CN107915797B - Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof - Google Patents
Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
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Abstract
The invention provides liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and a preparation method thereof, and relates to the field of rubber preparation. The preparation method of the liquid polybutadiene rubber comprises the following steps: mixing a polymerization-grade butadiene monomer with an organic solvent, mixing with an initiator and a telomerization agent at 30-50 ℃, carrying out polymerization reaction at 30-50 ℃ for 3-5 h, and then terminating the reaction. The liquid polybutadiene rubber glue solution can be obtained by the method, and the molecular weight and the structure of the liquid polybutadiene rubber are both adjustable. The preparation method of the epoxidized liquid polybutadiene rubber comprises the following steps: and mixing the liquid polybutadiene rubber glue solution with organic acid and hydrogen peroxide to perform epoxidation reaction. The reaction process is simple, the reaction in the epoxidation process is mild, and the prepared epoxidized liquid polybutadiene has stable performance.
Description
Technical Field
The invention relates to the field of rubber preparation, and in particular relates to liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation methods thereof.
Background
The concept of "green tire" is gradually emerging in today's society. Compared with the traditional tire, the green tire has obvious advantages in the aspects of energy conservation, safety, environmental protection and the like. Due to the characteristics of polybutadiene carbon chains, the molecular chain polarity of polybutadiene is very low, the polybutadiene carbon chains are difficult to be compatible with other polar materials to achieve the performance synergistic effect, the application of the polybutadiene carbon chains is limited, and the polybutadiene rubber can overcome the defects through epoxidation modification.
Patents and research reports on the preparation of epoxidized rubber are reported at home and abroad. A preparation method of epoxidized trans-isoprene rubber by a patent (CN103910816A) emulsion method is characterized in that organic acid and hydrogen peroxide are directly added into trans-isoprene rubber emulsion for epoxidation. Kosel et al reported epoxidizing low molecular weight high cis polybutadiene in solution using a complex system of molybdenum acetylacetonate and tert-butyl hydroperoxide. Gahagan and Cole-Hamilton et al reported that polybutadiene rubber of 1, 4-structure can be epoxidized with high selectivity using a molybdenum compound coordinated with a phosphinoxy complex as a catalyst and tert-butyl hydroperoxide as an oxidant.
In the presence of peroxy acid, the molecular chain of polybutadiene rubber has various side reactions while undergoing the main epoxidation reaction: hydrolysis reaction, acidolysis reaction, cyclization reaction, crosslinking reaction, and the like. These side reactions are caused by the influence of various factors such as reaction temperature, acid concentration, catalytic system, reaction time, glue solution concentration, etc. Due to the diversity of epoxidation side reactions and the difficulty in avoiding the ring-opening reaction of the epoxy group under the catalysis of the acid catalyst, the higher the epoxidation degree is, the more serious the side reactions are.
Disclosure of Invention
The first purpose of the invention is to provide a liquid polybutadiene rubber and a preparation method thereof, wherein the liquid polybutadiene rubber is obtained by adding an initiator and a polymerization regulator into a reaction system and performing polymerization chain transfer, and the molecular weight and the structure of the polybutadiene rubber are adjustable.
The second purpose of the invention is to provide an epoxidized liquid polybutadiene rubber and a preparation method thereof, the method directly adopts the liquid polybutadiene rubber glue solution to carry out epoxidation reaction, the reaction procedure is simple, the reaction in the epoxidation process is mild, and the prepared epoxidized product has stable performance.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method of preparing a liquid polybutadiene rubber, comprising:
mixing a polymerization-grade butadiene monomer with an organic solvent, mixing with an initiator and a telomerization agent at 30-50 ℃, carrying out polymerization reaction at 30-50 ℃ for 3-5 h, and then terminating the reaction.
A liquid polybutadiene rubber glue solution prepared by the preparation method.
A method of preparing an epoxidized liquid polybutadiene rubber, comprising: mixing the liquid polybutadiene rubber solution with organic acid and hydrogen peroxide for epoxidation reaction.
An epoxidized liquid polybutadiene rubber prepared by the preparation method.
