CN101696222B - Method for synthesizing dimethyl [2-(methacryloyl) ethyl] [3-(trimethoxy silane) propyl] ammonium chloride - Google Patents
Method for synthesizing dimethyl [2-(methacryloyl) ethyl] [3-(trimethoxy silane) propyl] ammonium chloride Download PDFInfo
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- CN101696222B CN101696222B CN2009102725480A CN200910272548A CN101696222B CN 101696222 B CN101696222 B CN 101696222B CN 2009102725480 A CN2009102725480 A CN 2009102725480A CN 200910272548 A CN200910272548 A CN 200910272548A CN 101696222 B CN101696222 B CN 101696222B
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- OFRMVBJHGSBENG-UHFFFAOYSA-N CC(C(O)OCC[N](C)(C)CCC[Si](OC)(OC)OC)=C Chemical compound CC(C(O)OCC[N](C)(C)CCC[Si](OC)(OC)OC)=C OFRMVBJHGSBENG-UHFFFAOYSA-N 0.000 description 1
- QWSZODPWSQLCJO-UHFFFAOYSA-N CO[Si+](CCCCl)(OC)[O](C)C Chemical compound CO[Si+](CCCCl)(OC)[O](C)C QWSZODPWSQLCJO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for synthesizing dimethyl [2-(methacryloyl) ethyl] [3-(trimethoxy silane) propyl] ammonium chloride. The method comprises the following steps: adding a solvent and a polymerization inhibitor into dimethylamino ethyl methacrylate and gamma-chloropropyl trimethoxysilane which are used as raw materials; introducing N2 for protection; undergoing synthetic reaction under the conditions of heating and stirring; performing vacuum distillation (introducing N2 for protection); distilling front cut fraction out at the temperature of less than 60 DEG C; recovering the solvent and unreacted raw materials at the temperature ranging from 60 DEG C to 80 DEG C; and controlling the temperature of distillate to not exceed 120 DEG C. When the temperature is lowered to 60 DEG C and below, liquid in a distillation flask becomes sticky to obtain a product. The invention has the advantages of short synthesis time, no need of catalyst and molar yield of 90 percent to 93 percent. Brown-red solutions with different concentrations are prepared by dissolving the obtained product into methanol and are convenient to use. The recovered solvent and the raw materials can be recycled. No waste water and waste residues are generated in the whole process, therefore, the method is a typical green chemical synthesis method.
Description
Technical field
The present invention relates to the synthetic method of silane, more specifically relate to the synthetic method of a kind of dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride, belong to the synthetic of fine chemical product.
Background technology
Dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride is a kind of broad-spectrum positively charged ion hydrocarbyl si lanes (salt), and it has good water-solubility and stability.Be different from amino-alkyl silicane, in aqueous systems, NH can not take place
2With the interior complexing action of Si-OH, thereby keep best coupling effect, have surfactivity efficiently simultaneously, bactericidal properties and static resistance.Because the hydrolysis-condensation reaction of Si-OR makes it have very strong surfactivity, be widely used in the processing of fabric face, as working suit, underwear, sheet, [US 5073195 for footgears etc.; JP 57098578; JP 50028592].With titanic acid ester or when acting on fiberglass surfacing separately, can not only improve its toughness and cohesiveness, [US 5525677 more to strengthen its MOR and shock strength; CS 259292].When adding this silane in nano composite oxide that is mixed with rare earth element or clay, can increase its water absorption resistance, [CN 1431255 to help the research of luminosity; CN 1200046; Zhou, Ningli, et.al., Studies on nanostructured polyurethane/clayinterpenetrating polymer networks[J] .Materials Science Forum (2005), 475-479].Sneak into when suppressing laminate in the polyester, can not only improve the flexural strength of polyester stratified plastics, can also improve its water absorption resistance, thermotolerance and cementability [CS 191493].In addition, because its static resistance efficiently, be widely used in that [DE 3330380 in lighting apparatus and the xerography technology; US 4407920; JP 57039416].
The synthetic domestic almost report not of relevant this product, the DOW CORNING of the U.S. is arranged abroad, and [US 3884886,1975; DE 2050466,1971] did the work of this respect.They add sulphur and halogenide is made catalyzer, react 74h down at 95 ℃ and obtain product.This synthetic method duration of the reaction is long, and energy consumption is many, and economic benefit is not obvious, is unfavorable for industrial production.
Summary of the invention
The object of the present invention is to provide the efficient synthesis of a kind of dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride.This synthetic method is easy and simple to handle, and cost is low, the productive rate height, and recovery liquid can be recycled.
