternary ammonium salt and synthetic method thereof - Google Patents
Organosilicone gemini quaternary ammonium salt and synthetic method thereof Download PDFInfo
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 24
- 238000010189 synthetic method Methods 0.000 title claims 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000003093 cationic surfactant Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract 2
- 239000003899 bactericide agent Substances 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000675 fabric finishing Substances 0.000 description 2
- 238000009962 finishing (textile) Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KZPKNXDCUWKKET-UHFFFAOYSA-M [2-hydroxy-3-(4-nonylphenoxy)propyl]-trimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCC1=CC=C(OCC(O)C[N+](C)(C)C)C=C1 KZPKNXDCUWKKET-UHFFFAOYSA-M 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004663 bisphosphonates Chemical class 0.000 description 1
- -1 carboxylate compound Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种有机硅双子季铵盐及其合成方法，其结构式如右所示，该有机硅双子季铵盐的合成方法如下：将(RO)2CH3Si(CH2)3Cl与溶剂混合升温，然后滴加(CH3)2 NR1N(CH3)2，控制反应条件即可得到有机硅双子季铵盐。本发明的优点是原料易得，反应条件简单易控制。所得化合物具有较高的表面活性，可作为有机硅阳离子表面活性剂使用，也可用于杀菌、抗菌剂。有机硅的引入增加了产品的柔顺性和安全性，可作为织物的柔软抗菌剂应用，是对人体安全的抗菌产品。
An organosilicon gemini quaternary ammonium salt and its synthesis method. Its structural formula is shown on the right. The synthesis method of the organosilicon gemini quaternary ammonium salt is as follows: mix (RO) 2 CH 3 Si(CH 2 ) 3 Cl with a solvent and heat up , and then drop (CH 3 ) 2 NR 1 N(CH 3 ) 2 , and control the reaction conditions to obtain organosilicon gemini quaternary ammonium salt. The invention has the advantages that the raw materials are easy to obtain, and the reaction conditions are simple and easy to control. The obtained compound has high surface activity and can be used as organosilicon cationic surfactant, as well as bactericidal and antibacterial agent. The introduction of silicone increases the flexibility and safety of the product, and it can be used as a soft antibacterial agent for fabrics, which is an antibacterial product that is safe for the human body.
Description
技术领域： Technical field:
本发明涉及一类性能优良的新型表面活性剂的合成，尤其是有机硅双子季铵盐表面活性剂的合成，该表面活性剂可用于制备日用化学品、织物整理剂等，属于精细化工领域。The present invention relates to the synthesis of a class of novel surfactants with excellent performance, especially the synthesis of organosilicon gemini quaternary ammonium salt surfactants, which can be used to prepare daily chemicals, fabric finishing agents, etc., and belong to the field of fine chemicals .
背景技术： Background technique:
双子表面活性剂含有两个亲水头基和两个疏水链，由联结基团通过化学键连接而成。这类化合物显示了极好的表面活性，如很小的临界胶束浓度(cmc)、非常低的最低表面张力值等。一系列的研究表明Gemini表面活性剂具有较单烷烃链和单离子头基组成的传统表面活性剂高得多的表面活性。Gemini surfactants contain two hydrophilic head groups and two hydrophobic chains connected by linking groups through chemical bonds. This kind of compound shows excellent surface activity, such as very small critical micelle concentration (cmc), very low minimum surface tension value and so on. A series of studies have shown that Gemini surfactants have much higher surface activity than traditional surfactants composed of a single alkane chain and a single ionic head group.
最早报道的双子表面活性剂是1950年的美国专利US2524218中Frederick C.B.等合成的系列洗涤助剂中有一种结构为双子型的羧酸盐化合物，主要起鳌合、分散、润湿作用。The earliest reported gemini surfactant is a series of detergent builders synthesized by Frederick C.B. in the US patent US2524218 in 1950. There is a carboxylate compound with a gemini structure, which mainly plays the role of chelation, dispersion and wetting.