Compared with the prior art, the beneficial effects of the disclosure include:
the present disclosure provides a method for preparing liquid polybutadiene rubber, based on an anionic polymerization method, by adding an initiator and a polymerization regulator into a reaction system, and obtaining liquid polybutadiene rubber with lower molecular weight through polymerization chain transfer. In the method, the dosage of the initiator and the nonpolar solvent is small, and the molecular weight of the polymer is easy to control; the molecular weight and structure of the polymer can be adjusted by the polymerization regulator. The molecular weight and the structure of the liquid polybutadiene rubber prepared by the method are adjustable.
In the process of preparing the epoxidized liquid polybutadiene rubber, the liquid polybutadiene rubber liquid solution can be directly adopted for epoxidation reaction without the steps of coagulation, washing and drying of the liquid polybutadiene rubber liquid solution, the production process is simple, the reaction in the epoxidation process is mild, and the prepared epoxidized product has stable performance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment provides a liquid polybutadiene rubber, and the preparation method comprises the following steps:
step S1: and mixing the polymerization-grade butadiene monomer with an organic solvent to obtain a butadiene monomer solution.
Further, the organic solvent includes a weakly polar organic solvent such as toluene, xylene, etc. Preferably, the organic solvent is xylene.
Step S2: and (3) mixing the butadiene monomer solution with an initiator and a telomerization agent at the temperature of 30-50 ℃, carrying out polymerization reaction for 3-5 h at the temperature of 30-50 ℃, and then terminating the reaction.
Wherein the initiator comprises at least one of n-butyllithium, sec-butyllithium, tert-butyllithium and isobutyllithium. It should be noted that, in this embodiment, such butyl lithium reagent not only functions as an initiator, but also functions as a impurity killer during the reaction process, so as to remove impurities such as water and oxygen in the reaction system. The amount of initiator added can be determined according to the size of the target molecular weight and the amount of impurities to be removed. Preferably, n-butyllithium is used as an initiator, and the system adopting the n-butyllithium has stable reaction and easily controlled polymer molecular weight.
The telomerization agent is added in the polymerization reaction, so that the polymerization degree can be adjusted, and the molecular weight of the polymer can be controlled. The addition amount of the telogen can be determined by selecting the molar ratio of the telogen to the n-butyllithium according to the target molecular weight. Further, the telogen includes at least one of potassium tert-butoxide, sodium tert-butoxide, and lithium tert-butoxide. Optionally, potassium tert-butoxide is used as a telogen, and the molecular weight obtained by polymerization when potassium tert-butoxide is used as the telogen is small and the distribution range of the molecular weight is wide.
Further, before mixing the initiator and the telomerization agent with the butadiene monomer solution, the method further comprises the following steps: and mixing the butadiene monomer solution with the impurity-killing color developing agent at the temperature of 30-50 ℃.
The color development can be achieved by the reaction of the impurity-killing color developing agent and the butyl lithium reagent (such as n-butyl lithium), the amount of impurities such as water, oxygen and the like in the reaction system can be determined by the change of the color, and the amount of the added butyl lithium reagent can be further determined. Further, the color developer includes diethylene glycol dimethyl ether.
Further, before mixing the initiator and the telomerization agent with the butadiene monomer solution, the method further comprises the following steps: and mixing the butadiene monomer solution with the polar additive at the temperature of 30-50 ℃.
A polar additive capable of adjusting the vinyl structure in the polymer. The content of vinyl structure in the polymer increases with the increase of the amount of the polar additive added, and if a polymer having a high vinyl structure or a medium vinyl structure is required, a fixed amount of the polar additive is required. Further, the polar additive includes diethylene glycol dimethyl ether, diethyl ether, tetrahydrofuran, or dioxane. It should be noted that, in the embodiment provided by the present invention, the butadiene monomer can be directly dissolved by using the organic solvent with higher polarity in step S1 to achieve the purpose of adjusting the vinyl structure in the polymer, but this method has the disadvantages that the content of the vinyl structure in the prepared polymer is not easy to control, and the economic cost is high, which is not favorable for industrial mass production.
Preferably, the polar additive is diethylene glycol dimethyl ether. The diethylene glycol dimethyl ether has two functions in a reaction system, and specifically comprises the following steps: 1. as the miscellaneous color developing agent: the diethylene glycol dimethyl ether can be reacted with n-butyl lithium to develop color, and the amount of impurities such as water, oxygen and the like in a reaction system can be determined through the color change; 2. as a polar additive, the structure of the polymer is adjusted, the structure of polybutadiene and the addition amount of diethylene glycol dimethyl ether have a certain relationship, and the addition amount of the diethylene glycol dimethyl ether can be adjusted according to the structural value of the polybutadiene which needs to be adjusted.