At the problem that exists, the present invention starts with from optimizing synthetic method, simplifies technical process, reduces production costs, and improves product yield and quality.Synthesis condition among the present invention is easy to control, and is easy and simple to handle, and synthesising reacting time is short, need not catalyzer, the molar yield height, byproduct of reaction is few, quality product height and recovered solvent and raw material can be recycled, and whole process does not have the generation of waste water, waste residue, are that typical Green Chemistry is synthetic.The steps include:
With dimethylaminoethyl acrylate methyl amido ethyl ester and γ-r-chloropropyl trimethoxyl silane is raw material, adds certain solvent and stopper, logical N
2Protection under the heated and stirred, is reacted 3～6h down at 130～140 ℃.Wherein the reaction mol ratio of dimethylaminoethyl acrylate methyl amido ethyl ester, γ-r-chloropropyl trimethoxyl silane, solvent and stopper is 1～1.1: 0.9～1.1: 2～2.5: 0.15～0.20.Logical N
2Protection down, the 0～667Pa that reduces pressure distillation steams front-end volatiles in temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, control distillment temperature is no more than 120 ℃.When the temperature of still head drops to 60 ℃ and following, the liquid in the matrass becomes thick, is product.This product is dissolved in methyl alcohol and obtains brown liquid; Raw material γ-the r-chloropropyl trimethoxyl silane that adopts in the synthetic method is necessary for neutrality, otherwise is unfavorable for the carrying out that reacts and reduces productive rate.
Described solvent is a diacetone alcohol, n-hexyl alcohol, dimethyl formamide, dimethylbenzene.
Described stopper is a 2,5 di tert butyl hydroquinone, nitroxyl free radical piperidines alcohol, 4-dimethylamine pyridine.
Synthetic method craft provided by the invention is simple, and is easy and simple to handle, need not catalyzer, and be convenient to suitability for industrialized production and increase economic efficiency.By product is few, is easy to separate purify; Recovered solvent and raw material can be recycled, and whole process does not have the generation of waste water, waste residue, are that typical Green Chemistry is synthetic.
Embodiment
Synthesizing of dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride: dimethylaminoethyl acrylate methyl amido ethyl ester, γ-r-chloropropyl trimethoxyl silane, solvent and stopper, 1.1: 0.9 in molar ratio～1.1: 2～2.5: 0.15～0.20 feeds intake and makes reactant under the heated and stirred, logical N
2Protection, mechanical stirring is at 130～140 ℃ of internal reaction 3～6h.When being cooled to 80 ℃, logical N
2Down employing oil pump 0～667Pa distillation of reducing pressure of protection steams front-end volatiles in head temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, and control distillment temperature is no more than 120 ℃.When head temperature drops to 60 ℃ and following, get thick liquid and be product.This product is dissolved in methyl alcohol and obtains brown liquid, and mean specific gravity is 0.948 during 20 ℃ of this liquid, n
D 20Be 1.3966, M during mass spectroscopy
++ 1 peak 321 is obvious; Molar yield 90～93%.Recovered solvent and unreacted raw material can be recycled.The reaction formula of said process is as follows:
Embodiment 1: add dimethylaminoethyl acrylate methyl amido ethyl ester 320g, γ-r-chloropropyl trimethoxyl silane 400g, diacetone alcohol 500g in the three-necked flask of 2000ml band thermometer, spherical condensation tube, airway and mechanical stirring device, dimethyl formamide 1.0g and nitroxyl free radical are sent pyridine alcohol 0.6g, the electric heating cooker heating, logical N
2Gas, mechanical stirring is at 130～140 ℃ of internal reaction 4h.When being cooled to 80 ℃, logical N
2Down employing oil pump 0～667Pa distillation of reducing pressure of protection steams front-end volatiles in head temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, and control distillment temperature is no more than 120 ℃.When head temperature drops to 60 ℃ and following, get thick liquid and be product, quality is 660.2g.This product is dissolved in methyl alcohol and obtains brown liquid, and proportion is 0.948 during 20 ℃ of this liquid, n
D 20Be 1.3966, M during mass spectroscopy
++ 1 peak 321 is obvious; Molar yield is 92.4%.
Embodiment 2: add dimethylaminoethyl acrylate methyl amido ethyl ester 256g, γ-r-chloropropyl trimethoxyl silane 320g, diacetone alcohol 20g in the three-necked flask of 2000ml band thermometer, spherical condensation tube, airway and mechanical stirring device, the solution 650g that reclaims when last time preparing (contains the about 460g of diacetone alcohol, unreacted dimethylaminoethyl acrylate methyl amido ethyl ester 70g, the about 80g of γ-r-chloropropyl trimethoxyl silane), dimethyl formamide 1.0g and nitroxyl free radical are sent pyridine alcohol 0.6g, the electric heating cooker heating, logical N
2Gas, mechanical stirring is at 130～140 ℃ of internal reaction 6h.When being cooled to 80 ℃, logical N
2Down employing oil pump 0～667Pa distillation of reducing pressure of protection steams front-end volatiles in head temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, and control distillment temperature is no more than 120 ℃.When head temperature drops to 60 ℃ and following, get thick liquid and be product, quality is 664.5g.This product is dissolved in methyl alcohol and obtains brown liquid, and proportion is 0.947 during 20 ℃ of this liquid, n
D 20Be 1.3965, M during mass spectroscopy
++ 1 peak 321 is obvious; Molar yield is 93.0%.