赵剑曦等[赵剑曦等Gemini阳离子表面活性剂的合成及其胶束生成物理化学学报200117(1)]对阳离子型的Gemini表面活性剂的合成进行了一些研究，以1-溴代烷与四甲基乙(己)二胺反应制备了阳离子型二溴化-N，N-二(二甲基烷基)乙(己)二胺系列Gemini表面活性剂，该类化合物在水溶液中具有较强的胶束化倾向。[Synthesis of Gemini cationic surfactants such as Zhao Jianxi and its micelle formation Acta Physicochemical Society 200117 (1)] conducted some research on the synthesis of cationic Gemini surfactants, using 1-bromoalkane and tetramethyl Cationic dibromide-N,N-bis(dimethylalkyl)ethylene(hexane)diamine series Gemini surfactants were prepared by reacting ethyl(hexane)diamine. bundle tendency.
北京航空航天大学陈功等的专利CN200510126037.X涉及一种双子表面活性剂(GAP)及其制备方法。该表面活性剂以3-对壬基苯氧基-2-羟基丙基三甲基氯化铵(NPQT)为单体，将两分子NPQT偶联得到。通过临界胶束浓度(CMC)测量发现，GAP的CMC值比NPQT低两个数量级，表面活性有显著提高。The patent CN200510126037.X of Beihang University Chen Gong et al. relates to a gemini surfactant (GAP) and its preparation method. The surfactant uses 3-p-nonylphenoxy-2-hydroxypropyltrimethylammonium chloride (NPQT) as a monomer, and is obtained by coupling two molecules of NPQT. The critical micelle concentration (CMC) measurement found that the CMC value of GAP was two orders of magnitude lower than that of NPQT, and the surface activity was significantly improved.
Dipti Shukla与Vinod K.Tyagi[Dipti Shukla，Vinod K.Tyagi Synthesis and properties ofgeminis with two alkyl and two phosphate headgroups Eur.J.Lipid Sci.Technol.2008，110，576-580]研究了双磷酸酯类的表面活性剂，以焦磷酸、十二醇、氢氧化四甲胺、1，6-二溴己烷为原料，经过两步反应得到了阴离子型双子表面活性剂，具有优良的水溶性、发泡剂润湿性能。Dipti Shukla and Vinod K.Tyagi [Dipti Shukla, Vinod K.Tyagi Synthesis and properties of geminis with two alkyl and two phosphate headgroups Eur.J.Lipid Sci.Technol.2008, 110, 576-580] studied the bisphosphonate Surfactant, using pyrophosphoric acid, lauryl alcohol, tetramethylamine hydroxide, and 1,6-dibromohexane as raw materials, anionic gemini surfactants are obtained through two-step reactions, which have excellent water solubility and foaming agent wetting properties.
齐齐哈尔大学的郭祥峰等[郭祥峰等甘氨酸酯衍生物双子季铵盐表面活性剂应用化学Vol.19 No.7]用二元醇双氯乙酸酯与N，N-二甲基十二烷基胺反应，合成了新型结构的甘氨酸酯衍生物双子季铵盐表面活性剂，具有较低的临界胶束浓度和良好的起泡、稳泡性。Guo Xiangfeng from Qiqihar University [Guo Xiangfeng et al. Glycine ester derivatives Gemini quaternary ammonium salt surfactant Applied Chemistry Vol.19 No.7] used dibasic alcohol dichloroacetate and N, N-dimethyl dodecylamine reaction, a novel structure of glycinate derivatives gemini quaternary ammonium surfactants was synthesized, which has a lower critical micelle concentration and good foaming and foam stabilizing properties.
乔治·G·I·摩尔与迈克尔·特拉萨斯的专利CN200680042890.6报导了氟化双子表面活性剂的制备，该类表面活性剂可有效降低溶液的表面张力，可用于消泡乳化剂、分散剂、润湿助剂等。The patent CN200680042890.6 of George G.I. Moore and Michael Terrazas reported the preparation of fluorinated gemini surfactants, which can effectively reduce the surface tension of the solution and can be used for defoaming emulsifiers, dispersing agents, wetting aids, etc.
