CN103396433A - Diacylthioxo silane coupling agent and preparation method thereof - Google Patents
Diacylthioxo silane coupling agent and preparation method thereof Download PDFInfo
- Publication number
- CN103396433A CN103396433A CN2013103021560A CN201310302156A CN103396433A CN 103396433 A CN103396433 A CN 103396433A CN 2013103021560 A CN2013103021560 A CN 2013103021560A CN 201310302156 A CN201310302156 A CN 201310302156A CN 103396433 A CN103396433 A CN 103396433A
- Authority
- CN
- China
- Prior art keywords
- silane coupling
- coupling agent
- preparation
- acyl sulfenyl
- diacid chloride
- 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
Abstract
The invention discloses a diacylthioxo silane coupling agent and a preparation method thereof. A structural general formula of the silane coupling agent is shown in the specification, wherein in the formula, R1 is methyl or ethyl, and the X group is oxalyl group, phthaloyl/m-benezene diformyl/terephthaloyl, malonyl, succinyl, adipoyl, fumaryl, isodivaleryl, 2-methyladipyl, octanedioyl, decanedioyl and other dicapryloyl. The diacylthioxo silane coupling agent is accessible in raw materials and low in equipment requirements, can be produced in most plants or laboratories, can be widely used in rubber chemicals and effectively improves rubber properties.
Description
Technical field
The present invention relates to a kind of pair of acyl sulfenyl silane coupling agent and preparation method thereof.
Background technology
Silane coupler containing sulfur is the important auxiliary agent of rubber industry, can play the effect of bonding force between Reinforced Rubber and filler, and the multinomial performances such as the tensile strength of rubber item, wear resistance, moisture-proof slip are had significant effect of optimization.Silane coupler containing sulfur,, as two-[3-(triethoxysilicane) propyl group]-tetrasulfide (commodity are called Si-69), become rubber industry, especially indispensable product in the tire manufacturing.The most frequently used silane coupler containing sulfur of current rubber industry is polysulfide silane, and is wherein maximum with the Si-69 consumption again, usually contains the polysulfidic bond that a plurality of sulphur atoms are connected in polysulfide silane, and at high temperature, polysulfidic bond can rupture, thereby makes the unsaturated double-bond polymerization.But, the polysulfide silane that is used in a large number at present, take Si-69 as example, in rubber mixing process, polysulfidic bond easily ruptures in advance and causes the sulfuration in advance of rubber, causes rubber performance to descend and waste material even occurs.Equally, also there is this problem in the larger 3-mercaptopropyltriethoxysilane of activity.
Summary of the invention
The problem that the present invention vulcanizes in advance in order to solve rubber,, in conjunction with existing multiple silane coupler containing sulfur, proposed a kind of pair of acyl sulfenyl silane coupling agent and preparation method thereof.
The present invention for the technical scheme that provides is provided is: a kind of pair of acyl sulfenyl silane coupling agent, and the concrete structure general formula is as follows:
In formula, R
lFor methyl or ethyl; X is oxalyl group or has general structure
A class group, wherein G is a kind of in the alkyl that mixes of the alkyl of aryl, cladodification or straight chain, saturated or undersaturated alkyl, replacement or unsubstituted alkyl or aromatic/aliphatic.
Described general structure
A class group be selected from FUMARIC ACID TECH GRADE, succinyl, glutaryl-, adipyl, neighbour// a kind of in terephthaloyl or sebacoyl.
The present invention also provides two kinds of routes of the two acyl sulfenyl silane coupling agents of synthetic this class, two kinds of routes all can obtain identical product with different reactive modes, different raw materials, the silane raw material that two lines relate to be easy to get, the product of large-scale commercial production, can select suitable route to synthesize target product according to practical condition, two kinds of routes be as follows respectively:
Route one:
3-mercapto propyl trialkoxy silane and diacid chloride are reacted by the mode of dehydrochlorination, obtain after filtering, take off low boiling.
React by the mode of dehydrochlorination when 3-mercapto propyl trialkoxy silane and diacid chloride the solvent that uses for not with the solvent of 3-mercapto propyl trialkoxy silane or diacid chloride reaction, comprise a kind of in toluene, tetrahydrofuran (THF), alkane solvent or acetone.