Further, in the polymerization reaction, a terminator is added at the time of terminating the reaction. The terminating agent includes ethanol, methanol, hydrochloric acid, water or isopropanol.
The embodiment also provides an epoxidized liquid polybutadiene rubber, and the preparation method comprises the following steps:
mixing the liquid polybutadiene rubber solution with organic acid and hydrogen peroxide for epoxidation reaction.
Further, the molar ratio of hydrogen peroxide to organic acid is 1.0-1.5: 1, or 1.1-1.4: 1, or 1.1-1.3: 1, or 1.2: 1. preferably, the hydrogen peroxide is mixed with the solution containing the polybutadiene rubber glue solution and the organic acid by adopting a slow adding mode, so that the over-violent reaction is avoided.
Further, the reaction temperature of the epoxidation reaction is 30-60 ℃, or 33-50 ℃, or 38-45 ℃, or 40 ℃; the reaction time is 3-5 h, or 3.5-4.5 h, or 4 h.
Further, the molar ratio of the organic acid to the polybutadiene double bonds is 0.3-0.5: 1, or 0.4: 1.
and further, the method also comprises a post-treatment process of the reaction, for example, the post-treatment process comprises the steps of obtaining an epoxidized liquid polybutadiene rubber solution after the epoxidation reaction, adjusting the pH value of the system to be 7 by alkali washing and water washing, standing for layering, and removing the solvent by distillation to obtain the epoxidized liquid polybutadiene rubber.
The features and properties of the present invention are further described in detail below with reference to examples:
example 1
This example provides a liquid polybutadiene rubber, and the preparation method thereof includes:
after anhydrous and oxygen-free treatment, 1500mL of xylene and 180g of polymerization-grade butadiene monomer are added into a 3000mL flask, stirring is started, and the mixture is preheated to 40 ℃ in a constant-temperature water bath tank to obtain a butadiene monomer solution.
Adding 2.4mL of diethylene glycol dimethyl ether (a polarity regulator and a decolourizer, wherein the adding amount of the diethylene glycol dimethyl ether is determined according to the molar ratio of the diethylene glycol dimethyl ether to Li being 10) into a butadiene monomer solution, adding 0.8mL of n-butyllithium serving as an initiator required by the designed molecular weight and 2.0mL of potassium tert-butoxide (the adding amount of the telomerization agent is determined according to the molar ratio of K to Li being 1.0) when the solution is yellowish, continuously reacting for 4h at 40 ℃, and terminating the reaction by adopting ethanol as a terminator to obtain the liquid polybutadiene rubber.
After sampling to remove the solvent, the microstructure of the polymer was characterized by infrared testing. And (3) characterizing the molecular weight and the distribution of the polymer by adopting a gel permeation chromatograph. The results are as follows:
content of 1, 2-butadiene: 55.65%, cis-1, 4-butadiene content: 1.32%, content of Trans-1, 4-butadiene: 56.97%, molecular weight (Mn): 3200, Polymer Dispersibility Index (PDI): 1.79.
example 2
This example provides a liquid polybutadiene rubber, and the preparation method thereof includes:
after anhydrous and oxygen-free treatment, 1500mL of xylene solution and 180g of polymerization-grade butadiene monomer are added into a 3000mL flask, stirring is started, and the mixture is preheated to 40 ℃ in a constant-temperature water bath tank to obtain butadiene monomer solution.
Adding 1.2mL of diethylene glycol dimethyl ether (used as a polarity regulator and a decolouring agent, determining the addition amount of the diethylene glycol dimethyl ether according to the molar ratio of the diethylene glycol dimethyl ether to Li being 5) into a butadiene monomer solution, adding 0.8mL of n-butyllithium as an initiator required by the designed molecular weight and 2.0mL of potassium tert-butoxide (determining the addition amount of a telomerization agent according to the molar ratio of K to Li being 1.0) when the solution is yellowish, continuing to react at 40 ℃ for 4h, and terminating the reaction by using methanol as a terminator to obtain the liquid polybutadiene rubber.