韩富等[韩富等新型含硅表面活性剂的合成及性能研究化学学报2004年第62卷第7期]利用含有双胺基的三硅氧烷中的伯胺基与D-葡萄糖酸-δ-内酯进行酰胺化，仲胺基与低聚乙二醇甲醚缩水甘油醚、二缩水甘油醚进行烷基化，制备了系列新型含硅表面活性剂及含硅双子表面活性剂，具有低的表面张力及临界胶束浓度。Han Fu et al. [Synthesis and performance research of new silicon-containing surfactants such as Han Fu et al. Journal of Chemistry, Volume 62, No. 7, 2004] Utilize the primary amino group and D-gluconic acid- Amidation of δ-lactone, alkylation of secondary amino groups with oligoethylene glycol methyl ether glycidyl ether and diglycidyl ether, a series of new silicon-containing surfactants and silicon-containing gemini surfactants were prepared, with Low surface tension and critical micelle concentration.
目前的研究主要集中在疏水链以烷烃为主的结构上，对于含杂原子的双子表面活性剂的研究相对较少，其中以氟烃链结构的研究为主。对于含硅的双子表面活性剂的研究报导更少，而且现有的合成方法步骤复杂，成本较高。The current research mainly focuses on the structure of alkane as the main hydrophobic chain. There are relatively few studies on gemini surfactants containing heteroatoms, and the research on the structure of fluorocarbon chains is the main one. There are fewer research reports on silicon-containing gemini surfactants, and the existing synthesis methods have complicated steps and high costs.
发明内容： Invention content:
针对现有技术的不足，本发明要解决的问题是提供一种制备有机硅双子季铵盐的方法，该方法反应步骤简单，产品纯度较高，具有良好的应用性能。Aiming at the deficiencies of the prior art, the problem to be solved by the present invention is to provide a method for preparing organosilicon gemini quaternary ammonium salt, which has simple reaction steps, high product purity and good application performance.
下面将详述本发明的技术方案：The technical scheme of the present invention will be described in detail below:
本发明所述的有机硅双子季铵盐的制备方法可通过如下反应过程实现：The preparation method of organosilicon gemini quaternary ammonium salt of the present invention can be realized by following reaction process:
(RO)2CH3Si(CH2)3Cl+(CH3)2NR1N(CH3)2→(RO) 2 CH 3 Si(CH 2 ) 3 Cl+(CH 3 ) 2 NR 1 N(CH 3 ) 2 →
(CH3)2(RO)2CH3Si(CH2)3N+R1N+(RO)2CH3Si(CH2)3(CH3)2·2Cl- (CH 3 ) 2 (RO) 2 CH 3 Si(CH 2 ) 3 N + R 1 N + (RO) 2 CH 3 Si(CH 2 ) 3 (CH 3 ) 2 2Cl -
本发明提供一种有机硅双子季铵盐的制备方法，所述的制备方法如下：The present invention provides a kind of preparation method of organosilicon gemini quaternary ammonium salt, described preparation method is as follows:
将(RO)2CH3Si(CH2)3Cl与溶剂混合升温至50～130℃，然后滴加(CH3)2NR1N(CH3)2，(RO)2CH3Si(CH2)3Cl与(CH3)2NR1N(CH3)2的摩尔比为1∶2～6，在50～130℃，反应时间4～20小时，得到有机硅双子季铵盐(CH3)2(RO)2CH3Si(CH2)3N+R1N+(RO)2CH3Si(CH2)3(CH3)2·2Cl-的溶液。蒸除溶剂，得到有机硅双子季铵盐(CH3)2(RO)2CH3Si(CH2)3N+R1N+(CH2)3Si CH3(RO)2(CH3)2·2Cl-。R为甲基或乙基，R1为烷烃基。Mix (RO) 2 CH 3 Si(CH 2 ) 3 Cl with solvent and heat up to 50~130°C, then drop (CH 3 ) 2 NR 1 N(CH 3 ) 2 , (RO) 2 CH 3 Si(CH 2 ) The molar ratio of 3 Cl to (CH 3 ) 2 NR 1 N(CH 3 ) 2 is 1:2~6, at 50~130°C, the reaction time is 4~20 hours, and the organosilicon gemini quaternary ammonium salt (CH 3 ) 2 (RO) 2 CH 3 Si(CH 2 ) 3 N + R 1 N + (RO) 2 CH 3 Si(CH 2 ) 3 (CH 3 ) 2 ·2Cl - solution. The solvent was evaporated to obtain organosilicon gemini quaternary ammonium salt (CH 3 ) 2 (RO) 2 CH 3 Si(CH 2 ) 3 N + R 1 N + (CH 2 ) 3 Si CH 3 (RO) 2 (CH 3 ) 2 · 2Cl − . R is a methyl or ethyl group, and R 1 is an alkane group.