After 3-mercapto propyl trialkoxy silane and diacid chloride were reacted by the mode of dehydrochlorination, the hydrogenchloride that removes was drained or with alkali, absorbs in the gas mode.
Route two:
1), with sodium sulphite or the Sodium sulfhydrate aqueous solution, with the diacid chloride reaction, prepare the sulfo-Sodium Dicarboxylic Acid aqueous solution;
2) the sulfo-Sodium Dicarboxylic Acid aqueous solution for preparing of 3-chloropropyl trialkoxy silane and step 1) reaction under phase-transfer catalyst exists, through filtering, underpressure distillation obtains product after refining.
Described phase-transfer catalyst is a kind of in quaternary ammonium salt or season phosphonium salt,
Comprise a kind of in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, four hexyl ammonium chlorides, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, chlorineization four benzene Phosphonium or chlorination 16 alkyl three fourth base Phosphonium.
Beneficial effect of the present invention is presented as:
1, the two acyl sulfenyl silane coupling agent synthetic routes that the present invention relates to are reasonable in design, and equipment requirements is low, and most factories or laboratory all can realize producing;
2, raw material required for the present invention is easy to get;
3, provided by the present invention pair of acyl sulfenyl silane coupling agent can be used for rubber ingredients, tire auxiliary agent especially, and in the time of can overcoming the polysulfide silane coupling agents such as Si-69 as rubber ingredients, the problem that rubber vulcanizes in advance;
4, provided by the present invention pair of acyl sulfenyl silane coupling agent is used for rubber ingredients, but contain reactive group the same as the conventional silanes coupling agent can improve the interaction between rubber and filler equally, improves the properties of tire.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, modification or replacement to the inventive method, step or condition are done, all belong to scope of the present invention.
Embodiment 1
The present embodiment is pressed route one and is carried out.
add 476g(2mol in the 2L of drying flask) the 3-mercaptopropyltriethoxysilane, add 252.5g(2.5mol) anhydrous triethylamine, add the dilution of 200mL dry toluene, start mechanical stirring, after mixing, slowly splash into 127g(1mol from constant pressure funnel) oxalyl chloride, produce at once a large amount of white insoluble precipitations, dropwise after 30 minutes, keep stirring after 2 hours, remove by filter precipitation, after triethylamine and toluene are removed in underpressure distillation, obtain light yellow thick liquid, slightly muddy, after refiltering once, decompression removes low boiling, obtain the light yellow transparent thick liquid of 659g, be product oxalyl-two-[triethoxysilylpropyl sulphur], yield 98%.By gas chromatographic analysis, two kinds of material contents all have been reduced to 1% once, and by proton nmr spectra analysed preparation structure, result is
1H-NMR(CDCl
3, δ, ppm): 0.74(t, 4H, Si-CH
2-), 1.34(t, 18H, O-C-CH
3), 1.71(m, 4H, C-CH
2-C), 2.98(t, 4H, S-CH
2-), 3.54(m, 12H, O-CH
2-), its result is consistent with product structure.
Embodiment 2
The present embodiment is pressed route two and is carried out.
1) prepare dithio hexanodioic acid sodium water solution.In the there-necked flask of 2L, add nine water cure sodium solid 240g(1mol), add 150g water, obtain concentration after dissolving and be 20% sodium sulfide solution, under mechanical stirring, with 91.5g(0.5mol) Adipoyl Chloride splashes into from constant pressure funnel, approximately dropwised in 20 minutes, along with splashing into of Adipoyl Chloride, in bottle, temperature can rise to 70 ℃ of left and right, keep stirring, system is naturally cooled to room temperature, obtain the slightly transparent dithio hexanodioic acid sodium water solution of thickness.