After sampling and removing the solvent, an infrared test is adopted to represent the microstructure of the polymer, and a gel permeation chromatograph is adopted to represent the molecular weight and distribution of the polymer. The results are as follows:
content of 1, 2-butadiene: 50.65%, cis-1, 4-butadiene content: 4.52%, content of Trans-1, 4-butadiene: 44.83%, molecular weight (Mn): 3120, Polymer Dispersibility Index (PDI): 1.65.
example 3
This example provides a liquid polybutadiene rubber, and the preparation method thereof includes:
after anhydrous and oxygen-free treatment, 1500mL of xylene solution and 180g of polymerization-grade butadiene monomer are added into a 3000mL flask, stirring is started, and the mixture is preheated to 30 ℃ in a constant-temperature water bath tank to obtain butadiene monomer solution.
Adding diethyl ether into a butadiene monomer solution, uniformly mixing, adding 0.8mL of initiator sec-butyl lithium required by the designed molecular weight and 2.0mL of tert-butyl lithium (the addition amount of a telomerization agent is determined according to the molar ratio of the tert-butyl lithium to the sec-butyl lithium of 1.0), continuously reacting for 5h at 30 ℃, and terminating the reaction by adopting water as a terminator, namely obtaining the polybutadiene rubber.
After sampling and removing the solvent, an infrared test is adopted to represent the microstructure of the polymer, and a gel permeation chromatograph is adopted to represent the molecular weight and distribution of the polymer. The results are as follows:
content of 1, 2-butadiene: 48.71%, cis-1, 4-butadiene content: 3.98%, content of Trans-1, 4-butadiene: 43.19%, molecular weight (Mn): 3021, Polymer Dispersibility Index (PDI): 1.57.
example 4
This example provides a liquid polybutadiene rubber, and the preparation method thereof includes:
after anhydrous and oxygen-free treatment, 1500mL of xylene solution and 180g of polymerization-grade butadiene monomer are added into a 3000mL flask, stirring is started, and the mixture is preheated to 50 ℃ in a constant-temperature water bath tank to obtain butadiene monomer solution.
Adding tetrahydrofuran into a butadiene monomer solution, uniformly mixing, adding 0.8mL of initiator tert-butyl lithium required by designed molecular weight and 2.0mL of sodium tert-butoxide (the addition amount of a telomerization agent is determined according to the molar ratio of Na to Li of 1.0), continuously reacting at 50 ℃ for 3h, and terminating the reaction by adopting water as a terminator to obtain the liquid polybutadiene rubber.
After sampling and removing the solvent, an infrared test is adopted to represent the microstructure of the polymer, and a gel permeation chromatograph is adopted to represent the molecular weight and distribution of the polymer. The results are as follows:
content of 1, 2-butadiene: 46.72%, cis-1, 4-butadiene content: 3.78%, content of Trans-1, 4-butadiene: 41.98%, molecular weight (Mn): 3105, Polymer Dispersibility Index (PDI): 1.52.
example 5
This example provides an epoxidized liquid polybutadiene rubber, the preparation method of which comprises:
200mL of the liquid polybutadiene rubber cement solution prepared in example 1 is added into a 500mL clean three-neck flask provided with a spherical condenser tube, the temperature is preheated to 40 ℃ in a constant temperature water bath box, 12.9mL of formic acid is added according to the molar ratio of organic acid to polybutadiene double bond of 0.4, stirring is started, the rotating speed is 200rpm/min, then 45mL of hydrogen peroxide is added within 20min according to the molar ratio of the hydrogen peroxide to the organic acid of 1.2, and reaction is carried out for 4 h. And (3) carrying out alkali washing and water washing on the epoxidized liquid polybutadiene glue solution to adjust the pH of the system to be 7, standing for layering, removing the solvent by adopting a distillation method, and drying in a vacuum drying oven at 40 ℃ to constant weight.
20.5g of the obtained epoxidized liquid polybutadiene rubber had an epoxy degree of 45.6% as determined by the hydrochloric acid-acetone method.
Example 6
This example provides an epoxidized liquid polybutadiene rubber, the preparation method of which comprises:
200mL of the liquid polybutadiene rubber glue solution prepared in the example 2 is added into a 500mL clean three-neck flask provided with a spherical condenser tube, the temperature is preheated to 60 ℃ in a constant temperature water bath box, 12.9mL of formic acid is added according to the molar ratio of organic acid to polybutadiene double bond of 0.4, stirring is started, the rotating speed is 200rpm/min, then 45mL of hydrogen peroxide is added within 20min according to the molar ratio of the hydrogen peroxide to the organic acid of 1.2, and reaction is carried out for 4 h. And (3) carrying out alkali washing and water washing on the epoxidized liquid polybutadiene glue solution to adjust the pH of the system to be 7, standing for layering, removing the solvent by adopting a distillation method, and drying in a vacuum drying oven at 40 ℃ to constant weight.