优选的，在惰性气体保护下进行。所述惰性气体选自氮气或氩气。Preferably, it is carried out under the protection of an inert gas. The inert gas is selected from nitrogen or argon.
优选的，反应温度为75～110℃，反应时间8～16小时。Preferably, the reaction temperature is 75-110° C., and the reaction time is 8-16 hours.
更优选的，反应温度为80-100℃，应时间为10-14小时，(RO)2CH3Si(CH2)3Cl与(CH3)2NR1N(CH3)2摩尔比为1∶(2-2.3)。More preferably, the reaction temperature is 80-100°C, the reaction time is 10-14 hours, and the molar ratio of (RO) 2 CH 3 Si(CH 2 ) 3 Cl to (CH 3 ) 2 NR 1 N(CH 3 ) 2 is 1: (2-2.3).
优选的，R1选自(CH2)2、(CH2)4、(CH2)6、(CH2)8、(CH2)10、(CH2)12或
本发明所述的制备方法还可以包括对有机硅双子季铵盐(CH3)2(RO)2CH3Si(CH2)3N+R1N+(RO)2CH3Si(CH2)3(CH3)2·2Cl-的进一步提纯等。The preparation method of the present invention may also include the preparation of organosilicon gemini quaternary ammonium salt (CH 3 ) 2 (RO) 2 CH 3 Si(CH 2 ) 3 N + R 1 N + (RO) 2 CH 3 Si(CH 2 ) 3 (CH 3 ) 2 ·2Cl - further purification and so on.
所述溶剂为无水甲醇、无水乙醇、异丙醇中的一种或它们的混合物。优选的，溶剂为无水乙醇。The solvent is one of absolute methanol, absolute ethanol, isopropanol or a mixture thereof. Preferably, the solvent is absolute ethanol.
通过该方法可制备的化合物有：Compounds that can be prepared by this method are:
(CH3O)2CH3Si(CH2)3N+(CH2)2N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 2 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3N+(CH2)4N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 4 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3N+(CH2)6N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 6 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3N+(CH2)8N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 8 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3N+(CH2)10N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 10 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3N+(CH2)12N+(CH2)3Si CH3(CH3O)2·2Cl-、(CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 12 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 2Cl - ,
(CH3O)2CH3Si(CH2)3 
(C2H5O)2CH3Si(CH2)3N+(CH2)2N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 2 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(C2H5O)2CH3Si(CH2)3N+(CH2)4N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 4 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(C2H5O)2CH3Si(CH2)3N+(CH2)6N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 6 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(C2H5O)2CH3Si(CH2)3N+(CH2)8N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 8 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(C2H5O)2CH3Si(CH2)3N+(CH2)10N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 10 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(C2H5O)2CH3Si(CH2)3N+(CH2)12N+(CH2)3Si CH3(C2H5O)2·2Cl-、(C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 12 N + (CH 2 ) 3 Si CH 3 (C 2 H 5 O) 2 2Cl - ,
(CH3CH2O)2CH3Si(CH2)3 (CH2)3Si CH3(CH3CH2O)22Cl- (CH 3 CH 2 O) 2 CH 3 Si(CH 2 ) 3 (CH 2 ) 3 Si CH 3 (CH 3 CH 2 O) 2 2Cl -
本发明所述的有机硅双子季铵盐是性能优良的表面活性剂，可用于洗涤、杀菌、乳化、防腐等方面，适用于日用品或织物整理剂中。The organosilicon gemini quaternary ammonium salt of the present invention is a surfactant with excellent performance, which can be used in washing, sterilization, emulsification, anticorrosion, etc., and is suitable for daily necessities or fabric finishing agents.