2) prepare hexanedioyl-two-[triethoxysilylpropyl sulphur].add the saturated four hexyl ammonium chloride solutions of 3g in the solution that step 1) makes, under mechanical stirring, with 240g(1mol) the 3-chloropropyl triethoxysilane splashes into from constant pressure funnel, dropwise in 15 minutes, after completing, being warming up to 50 ℃ kept after 2 hours, reaction is 4 hours under 70-80 ℃, gas chromatographic detection 3-chloropropyl triethoxysilane content is less than 3%, stop stirring, separatory goes out the upper strata organic layer, after filtering once, low boiling taken off in decompression, remove wherein low-boiling point material and a small amount of unreacted 3-chloropropyl triethoxysilane, obtain light yellow thickness liquid product 281g, yield 96%.Gas chromatographic analysis, in product, the content of 3-chloropropyl triethoxysilane is less than 1%, and proton nmr spectra is identified product structure, and result is
1H-NMR(CDCl
3, δ, ppm): 0.74(t, 4H, Si-CH
2-), 1.34(t, 18H, Si-O-C-CH
3), 1.55～1.84(br, 8H, C-CH
2-C), 2.55(t, 4H, S-CO-CH
2-), 2.99(t, 4H ,-S-CH
2-), 3.55(m, 12H, Si-O-CH
2-), the proton nmr spectra result shows, the product of acquisition is hexanedioyl-two-[triethoxysilylpropyl sulphur].
Embodiment 3
The present embodiment is pressed route one and is carried out.
add 238g(1mol in the 2L of drying flask) the 3-mercaptopropyltriethoxysilane, add the dilution of 50mL anhydrous tetrahydro furan, get 101.5g(0.5mol) after p-phthaloyl chloride dissolves with the 200mL anhydrous tetrahydro furan, slowly splash into from constant pressure funnel, under mechanical stirring, the hydrogenchloride that produces is discharged with nitrogen, dropwise after 30 minutes, keep stirring 2 hours, toluene is removed in underpressure distillation, this moment, system pH was about 4, add in the 5g sodium ethylate and after, filter, obtain light yellow thick liquid, decompression removes low boiling, obtain the light yellow transparent thick liquid of 294g, be product phenyl-diformyl-two-[triethoxysilylpropyl sulphur], yield 97%.Gas chromatographic analysis, 3-mercaptopropyltriethoxysilane content wherein has been less than 1%, proton nmr spectra analysed preparation structure, result is
1H-NMR(CDCl
3, δ, ppm): 0.74(t, 4H, Si-CH
2-), 1.34(t, 18H, O-C-CH
3), 1.71(m, 4H, C-CH
2-C), 2.99(t, 4H, S-CH
2-), 3.56(m, 12H, O-CH
2-), 8.25(s, 4H, C
6H
4) its result is consistent with product structure.
Embodiment 4
The present embodiment is pressed route two and is carried out.
1) prepare dithio sebacic acid sodium water solution.In the there-necked flask of 2L, add Sodium sulfhydrate solid 105g(2mol), add 478g water, obtain concentration after dissolving and be 18% sodium hydrosulfide, under mechanical stirring, with 120g(0.5mol) sebacoyl chloride splashes into from constant pressure funnel, approximately dropwised in 20 minutes, along with splashing into of sebacoyl chloride, in bottle, temperature can rise, and suitably uses frozen water cooling, and the hydrogen sulfide of generation passes into the absorption of absorbing by liquid caustic soda pond and removes, keep stirring after 3 hours, obtain the slightly transparent dithio sebacic acid sodium water solution of thickness.
2) add saturated nacl aqueous solution 50mL in the dithio sebacic acid sodium water solution that step 1 prepares, add methyl tricapryl ammonium chloride saturated solution 5mL as phase-transfer catalyst, under mechanical stirring, with 198g(1mol) the 3-r-chloropropyl trimethoxyl silane splashes into from constant pressure funnel, dropwise in 15 minutes, after completing, being warming up to 50 ℃ kept after 2 hours, reaction is 4 hours under 70-80 ℃, gas chromatographic detection 3-r-chloropropyl trimethoxyl silane content is less than 3%, stop stirring, separatory goes out the upper strata organic layer, after removing by filter a small amount of hydrolyzate, low boiling taken off in decompression, remove wherein low-boiling point material and a small amount of unreacted 3-r-chloropropyl trimethoxyl silane, obtain the light yellow thickness liquid product of 260g sebacoyl-two-[trimethoxy silicon propylthio], yield 89%.Gas chromatographic analysis, in product, the content of 3-r-chloropropyl trimethoxyl silane is less than 1%, and proton nmr spectra is identified product structure, and result is
1H-NMR(CDCl
3, δ, ppm): 0.74(t, 4H, Si-CH
2-), 1.52～1.85(br, 16H, C-CH
2-C), 2.55(t, 4H, S-CO-CH
2-), 2.98(t, 4H ,-S-CH
2-), 3.58(s, 18H, Si-O-CH
3), the proton nmr spectra result conforms to product structure.