20.0g of the obtained epoxidized liquid polybutadiene rubber had an epoxy degree of 35.6% as determined by the hydrochloric acid-acetone method.
Example 7
This example provides an epoxidized liquid polybutadiene rubber, the preparation method of which comprises:
200mL of the liquid polybutadiene rubber cement solution prepared in example 3 was added into a 500mL clean three-necked flask equipped with a spherical condenser tube, preheated to 30 ℃ in a constant temperature water bath, 19.4mL of formic acid was added and stirred at a rotation speed of 200rpm/min according to a molar ratio of organic acid to polybutadiene double bond of 0.6, and then 45mL of hydrogen peroxide was added within 20min according to a molar ratio of hydrogen peroxide to organic acid of 1.2, and reacted for 4 h. And (3) carrying out alkali washing and water washing on the epoxidized liquid polybutadiene glue solution to adjust the pH of the system to be 7, standing for layering, removing the solvent by adopting a distillation method, and drying in a vacuum drying oven at 40 ℃ to constant weight.
19.5g of the obtained epoxidized liquid polybutadiene rubber had an epoxy degree of 32.0% as determined by the hydrochloric acid-acetone method.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (5)
1. A method for preparing liquid polybutadiene rubber is characterized in that the method comprises the following steps: mixing a polymerization-grade butadiene monomer with an organic solvent, mixing the mixture with an initiator and a telomerization agent at 30-50 ℃, carrying out polymerization reaction for 3-5 hours at 30-50 ℃, and then terminating the reaction, wherein the telomerization agent comprises at least one of potassium tert-butoxide, sodium tert-butoxide and lithium tert-butoxide, and the method further comprises the following steps of: mixing the solution dissolved with the butadiene monomer with a miscellaneous color-developing agent at 30-50 ℃, wherein the miscellaneous color-developing agent comprises diethylene glycol dimethyl ether, and before mixing the initiator, the telomerization agent and the solution dissolved with the butadiene monomer, the method further comprises the following steps: and mixing the solution dissolved with the butadiene monomer with a polar additive at the temperature of 30-50 ℃, wherein the polar additive comprises any one of diethylene glycol dimethyl ether, diethyl ether, tetrahydrofuran and dioxane.
2. The method of producing a liquid polybutadiene rubber according to claim 1, wherein the initiator includes at least one of n-butyllithium, sec-butyllithium, tert-butyllithium and isobutyllithium.
3. A liquid polybutadiene rubber obtained by the process according to claim 1.
4. A method for preparing epoxidized liquid polybutadiene rubber is characterized by comprising the following steps: mixing the liquid polybutadiene rubber cement as claimed in claim 3, organic acid and hydrogen peroxide, and carrying out epoxidation reaction.
5. An epoxidized liquid polybutadiene rubber obtained by the process according to claim 4.
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| JP2012116987A (en) * | 2010-12-02 | 2012-06-21 | Ube Industries Ltd | Method for producing epoxidized diene-based rubber, and rubber composition containing the rubber |
| CN102532377A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber as well as preparation method and application thereof |
| CN102702408A (en) * | 2012-06-04 | 2012-10-03 | 辽宁和运合成橡胶研究院有限公司 | Preparation method of diene-based liquid rubber |
| CN103665227A (en) * | 2013-11-28 | 2014-03-26 | 沈阳化工大学 | Preparation method of epoxidized 1, 2-polybutadiene |
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|---|---|---|---|---|
| JP2012116987A (en) * | 2010-12-02 | 2012-06-21 | Ube Industries Ltd | Method for producing epoxidized diene-based rubber, and rubber composition containing the rubber |
| CN102532377A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber as well as preparation method and application thereof |
| CN102702408A (en) * | 2012-06-04 | 2012-10-03 | 辽宁和运合成橡胶研究院有限公司 | Preparation method of diene-based liquid rubber |
| CN103665227A (en) * | 2013-11-28 | 2014-03-26 | 沈阳化工大学 | Preparation method of epoxidized 1, 2-polybutadiene |
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