CN107915797A - 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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- CN107915797A CN107915797A CN201711169696.0A CN201711169696A CN107915797A CN 107915797 A CN107915797 A CN 107915797A CN 201711169696 A CN201711169696 A CN 201711169696A CN 107915797 A CN107915797 A CN 107915797A
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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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- C—CHEMISTRY; METALLURGY
- 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 present invention provides a kind of liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof, it is related to field of rubber preparation.The preparation method of liquid polybutadiene rubber includes:After the divinylic monomer of polymer grade is mixed with organic solvent, mixed at 30~50 DEG C with initiator and telogen, after 3~5h of polymerisation at 30~50 DEG C, terminate reaction.Liquid polybutadiene rubber glue can obtain by this method, the molecular weight and structure of this liquid polybutadiene rubber are adjustable.The preparation method of epoxidized liquid polybutadiene rubber includes:Aforesaid liquid polybutadiene rubber glue is mixed with organic acid, hydrogen peroxide, carries out epoxidation reaction.This reaction process is simple, and epoxidation process reaction is gentle, and the epoxidized liquid polybutadiene performance of preparation is stablized.
Description
Technical field
The present invention relates to field of rubber preparation, gathers in particular to a kind of liquid polybutadiene rubber, epoxidized liquid
Butadiene rubber and preparation method thereof.
Background technology
Today's society " green tire " concept is gradually risen." green tire " is compared with conventional tire energy saving, safe and environment-friendly etc.
Aspect has obvious advantage.Since the characteristic of polybutadiene carbochain, its molecular-chain polarr are very low, it is difficult to and other polar materials
It is compatible to reach performance synergistic effect, its application is limited, epoxidation modification can make polybutadiene rubber overcome disadvantages mentioned above.
Patent and research in terms of the domestic and international preparation for being related to epoxidezed rubber report.Patent
(CN103910816A) emulsion method prepares epoxidation trans isoprene rubber preparation method, and this method is in trans-isoprene lotion
In be directly added into organic acid and hydrogen peroxide and carry out epoxidation.Kosel et al. is reported using acetyl acetone and tertiary-butylacetate
The complex system of peroxide, in the solution epoxidation low molecular weight high-cis polybutadiene.Gahagan and Cole-
It is catalyst that Hamilton et al., which reports the molybdenum compound containing the coordination of phosphine oxo complex, and tert-butyl hydroperoxide is oxygen
Agent, can epoxidation Isosorbide-5-Nitrae-structure with high selectivity polybutadiene rubber.
In the presence of peroxy acid, polybutadiene rubber strand also exists more while epoxidation main reaction is carried out
Kind side reaction:Hydrolysis, acidolysis reaction, cyclization, cross-linking reaction etc..The generation of these side reactions is common by many factors
Caused by influence, such as reaction temperature, acid concentration, catalyst system and catalyzing, reaction time, gelatin concentration etc..Due to epoxidation side reaction
Epoxide group ring-opening reaction under diversity and acid catalyst catalysis is difficult to avoid that epoxidation level is higher, and side reaction can also be got over
Seriously.
The content of the invention
The first object of the present invention is to provide a kind of liquid polybutadiene rubber and preparation method thereof, this method by
Initiator and polymerization regulator are added in reaction system, liquid polybutadiene rubber, this poly- fourth are obtained by polymerizeing chain tra nsfer
The molecular weight and structure of diene rubber are adjustable.
The second object of the present invention is to provide a kind of epoxidized liquid polybutadiene rubber and preparation method thereof, this method
Epoxidation reaction is directly carried out using aforesaid liquid polybutadiene rubber glue, reaction process is simple, epoxidation process reaction temperature
With the epoxidation product performance stabilization of preparation.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme:
A kind of preparation method of liquid polybutadiene rubber, it includes:
After the divinylic monomer of polymer grade is mixed with organic solvent, mixed at 30~50 DEG C with initiator and telogen
Close, after 3~5h of polymerisation at 30~50 DEG C, terminate reaction.