Embodiment 5
The present embodiment is pressed route one and is carried out.
Add 392g(2mol in the 2L of drying flask) the 3-mercaptopropyl trimethoxysilane, add the dilution of 250mL anhydrous n-hexane, add Anhydrous potassium carbonate 300g, get 153g(1mol) fumaryl chloride, slowly splash into from constant pressure funnel, under mechanical stirring, dropwise after 30 minutes, keep stirring after 4 hours stopped reaction, filter, after normal hexane is removed in underpressure distillation, take off lower boiling under low vacuum 1 hour, obtain the light yellow thick liquid of 455g, be product fumaroyl-two-[trimethoxy silicon propylthio], yield 96%.In the gas chromatographic detection product, the content of remaining 3-mercaptopropyl trimethoxysilane is less than 1%, and proton nmr spectra is identified product structure, and result is
1H-NMR(CDCl
3, δ, ppm): 0.75(t, 4H, Si-CH
2-), 1.73(m, 4H, C-CH
2-C), 2.98(t, 4H ,-S-CH
2-), 3.56(s, 18H, Si-O-CH
3), 7.14(s, 2H ,-CH=CH-), the proton nmr spectra result conforms to product structure, proves the product that has obtained expection.
Embodiment 6
The present embodiment is pressed route one and is carried out.
Add 476g(2mol in the 2L of drying flask) the 3-mercaptopropyltriethoxysilane, add the dilution of 250mL anhydrous propanone, add sodium ethylate 200g, get 168g(1mol) glutaryl chlorine, dissolve with the 200mL anhydrous propanone, slowly splash into from constant pressure funnel, under mechanical stirring, dropwise after 30 minutes, keep stirring after 4 hours, stopped reaction, filter, after acetone is removed in underpressure distillation, took off lower boiling under low vacuum 1 hour, obtain light yellow liquid, be the own glutaryl of product-two-[triethoxysilylpropyl sulphur].The content of 3-mercaptopropyltriethoxysilane in the gas chromatographic detection product, less than 1%, proton nmr spectra is identified product structure, result is
1H-NMR(CDCl
3, δ, ppm): 0.75(t, 4H, Si-CH
2-), 1.34(t, 18H, Si-O-C-CH
3), 1.54～1.86(br, 6H, C-CH
2-C), 2.55(t, 4H, S-CO-CH
2-), 2.96(t, 4H ,-S-CH
2-), 3.56(m, 12H, Si-O-CH
2-), the proton nmr spectra result conforms to product structure.
Embodiment 7
The present embodiment is pressed route one and is carried out.
Add 392g(2mol in the 2L of drying flask) the 3-mercaptopropyl trimethoxysilane, add the dilution of 250mL dry oil ether, add anhydrous pyridine 200mL, get 155g(1mol) succinic chloride, be dissolved in 150mL dry oil ether, slowly splash into from constant pressure funnel, under mechanical stirring, dropwise after 30 minutes, keep stirring after 4 hours, stopped reaction, filter, after sherwood oil is removed in underpressure distillation, took off lower boiling under low vacuum 1 hour, obtain light yellow liquid, be product succinyl-two-[trimethoxy silicon propylthio].Gas chromatographic analysis, 3-mercaptopropyl trimethoxysilane content wherein has been less than 1%, proton nmr spectra analysed preparation structure, result is
1H-NMR(CDCl
3, δ, ppm): 0.76(t, 4H, Si-CH
2-), 1.72(m, 4H, C-CH
2-C), 2.62(s, 4H, S-CO-CH
2-), 2.92(t, 4H, S-CH
2-), 3.59(s, 18H, Si-O-CH
3), its result is consistent with product structure.