Embodiment 3: add dimethylaminoethyl acrylate methyl amido ethyl ester 320g, γ-r-chloropropyl trimethoxyl silane 400g, n-hexyl alcohol 450g in the three-necked flask of 2000ml band thermometer, spherical condensation tube, airway and mechanical stirring device, dimethyl formamide 1.0g and 2,5-di-tert-butyl hydroquinone 0.8g, the electric heating cooker heating, logical N
2Gas, mechanical stirring is at 130～140 ℃ of internal reaction 4h.When being cooled to 80 ℃, logical N
2Down employing oil pump 0～667Pa distillation of reducing pressure of protection steams front-end volatiles in head temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, and control distillment temperature is no more than 120 ℃.When head temperature drops to 60 ℃ and following, get thick liquid and be product, quality is 653.8g.This product is dissolved in methyl alcohol and obtains brown liquid, and proportion is 0.948 during 20 ℃ of this liquid, n
D 20Be 1.3967, M during mass spectroscopy
++ 1 peak 321 is obvious; Molar yield is 91.5%.
Embodiment 4: add dimethylaminoethyl acrylate methyl amido ethyl ester 320g, γ-r-chloropropyl trimethoxyl silane 400g, dimethylbenzene 460g in the three-necked flask of 2000ml band thermometer, spherical condensation tube, airway and mechanical stirring device, dimethyl formamide 1.0g and 4-dimethylamine pyridine 0.4g, the electric heating cooker heating, logical N
2Gas, mechanical stirring is at 130～140 ℃ of internal reaction 4h.When being cooled to 80 ℃, logical N
2Down employing oil pump 0～667Pa distillation of reducing pressure of protection steams front-end volatiles in head temperature earlier during less than 60 ℃, reclaims solvent and unreacted raw material between 60～80 ℃, and control distillment temperature is no more than 120 ℃.When head temperature drops to 60 ℃ and following, get thick liquid and be product, quality is 660.9g.This product is dissolved in methyl alcohol and obtains brown liquid, and proportion is 0.949 during 20 ℃ of this liquid, n
D 20Be 1.3966, M during mass spectroscopy
++ 1 peak 321 is obvious; Molar yield is 92.5%.
Claims (3)
1. the synthetic method of a dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride, it is characterized in that: in organic solvent, nitrogen protection and stopper exist down, dimethylaminoethyl acrylate methyl amido ethyl ester and γ-r-chloropropyl trimethoxyl silane get mixture at 130～140 ℃ of stirring reaction 3～6h, and mixture obtains dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride through purification; Described organic solvent be diacetone alcohol, n-hexyl alcohol or dimethylbenzene respectively with the mixed solvent of dimethyl formamide combination; Described stopper is a 2,5 di tert butyl hydroquinone, nitroxyl free radical piperidines alcohol or 4-dimethylamine pyridine.
2. synthetic method according to claim 1 is characterized in that: the reaction mol ratio of dimethylaminoethyl acrylate methyl amido ethyl ester, γ-r-chloropropyl trimethoxyl silane, organic solvent and stopper is 1～1.1: 0.9～1.1: 2～2.5: 0.15～0.20.
3. synthetic method according to claim 1, it is characterized in that: described mixture is through purifying under nitrogen protection, 0～the 667Pa that reduces pressure distillation, steam front-end volatiles during less than 60 ℃ earlier in temperature, reclaim solvent and unreacted raw material between 60～80 ℃, control distillment temperature is no more than 120 ℃; When the temperature of still head drops to 60 ℃ and following, obtain viscous liquid dimethyl [2-(methacryloxy) ethyl] [3-(Trimethoxy silane) propyl group] ammonium chloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2050466A1 (en) * | 1969-05-15 | 1971-05-27 | Dow Corning | Amino functional unsatd cationic coupler |
| US3884886A (en) * | 1973-01-15 | 1975-05-20 | Dow Corning | Cationic unsaturated amine-functional silane coupling agents |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2050466A1 (en) * | 1969-05-15 | 1971-05-27 | Dow Corning | Amino functional unsatd cationic coupler |
| US3884886A (en) * | 1973-01-15 | 1975-05-20 | Dow Corning | Cationic unsaturated amine-functional silane coupling agents |
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