CN1167120A - Preparation of chloro-sulfonated polyvinyl by solid blend method - Google Patents
Preparation of chloro-sulfonated polyvinyl by solid blend method Download PDFInfo
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- CN1167120A CN1167120A CN 97100291 CN97100291A CN1167120A CN 1167120 A CN1167120 A CN 1167120A CN 97100291 CN97100291 CN 97100291 CN 97100291 A CN97100291 A CN 97100291A CN 1167120 A CN1167120 A CN 1167120A
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- chlorosulfonated polyethylene
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Abstract
The preparation method of chlorosulfonated polyethylene by solid state blending process is characterized by mixing chlorinated poly-ethylene powder material with mixed gas of sulfur dioxide and chlorine gas according to a certain proportion, and making them react at a certain temp. to produce chlorosulfonated polyethylene. Its toxicity and pollution to environment are low, and its installation cost also is lwo.
Description
The invention relates to a method for preparing chlorosulfonated polyethylene by using a solid state blending method.
Chlorosulfonated polyethylene is one of rubber polymer products, and the current industrial production mostly adopts a solvent method process, namely carbon tetrachloride (CCl) as a solvent4) The problems of toxicity and environmental pollution have caused many limitations in the solvent method production, and at present, no effective measures for overcoming the above-mentioned disadvantages have been provided.
Patents for the solvent process were first found in us patent 2,212,786 (1940); 2,503,252, 2,503,253 (1950); 2,640,048 (1953); the above patent also discloses a method for chlorination and chlorosulfonated polyethylene reactions using a catalyst (AZO) to generate chloride ions;
united states patent 2,879,261 (1959) combines the above inventions and proposes a relatively complete solvent process for the preparation of chlorosulfonated polyethylene;
us patent 3,299,014 (1967) proposes an improved discontinuous solvent process; subsequent us patent 3,542,747 (1970) discloses a design to change a discontinuous process to a continuous process;
us patent 2,889,259 (1959), 4,584,351 (1986) discloses a process for the production of chlorosulfonated polyethylene using a fluidized bed, wherein the reaction of chlorosulfonated polyethylene is assisted by uv light;
the solvent method for producing chlorosulfonated polyethylene reported in the above patent has problems of toxicity and environmental pollution, and the fluidized bed process must use a large amount of gas circulation to achieve the degree of fluidization, thereby causing an increase in the cost of constructing the apparatus and the cost of maintaining normal production. The invention aims to provide a method for preparing chlorosulfonated polyethylene by a solid state blending method, which has low toxicity and environmental pollution, and greatly reduces the cost for constructing the device and the cost for maintaining normal production.
The invention relates to a preparation method of chlorosulfonated polyethylene, which comprises the following steps:
putting the chlorinated polyethylene powder into a clean container with a stirrer;
heating the mixture to 30-100 ℃,
adding a mixed gas of preheated sulfur dioxide and chlorine in a certain ratio;
keeping the temperature for reaction, stirring, mixing and stopping the sulfuration reaction after 60-100 minutes;
discharging reaction by-products and residual gas into a washing tank;
taking out the product in the kettle, putting the product in a vacuum furnace, and keeping the residue in the product at the temperature of 80 DEG C
After the waste acid is removed, the chlorosulfonated polyethylene product is obtained.
The chlorosulfonated polyethylene product contains 1.0-3.0% of sulfur, preferably 1.0-1.5% of sulfur, and 20-45% of chlorine, preferably 30-42%;
the melt index of the above chlorosulfonated polyethylene product is 0.05 to 1.0, preferably 0.05 to 3.5;
the ratio of the sulfur dioxide to the chlorine is 2-6: 1;
the preheating temperature of the sulfur dioxide and the chlorine is 30-100 ℃, and preferably 30-60 ℃;
the reaction temperature is preferably 30-60 ℃;
the method of the present invention may also use a single processOxide powder catalyst or ultraviolet radiation assisted initial initiation reaction; the chlorosulfonated polyethylene product prepared by the method has the structural formula as follows:
in a reaction kettle, chlorosulfonation reaction process is as follows;
the invention is described below with reference to the drawings and examples, which do not limit the invention, the scope of which is defined by the claims;
FIG. 1 is a flow diagram of a solid state blending process for preparing chlorosulfonated polyethylene in accordance with the present invention;
wherein, the reaction kettle 1, the waste gas washing tank 2, the chlorinated polyethylene storage tower 3, the vacuum deacidification device 4, the heater 5 and the chlorine storage tank 6 are arranged in the reaction kettle;
the first embodiment is as follows: feeding pretreated powdered chlorinated polyethylene (with chlorine content of 35%) from a feed inlet at the upper end of a reaction kettle (1) into a chlorinated polyethylene storage tower (3), starting stirring, heating to 50 ℃, introducing sulfur dioxide and chlorine at a ratio from a chlorine storage tank (6) and a sulfur dioxide storage tank (7) and preheated by a heater (5), wherein the ratio of mixed gas is 3: 1, reacting at a constant temperature of 50 ℃, stopping chlorosulfonation reaction after 90 minutes, discharging reaction byproducts and residual gas into a washing tank (2), taking out the product, placing the product in a deacidification vacuum vessel (4) at a temperature of 80 ℃, removing residual waste acid in the product, and analyzing the product to obtain a chlorinated polyethylene powder with the sulfur content of 1.27% and the chlorine content of 35.3%. Example II:
adding powdery chlorinated polyethylene (with 35% of chlorine content) into a reaction kettle (1), stirring, adding 0.2% of peroxide catalyst, heating to 80 ℃, introducing preheated (80 ℃) chlorine, starting chlorination reaction, after 30 minutes, introducing preheated and predetermined ratio of sulfur dioxide and chlorine mixed gas (the ratio is 3: 1), reacting at the constant temperature of 80 ℃, stopping chlorosulfonation reaction after 60 minutes, discharging a reaction product and residual gas in the kettle (1) into a washing tank (2), taking the product out of the kettle (1), placing the product in a vacuum deacidifier (4) at the temperature of 80 ℃, removing residual waste acid in the product, analyzing the product, and obtaining the product with 2.54% of sulfur and 35.5% of chlorine, in the third embodiment:
as in the first example, powdery chlorinated polyethylene (chlorine content 35%) is stirred in a kettle (1), a 40W, 3200A light wave ultraviolet radiation lamp is added in the kettle (1), after the temperature reaches 50 ℃, preheated and mixed gas of sulfur dioxide and chlorine (the ratio is still 3: 1) with a preset ratio is introduced, the reaction is carried out at a constant temperature of 50 ℃, after 60 minutes, the chlorosulfonation reaction is stopped, reaction byproducts and residual gas in the kettle (1) are discharged into a washing tank (2), then the product in the kettle (1) is taken out and placed in a vacuum deacidification device (4), and residual waste acid in the product is removed at a temperature of 80 ℃, and after the product is analyzed, the sulfur content is 2.46%, and the chlorine content is 35.3%.