Claims (7)
1. a two acyl sulfenyl silane coupling agent, is characterized in that, the concrete structure general formula is as follows:
In formula, R
1For methyl or ethyl; X is oxalyl group or has general structure
A class group, wherein G is a kind of in the alkyl that mixes of the alkyl of aryl, cladodification or straight chain, saturated or undersaturated alkyl, replacement or unsubstituted alkyl or aromatic/aliphatic.
2. a kind of pair of acyl sulfenyl silane coupling agent according to claim 1, is characterized in that described general structure
A class group be selected from FUMARIC ACID TECH GRADE, succinyl, glutaryl-, adipyl, neighbour// a kind of in terephthaloyl or sebacoyl.
3. the preparation method of two acyl sulfenyl silane coupling agents, is characterized in that, and is specific as follows: 3-mercapto propyl trialkoxy silane and diacid chloride are reacted by the mode of dehydrochlorination, filter, take off to hang down after boiling and obtain.
4. the preparation method of a kind of pair of acyl sulfenyl silane coupling agent according to claim 3, it is characterized in that, 3-mercapto propyl trialkoxy silane and diacid chloride by the mode of dehydrochlorination react the solvent that uses for not with the solvent of 3-mercapto propyl trialkoxy silane or diacid chloride reaction, comprise a kind of in toluene, tetrahydrofuran (THF), alkane solvent or acetone.
5. the preparation method of a kind of pair of acyl sulfenyl silane coupling agent according to claim 3, is characterized in that, after 3-mercapto propyl trialkoxy silane and diacid chloride were reacted by the mode of dehydrochlorination, the hydrogenchloride that removes was drained or with alkali, absorbs in the gas mode.
6. the preparation method of two acyl sulfenyl silane coupling agents, is characterized in that, comprises the steps:
1), with sodium sulphite or the Sodium sulfhydrate aqueous solution, with the diacid chloride reaction, prepare the sulfo-Sodium Dicarboxylic Acid aqueous solution;
2) the sulfo-Sodium Dicarboxylic Acid aqueous solution for preparing of 3-chloropropyl trialkoxy silane and step 1) reaction under phase-transfer catalyst exists, through filtering, underpressure distillation obtains product after refining.
7. the preparation method of a kind of pair of acyl sulfenyl silane coupling agent according to claim 6, is characterized in that, described phase-transfer catalyst is a kind of in quaternary ammonium salt or season phosphonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103021560A CN103396433A (en) | 2013-07-16 | 2013-07-16 | Diacylthioxo silane coupling agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103021560A CN103396433A (en) | 2013-07-16 | 2013-07-16 | Diacylthioxo silane coupling agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103396433A true CN103396433A (en) | 2013-11-20 |
Family
ID=49560200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103021560A Pending CN103396433A (en) | 2013-07-16 | 2013-07-16 | Diacylthioxo silane coupling agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103396433A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709188A (en) * | 2013-12-06 | 2014-04-09 | 江西晨光新材料有限公司 | Technology for preparing terminated-type sulfur-containing silane coupling agent through hydrosilation method |
| WO2017169975A1 (en) * | 2016-03-31 | 2017-10-05 | 株式会社大阪ソーダ | Rubber composition for tires |
| CN108485023A (en) * | 2018-02-06 | 2018-09-04 | 山东大正新材料科技股份有限公司 | A kind of polythene material and preparation method thereof and product |
| CN109517006A (en) * | 2018-11-13 | 2019-03-26 | 江西宏柏新材料股份有限公司 | The method of tower organic method continuous production 3- Octanoylthio propyl-triethoxysilicane |
| WO2022215986A1 (en) * | 2021-04-06 | 2022-10-13 | 부산대학교 산학협력단 | Liquid butadiene compound with both ends modified, method for preparing same, and use of same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834099A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and its prepn. |