与现有技术相比，本发明具有如下优点：Compared with prior art, the present invention has following advantage:
1.引入有机硅烷链作为疏水基团，可以提高产品的综合性能1. The introduction of organosilane chains as hydrophobic groups can improve the overall performance of the product
2.合成步骤简单，一步即可完成2. The synthesis steps are simple and can be completed in one step
3.本发明产品具有较好的表面活性，并具有强的杀菌、抗菌性。3. The product of the present invention has better surface activity, and has strong bactericidal and antibacterial properties.
附图说明： Description of drawings:
附图为实施例1合成的有机硅双子季铵盐的1H-NMR谱图，CDCl3为氘代试剂。The accompanying drawing is the 1 H-NMR spectrum of the organosilicon gemini quaternary ammonium salt synthesized in Example 1, and CDCl 3 is a deuterated reagent.
具体实施方式 Detailed ways
下面的实施例中将对本发明作进一步的阐述，但本发明不限于此。The present invention will be further described in the following examples, but the present invention is not limited thereto.
实施例1Example 1
将18g(CH3O)2CH3Si(CH2)3Cl与10g乙醇加入装有滴液漏斗、温度计、回流冷凝管及氮气保护装置的四口瓶中，搅拌加热至回流，缓慢滴加四甲基乙二胺5g，80℃反应8小时，得到(CH3O)2CH3Si(CH2)3N+(CH2)2N+(CH2)3Si CH3(CH3O)2·2Cl-的乙醇溶液，蒸馏除去乙醇，用无水乙醚洗涤数次后真空干燥得黄色透明产物，收率40％。Add 18g(CH 3 O) 2 CH 3 Si(CH 2 ) 3 Cl and 10g ethanol into a four-necked flask equipped with a dropping funnel, a thermometer, a reflux condenser and a nitrogen protection device, stir and heat to reflux, and slowly drop 5g of tetramethylethylenediamine was reacted at 80°C for 8 hours to obtain (CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 2 N + (CH 2 ) 3 Si CH 3 (CH 3 O ) 2 · 2Cl - in ethanol solution, distill off the ethanol, wash with anhydrous ether for several times and then vacuum dry to obtain a yellow transparent product with a yield of 40%.
附图为该化合物的1H-NMR谱图，对应的化学位移分别为：0.042ppm为-Si-CH 3 ，1.1ppm为与硅相连的亚甲基峰-Si-CH 3 -CH2-CH2-，2.18ppm为-N+-CH 2 -CH2-CH2-Si-，2.7ppm为-N+-CH 2 -CH 2 -N+-，3.6ppm为Si-O-CH 3 ，3.25ppm为CH 3 -N+-，1.5ppm为-N+-CH2-CH 2 -CH2-Si-。The attached figure is the 1 H-NMR spectrum of the compound, and the corresponding chemical shifts are: 0.042ppm is -Si- CH 3 , and 1.1ppm is the methylene peak connected to silicon -Si- CH 3 -CH 2 -CH2- , 2.18ppm as -N + -CH2 - CH2 - CH2 - Si-, 2.7ppm as -N + -CH2 - CH2 - N + -, 3.6ppm as Si-OC H 3 , 3.25ppm is CH 3 -N + - , 1.5ppm is -N + -CH 2 -CH 2 -CH 2 -Si-.
实施例2Example 2
将15.8g(CH3O)2CH3Si(CH2)3Cl与10g甲醇加入装有滴液漏斗、温度计、回流冷凝管及氮气保护装置的四口瓶中，搅拌加热至回流，缓慢滴加四甲基己二胺8g，70℃反应12小时，得到(CH3O)2CH3Si(CH2)3N+(CH2)6N+(CH2)3Si CH3(CH3O)2·2Cl-的甲醇溶液，转化率21.6％。Add 15.8g(CH 3 O) 2 CH 3 Si(CH 2 ) 3 Cl and 10g methanol into a four-necked flask equipped with a dropping funnel, a thermometer, a reflux condenser and a nitrogen protection device, stir and heat to reflux, and slowly drop Add 8g of tetramethylhexamethylenediamine and react at 70°C for 12 hours to obtain (CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 6 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 ·2Cl - in methanol solution, the conversion rate is 21.6%.