Claims (8)
- The preparation method of chlorosulfonated polyethylene comprises the following steps:putting the chlorinated polyethylene powder into a clean container with a stirrer;heating the mixture to 30-100 ℃,adding a preheated mixed gas of sulfur dioxide and chlorine according to a certain ratio;keeping constant temperature reaction, stirring, mixing, and stopping the sulfuration reaction after 60-100 minutes;discharging reaction by-products and residual gas into a washing tank;taking out the product in the kettle, placing the product in a vacuum furnace, and removing residual waste acid in the product at the temperature of 80 ℃ to obtain chlorosulfonated polyethylene of the invention;
- a process according to claim 1, characterized in that the chlorosulfonated polyethylene product contains 1.0 to 3.0%, preferably 1.0 to 1.5%, sulfur, 20 to 45%, preferably 30 to 42%, chlorine;
- a process according to claim 1, characterized in that the chlorosulfonated polyethylene product has a melt index of 0.05 to 10, preferably 0.05 to 3.5;
- the process of claim 1, wherein the ratio of sulfur dioxide to chlorine is 2-6: 1;
- the process of claim 1, characterized in that the preheating temperature of sulfur dioxide and chlorine is 30 to 100 ℃, preferably 30 to 60 ℃;
- the process as claimed in claim 1, wherein the reaction temperature is preferably from 30 to 60 ℃;
- the process of claim 1, wherein the initial initiation is further assisted by a peroxide powder catalyst or ultraviolet radiation;
- a chlorosulfonated polyethylene product prepared by the process of 1 of claims 1 to 6, having the formula
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100291A CN1068604C (en) | 1997-01-24 | 1997-01-24 | Preparation of chloro-sulfonated polyvinyl by solid blend method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100291A CN1068604C (en) | 1997-01-24 | 1997-01-24 | Preparation of chloro-sulfonated polyvinyl by solid blend method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167120A true CN1167120A (en) | 1997-12-10 |
| CN1068604C CN1068604C (en) | 2001-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97100291A Expired - Fee Related CN1068604C (en) | 1997-01-24 | 1997-01-24 | Preparation of chloro-sulfonated polyvinyl by solid blend method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759819B (en) * | 2009-12-22 | 2011-07-27 | 连云港金泰达橡胶材料有限公司 | Device for preparing chlorosulfonated polyethylene by gas-solid phase method |
| CN102153684A (en) * | 2011-01-13 | 2011-08-17 | 杭州新元化工技术开发有限公司 | Method for preparing chlorosulfonated polyethylene by gas-solid reaction |
| CN105713117A (en) * | 2016-03-02 | 2016-06-29 | 中国石油天然气股份有限公司吉林石化分公司 | Improved chlorosulfonated polyethylene production system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4452953A (en) * | 1982-07-28 | 1984-06-05 | The B. F. Goodrich Company | Process for the vapor phase chlorosulfonation of polyolefins in the presence of finely divided inorganic materials |
| JPS6145232A (en) * | 1984-08-09 | 1986-03-05 | Matsushita Electric Ind Co Ltd | Acoustooptic device |
-
1997
- 1997-01-24 CN CN97100291A patent/CN1068604C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759819B (en) * | 2009-12-22 | 2011-07-27 | 连云港金泰达橡胶材料有限公司 | Device for preparing chlorosulfonated polyethylene by gas-solid phase method |
| CN102153684A (en) * | 2011-01-13 | 2011-08-17 | 杭州新元化工技术开发有限公司 | Method for preparing chlorosulfonated polyethylene by gas-solid reaction |
| CN102153684B (en) * | 2011-01-13 | 2013-02-06 | 杭州新元化工技术开发有限公司 | Method for preparing chlorosulfonated polyethylene by gas-solid reaction |
| CN105713117A (en) * | 2016-03-02 | 2016-06-29 | 中国石油天然气股份有限公司吉林石化分公司 | Improved chlorosulfonated polyethylene production system |
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| CN1068604C (en) | 2001-07-18 |
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