CN1706849A - Phase transfer catalyst process of preparing silicon-69 - Google Patents
Phase transfer catalyst process of preparing silicon-69 Download PDFInfo
- Publication number
- CN1706849A CN1706849A CN 200410025002 CN200410025002A CN1706849A CN 1706849 A CN1706849 A CN 1706849A CN 200410025002 CN200410025002 CN 200410025002 CN 200410025002 A CN200410025002 A CN 200410025002A CN 1706849 A CN1706849 A CN 1706849A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- silicon
- gamma
- phase transfer
- salt
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to phase transfer catalyst process of preparing silicon-69, which is used in produced radial ply tyre and other rubber product. The material includes water, Na2S.9H2O, sulfur powder, salt, catalyst and gamma-chloropropyl triethoxyl silane in certain proportion and has no organic solvent. The technological process includes filling enamel reactor with N2; adding water, Na2S.9H2O, sulfur powder and salt while stirring and heating to 70-90 deg.c for dissolving completely and maintaining for some period; adding catalyst ammonium tetrabutyl bromide and gamma-chloropropyl triethoxyl silane while stirring until no red color; depositing, eliminating waste water in the lower layer and leaving the transparent oily liquid in the upper layer as the coarse silicon-69; and filtering to obtain refined silicon-69. The present invention has the advantages of low cost, short production period, high product yield, environment friendship, etc.
Description
Technical Field
The invention relates to a process for preparing silicon-69 by using a phase transfer catalyst, wherein the silicon-69 can be used in radial tires and rubber products thereof, and belongs to the technical field of coupling agents.
Background
Silicon-69 is a silane coupling agent, can be used as a high-grade vulcanizing agent, an activating agent, a reinforcing agent, a softening agent and a softening agent in the rubber industry, can improve the tensile strength, the wear resistance, the fatigue resistance and the elasticity of colloidal particles, and can be used for treating rubber and fillers to enable the obtained rubber material to achieve the effects of delaying coking, accelerating vulcanization and improving reinforcement.
The earliest invention in 1955, Degussa, Germany, produced Si-69 by direct synthesis, specifically, sodium polysulfide was dissolved in an organic solvent such as absolute ethanol or petroleum ether, chloropropyltriethoxysilane was added, and a light yellow transparent liquid product, i.e., Si-69, was produced by controlling the temperature and time.
The production process of Nippon Shicheng chemical industry Co., Ltd includes dissolving sodium sulfide in mixed solvent of ethanol and benzene in certain ratio, eliminating water content in sodium sulfide by means of three-phase azeotropic principle to produce anhydrous sodium sulfide, adding anhydrous ethanol and sulfur to produce sodium polysulfide, and dropping chloropropyl triethoxy silane at certain temperature and for certain time to produce Si-69 product. Both of these methods have disadvantages:
1. the reaction must be ensured to be carried out under the anhydrous state and is easy to hydrolyze when meeting water;
2. the reaction time is longer, generally between 5 and 9 hours;
3. the sediment is more, and the waste treatment is more troublesome;
4. organic solvents must be used as the medium.
The united states company adopts the phase transfer catalysis method to produce silicon-69, although the reaction speed is accelerated and the reaction time is shortened, the product yield is lower, generally below 90 percent, but the method also needs to add benzene organic solvent before the reaction, and a large amount of salt crystals precipitated after the generation need to be treated.
Disclosure of Invention
The invention aims to provide a process for preparing silicon-69 by using a phase transfer catalyst which does not contain any organic solvent, has short production time and less precipitates.
In order to achieve the purpose, the technical scheme of the invention is to provide a process for preparing silicon-69 by using a phase transfer catalyst, which is characterized by being prepared from the following raw materials in parts by weight:
in water 100
Na2S·9H2O (analytical purity) 120-
40-60 parts of sulfur powder
Salt 8-12
Catalyst 6-10
Gamma-chloropropyltriethoxysilane 230-
The catalyst is tetrabutylammonium bromide.
A process for preparing Si-69 by phase-transfer catalyst features that no organic solvent is added,
the process comprises the following steps:
(1) weighing the raw materials according to the weight ratio;
(2) firstly using nitrogen N in enamel reaction pot2Replacement;
(3) adding water and Na2S·9H2Stirring O (analytically pure), sulfur powder and salt, heating to 70-90 deg.C for 25-40 min until all the components are dissolved, holding the temperature for 25-40 min, and stirring;
(4) adding catalyst tetrabutylammonium bromide and gamma-chloropropyltriethoxysilane until the red color is completely removed, and stopping stirring;
(5) settling for 10-20 minutes, completely discharging the lower colorless transparent wastewater into a wastewater tank, and leaving yellow transparent oily liquid as crude silicon-69;
(6) filtering the yellow transparent oily liquid to obtain refined silicon-69.
The invention does not add any organic solvent, and uses phase transfer catalyst to produce silicon-69.