实施例3Example 3
在装有温度计、回流冷凝管、滴液漏斗及氮气保护装置的四口瓶中，加入33g(C2H5O)2CH3Si(CH2)3Cl和10g无水甲醇，电磁搅拌下升温至回流，缓慢滴加10g四甲基乙二胺，反应14小时即得(C2H5O)2CH3Si(CH2)3N+(CH2)2N+(CH2)3Si CH3(C2H5O)2·2Cl-的甲醇溶液，转化率24％。In a four-neck flask equipped with a thermometer, a reflux condenser, a dropping funnel, and a nitrogen protection device, add 33g (C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 Cl and 10 g of anhydrous methanol, under electromagnetic stirring Raise the temperature to reflux, slowly add 10g of tetramethylethylenediamine dropwise, and react for 14 hours to obtain (C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 2 N + (CH 2 ) 3 Methanol solution of Si CH 3 (C 2 H 5 O) 2 ·2Cl - , the conversion rate is 24%.
实施例4Example 4
在装有温度计、回流冷凝管、滴液漏斗及氮气保护装置的四口瓶中，加入30g(C2H5O)2CH3Si(CH2)3Cl和10g异丙醇，电磁搅拌下加热至回流，缓慢滴加7g四甲基乙二胺，反应20小时即得(CH3O)2CH3Si(CH2)3N+(CH2)4N+(CH2)3Si CH3(CH3O)2·2Cl-的异丙醇溶液，转化率10％。In a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel, and a nitrogen protection device, add 30g (C 2 H 5 O) 2 CH 3 Si(CH 2 ) 3 Cl and 10 g of isopropanol, under electromagnetic stirring Heat to reflux, slowly add 7g of tetramethylethylenediamine dropwise, and react for 20 hours to obtain (CH 3 O) 2 CH 3 Si(CH 2 ) 3 N + (CH 2 ) 4 N + (CH 2 ) 3 Si CH 3 (CH 3 O) 2 ·2Cl - in isopropanol solution, the conversion rate is 10%.
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| CN102503837A (en) * | 2011-10-17 | 2012-06-20 | 太原理工大学 | Tertiary amines and organic silicon quaternary ammonium salts containing double long chains and benzyl groups and preparation methods thereof |
| CN106928267A (en) * | 2017-03-06 | 2017-07-07 | 汕头大学 | The preparation method of quaternary trisiloxanes Gemini surface active agent |
| CN107445983A (en) * | 2017-08-13 | 2017-12-08 | 上海应用技术大学 | Symmetrical Shuangzi silicone Quaternary Ammonium Salt Antimicrobial Agent and preparation method thereof |
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| CN102503837A (en) * | 2011-10-17 | 2012-06-20 | 太原理工大学 | Tertiary amines and organic silicon quaternary ammonium salts containing double long chains and benzyl groups and preparation methods thereof |
| CN106928267A (en) * | 2017-03-06 | 2017-07-07 | 汕头大学 | The preparation method of quaternary trisiloxanes Gemini surface active agent |
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| CN109762548A (en) * | 2019-03-05 | 2019-05-17 | 西安市轻工业研究所 | A kind of increasing injection oil displacement agent of the low permeability oil field containing Gemini surface active agent |
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| CN110240612A (en) * | 2019-07-17 | 2019-09-17 | 南京神奇科技开发有限公司 | A kind of novel quaternary ammonium compound and its preparation method and application |
| CN110240612B (en) * | 2019-07-17 | 2022-01-25 | 南京神奇科技开发有限公司 | Novel quaternary ammonium salt compound and preparation method and application thereof |
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| CN113244124A (en) * | 2021-05-10 | 2021-08-13 | 扬州工业职业技术学院 | Nicotinamide type synergistic phenol bactericide and preparation method thereof |
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