| CN1845930A (en) * | 2003-07-03 | 2006-10-11 | 通用电气公司 | Process for the preparation of thiocarboxylate silane |
-
2013
- 2013-07-16 CN CN2013103021560A patent/CN103396433A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845930A (en) * | 2003-07-03 | 2006-10-11 | 通用电气公司 | Process for the preparation of thiocarboxylate silane |
| CN1834099A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and its prepn. |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709188A (en) * | 2013-12-06 | 2014-04-09 | 江西晨光新材料有限公司 | Technology for preparing terminated-type sulfur-containing silane coupling agent through hydrosilation method |
| WO2017169975A1 (en) * | 2016-03-31 | 2017-10-05 | 株式会社大阪ソーダ | Rubber composition for tires |
| CN108485023A (en) * | 2018-02-06 | 2018-09-04 | 山东大正新材料科技股份有限公司 | A kind of polythene material and preparation method thereof and product |
| CN108485023B (en) * | 2018-02-06 | 2021-05-28 | 山东大正新材料科技股份有限公司 | Polyethylene material, preparation method and product thereof |
| CN109517006A (en) * | 2018-11-13 | 2019-03-26 | 江西宏柏新材料股份有限公司 | The method of tower organic method continuous production 3- Octanoylthio propyl-triethoxysilicane |
| WO2022215986A1 (en) * | 2021-04-06 | 2022-10-13 | 부산대학교 산학협력단 | Liquid butadiene compound with both ends modified, method for preparing same, and use of same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103396433A (en) | Diacylthioxo silane coupling agent and preparation method thereof | |
| CN101184767B (en) | Aqueous catalytic process for the preparation of thiocarboxylate silane | |
| CN1156149A (en) | Di(silyl alkyl) dithioalkane producing method | |
| CN105435706B (en) | A kind of sulfonate type anionic gemini surfactant and preparation method thereof | |
| CN104945286A (en) | Method for compounding high-purity sulfuric acid esters | |
| CN101260118B (en) | Water-phase synthesis method for di-[(triethoxylsilicon)propyl]-bisulfide | |
| CN101157681A (en) | Method for preparing 1,3 propane sultone | |
| CN107827833A (en) | Triazines multifunctional light absorbs antioxidant class compound and its preparation method and application | |
| CN107312565A (en) | A kind of method of three components eutectic agent abstraction desulfurization | |
| CN103709188A (en) | Technology for preparing terminated-type sulfur-containing silane coupling agent through hydrosilation method | |
| CN102755855A (en) | Alkylaryl sulfonate type hyperbranched polymer surface active agent and preparation method thereof | |
| CN103755613A (en) | Preparation method of rubber vulcanization accelerator zinc dibenzyl dithiocarbamate | |
| CN104844648B (en) | A kind of synthetic method of group thiophosphate compound | |
| CN104230722A (en) | Preparation method of bifluorosulfonyl imide onium salt | |
| CN106829876B (en) | The recoverying and utilizing method of oil plant sulfur removal plant sulphur steam | |
| BR102018074583B1 (en) | SILANE MIXTURES AND PROCESSES FOR PREPARING THEM | |
| CN103073421A (en) | High-efficiency simple synthetic method for delta-chlorobutyl ester | |
| Singh et al. | Kinetic investigation on liquid–liquid–solid phase transfer catalyzed synthesis of dibenzyl disulfide with H2S-laden monoethanolamine | |
| CN100436522C (en) | Double-bond-containing silicane coupling agent and preparing method thereof | |
| CN103804410A (en) | Water-phase preparation method of low-impurity light-smell polysulfide silane coupling agent | |
| CN102993114A (en) | Method for producing 1H-tetrazole-5-acetic acid | |
| CN103242261A (en) | Synthetic method of alpha-amino aromatic ketone compound | |
| CN105176569A (en) | Extraction method for dibenzothiophene | |
| CN102276415B (en) | Method for improving fluorine-containing alkyl alcohol yield | |
| CN107759637A (en) | The fluoridation catalyst of a kind of phosphonitrile and phosphazene derivative and its synthetic method of fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131120 |
|
| WD01 | Invention patent application deemed withdrawn after publication |