The reaction principle of the invention is as follows:
in the formula Q+X-Represents a catalyst, MY represents a reactant dissolved in the aqueous phase, RX is a reactant dissolved in the oil phase, RY is the product to be synthesizedProduct, catalyst Q+X-Firstly, the ionic pair reacts with a reactant MY to form an ionic pair with certain solubility in an oil phase, the ionic pair is extracted into the oil phase under strong stirring, the ionic pair and a reactant RX existing in the oil phase quickly react to generate a required product RY, and a catalyst Q is separated out+X returns to the water phase again, and the reaction is continuously carried out by circulating the X.
The chemical reaction formula of the invention is as follows:
wherein X is Cl or Br.
The invention has the advantages that:
1. the equipment investment is low, and the operation is simple, convenient and safe;
2. the production period is short, and the time from feeding to discharging is less than 2 hours;
3. the product yield is high and is more than 95 percent;
4. flammable, explosive and toxic organic solvents are not used, fire safety management of factories is facilitated, and the operating environment is improved;
5. the invention has no waste residue discharge, and the waste water contains NaCl and catalyst for continuous reuse, thereby obviously improving the three-waste treatment and being beneficial to environmental protection.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to the following examples:
examples
Firstly using nitrogen N in enamel reaction pot2Replacement; adding 100Kg of water and Na2S·9H2125Kg of O (analytically pure), 50Kg of sulfur powder and 10Kg of salt are stirred, heated to 80 ℃ for 30 minutes until the materials are completely dissolved, kept at the constant temperature for 30 minutes, stirred continuously and stopped heating; adding 8Kg of tetrabutylammonium bromide and 240Kg of gamma-chloropropyltriethoxysilane serving as catalysts, and stopping stirring after the red color is completely faded for 20-25 minutes; settling for 15 minutes, completely discharging the lower colorless and transparent wastewater into a wastewater tank, and leaving yellow transparent oily liquid as crude silicon-69; yellow color will beFiltering the transparent oily liquid to obtain refined silicon-69 with the weight of 258.7 Kg.
Sampling and analyzing: the total S was 23.04% and the product yield was 96.1%.
Claims (4)
1. A process for preparing silicon-69 by using a phase transfer catalyst is characterized by being prepared from the following raw materials in parts by weight:
in water 100
Na2S·9H2O (analytical purity) 120-
40-60 parts of sulfur powder
Salt 8-12
Catalyst 6-10
Gamma-chloropropyltriethoxysilane 230-
2. A process for preparing silicon-69 by phase transfer catalyst comprises the following steps:
in water 100
Na2S·9H2O (analytically pure) 125
Sulfur powder 50
Salt 10
Catalyst 8
Gamma-chloropropyltriethoxysilane 240
3. The process of claim 1 wherein said catalyst is tetrabutylammonium bromide.
4. A process for preparing silicon-69 by using phase transfer catalyst, which is characterized by that it does not add any organic solvent, and its process is as follows:
(1) weighing the raw materials according to the weight ratio;
(2) firstly using nitrogen N in enamel reaction pot2Replacement;
(3) adding water and Na2S·9H2Stirring O (analytically pure), sulfur powder and salt, heating to 70-90 deg.C for 25-40 min until all the components are dissolved, keeping the temperature for 25-40 min, stirring, and stopping heating;
(4) adding catalyst tetrabutylammonium bromide and gamma-chloropropyltriethoxysilane until the red color is completely removed, and stopping stirring;
(5) settling for 10-20 minutes, completely discharging the lower colorless transparent wastewater into a wastewater tank, and leaving yellow transparent oily liquid as crude silicon-69;
(6) filtering the yellow transparent oily liquid to obtain refined silicon-69.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100250022A CN1305879C (en) | 2004-06-09 | 2004-06-09 | Phase transfer catalyst process of preparing silicon-69 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100250022A CN1305879C (en) | 2004-06-09 | 2004-06-09 | Phase transfer catalyst process of preparing silicon-69 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1706849A true CN1706849A (en) | 2005-12-14 |
| CN1305879C CN1305879C (en) | 2007-03-21 |
Family
ID=35580977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100250022A Expired - Fee Related CN1305879C (en) | 2004-06-09 | 2004-06-09 | Phase transfer catalyst process of preparing silicon-69 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1305879C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511848B (en) * | 2006-09-01 | 2012-08-29 | 赢创德固赛有限责任公司 | Method for producing organosilanes |
| CN103755736A (en) * | 2014-01-27 | 2014-04-30 | 南昌赣宇有机硅有限公司 | Solvent synthesis process for bis-(Y-triethoxypropylsilane) tetrasulfide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405985A (en) * | 1994-07-08 | 1995-04-11 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US5468893A (en) * | 1994-07-08 | 1995-11-21 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US5583245A (en) * | 1996-03-06 | 1996-12-10 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US6448426B1 (en) * | 2001-06-29 | 2002-09-10 | Dow Corning Corporation | Process for the preparation of sulfur-containing organosilicon compounds |
| US6534668B2 (en) * | 2001-06-29 | 2003-03-18 | Dow Corning Corporation | Preparation of sulfur-containing organosilicon compounds using a buffered phase transfer catalysis process |
| US6740767B1 (en) * | 2002-11-12 | 2004-05-25 | Dow Corning Corporation | Method of making sulfur containing organosilicon compounds |
-
2004
- 2004-06-09 CN CNB2004100250022A patent/CN1305879C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101511848B (en) * | 2006-09-01 | 2012-08-29 | 赢创德固赛有限责任公司 | Method for producing organosilanes |
| CN103755736A (en) * | 2014-01-27 | 2014-04-30 | 南昌赣宇有机硅有限公司 | Solvent synthesis process for bis-(Y-triethoxypropylsilane) tetrasulfide |
| CN103755736B (en) * | 2014-01-27 | 2016-06-29 | 南昌赣宇有机硅有限公司 | A kind of solvent method synthesis technique of tetra-sulfurized pair-(γ-propyl-triethoxysilicane) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1305879C (en) | 2007-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1128834C (en) | Sulfur functionized polyorganic siloxanes | |
| TWI391398B (en) | Process for making organofunctional silanes and mixtures thereof | |
| EP1480989B1 (en) | Preparation of sulfur-containing organosilicon compounds using a buffered phase transfer catalysis process | |
| WO2010011345A1 (en) | Processes for making silane, hydrophobated silica, silica masterbatch and rubber products | |
| EP1770097B1 (en) | Preparation of sulfide chain-bearing organosilicon compounds | |
| KR19990083029A (en) | Process for producing sulfur-containing organosilicon compounds and synthetic intermediates thereof | |
| CN102295592A (en) | Preparation method of rubber vulcanization accelerator zinc dimethyldithiocarbamate | |
| CN102127227B (en) | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof | |
| CN109796625A (en) | A kind of environmental friendly regenerated dose and preparation method thereof for rubber regeneration | |
| CN1305879C (en) | Phase transfer catalyst process of preparing silicon-69 | |
| CN101885734B (en) | Method for synthesizing di-[propyltriethoxysilane]-tetrasulfide | |
| CN114989051A (en) | Production method of low-chlorine-content antioxidant 323 | |
| CN1793117A (en) | Preparation method of 3-mercaptopropionic acid | |
| CN110591396A (en) | High-performance sulfur-based modified asphalt and preparation method thereof | |
| CN114790156B (en) | Preparation method of tetra-alkyl thiuram monosulfide | |
| CN101125827A (en) | Preparation method of 3-mercaptopropionic acid | |
| CN103848933A (en) | Preparation method and application of flocculant | |
| CN1073594C (en) | Vulcanization acceralator for rare earth rubber and its preparation method | |
| CN110003266B (en) | Environment-friendly production method of high-quality 3-octanoyl thio-1-propyltriethoxysilane | |
| CN110627653B (en) | Method for synthesizing 3, 3' -dichlorobenzidine hydrochloride by hydrochloric acid transposition | |
| KR101748286B1 (en) | Method for Preparing Poly Aluminum Sulfate Silicate Using Waste Catalysts of Aluminum Oxide and Silicon Oxide | |
| CN108101865B (en) | Preparation method of rubber vulcanization accelerator CBBS | |
| CN1289476C (en) | Method of preparing dimethyl thioether using methyl sodium sulphate | |
| CN1039575C (en) | Compound liquid AlCl3 catalyst and its preparing process | |
| US5432257A (en) | Process for manufacturing a polysulfide polymer from the heavy ends waste of chlorinated hydrocarbon production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shanghai Renyi Fine Chemical Co., Ltd. Assignor: Dalian Sheng Chemical Co., Ltd. Contract record no.: 2010210000171 Denomination of invention: Phase transfer catalyst process of preparing silicon-69 Granted publication date: 20070321 License type: Exclusive License Open date: 20051214 Record date: 20101101 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Dalian Sheng Chemical Co., Ltd. Assignor: Shanghai Renyi Fine Chemical Co., Ltd. Contract record no.: 2010210000171 Date of cancellation: 20110112 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Dalian Sheng Chemical Co., Ltd. Assignor: Shanghai Renyi Fine Chemical Co., Ltd. Contract record no.: 2011210000001 Denomination of invention: Phase transfer catalyst process of preparing silicon-69 Granted publication date: 20070321 License type: Exclusive License Open date: 20051214 Record date: 20110112 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Dalian Sheng Chemical Co., Ltd. Assignor: Shanghai Renyi Fine Chemical Co., Ltd. Contract record no.: 2010210000171 Denomination of invention: Phase transfer catalyst process of preparing silicon-69 Granted publication date: 20070321 License type: Exclusive License Open date: 20051214 Record date: 20101101 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070321 Termination date: 20100609 |