A kind of liquid polybutadiene rubber glue as obtained by above-mentioned preparation method.
A kind of preparation method of epoxidized liquid polybutadiene rubber, it includes:By aforesaid liquid polybutadiene rubber
Glue is mixed with organic acid, hydrogen peroxide, carries out epoxidation reaction.
A kind of epoxidized liquid polybutadiene rubber obtained by above-mentioned preparation method.
Compared with prior art, beneficial effect in the present disclosure for example including:
The preparation method for the liquid polybutadiene rubber that present disclosure provides, the method based on anionic polymerisation, passes through
Initiator and polymerization regulator are added in the reaction system, and the liquid polybutadiene of more low molecular weight is obtained by polymerizeing chain tra nsfer
Alkene rubber.In this method, the dosage of initiator and nonpolar solvent is small, and the molecular weight of polymer is easy to control;Adjusted by polymerizeing
Agent is saved, the molecular weight and structure of polymer can be adjusted.Obtained liquid polybutadiene rubber molecular weight by this method
It is adjustable with structure.
During epoxidized liquid polybutadiene rubber is prepared, aforesaid liquid polybutadiene rubber can be directly used
Glue carries out epoxidation reaction, without the step that liquid polybutadiene rubber glue is condensed, washes and is dried, produces work
Sequence is simple, and epoxidation process reaction is gentle, and the epoxidation product performance of preparation is stablized.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
Present embodiment provides a kind of liquid polybutadiene rubber, and its preparation method includes:
Step S1:After the divinylic monomer of polymer grade is mixed with organic solvent, divinylic monomer solution is obtained.
Further, organic solvent includes the weakly polar organic solvents such as toluene, dimethylbenzene.It is more preferable, organic solvent
For dimethylbenzene.
Step S2:Divinylic monomer solution is mixed at 30~50 DEG C with initiator and telogen, and at 30~50 DEG C
After 3~5h of lower polymerisation, reaction is terminated.
Wherein, initiator includes at least one of n-BuLi, s-butyl lithium, tert-butyl lithium and isobutyl group lithium.It is worth
It is noted that in the present embodiment, this kind of butyl lithium reagent during the reaction, not only plays the role of initiator, also has
Miscellaneous dose is killed, the impurity such as water oxygen in reaction system can be removed.The addition of initiator, can be according to target molecular weight
Size and the amount that needs to remove impurity determine.It is more preferable, it is this using just using n-BuLi as initiator
The system of butyl lithium, reacting balance, polymer molecular weight are easily controllable.
Telogen, adds telogen in the polymerization, can adjust the degree of polymerization, control the molecular weight of polymer.Telomerization
The addition of agent, can select using the molar ratio of telogen and n-BuLi according to target molecular weight to be determined.Into one
Step, telogen includes at least one of potassium tert-butoxide, sodium tert-butoxide and tert-butyl alcohol lithium.Optionally, use potassium tert-butoxide for
It polymerize that obtained molecular weight is smaller when telogen using potassium tert-butoxide is telogen, and the distribution of molecular weight is wider.
Further, before initiator and telogen are mixed with divinylic monomer solution, further include:By divinylic monomer
Solution mixes at 30~50 DEG C with killing miscellaneous color developing agent.
Killing miscellaneous color developing agent and butyl lithium class reagent reacting (such as n-BuLi) reaction can develop the color, and then pass through color
Change can determine that the amount of the impurity such as the water oxygen in reaction system, and then can further determine that the amount for adding butyl lithium class reagent.Into
One step, killing miscellaneous color developing agent includes diethylene glycol dimethyl ether.
Further, before initiator and telogen are mixed with divinylic monomer solution, further include:By divinylic monomer
Solution mixes at 30~50 DEG C with polar additive.
Polar additive, it can adjust the vinyl structure in polymer.With the increasing of the addition of polar additive
More, the vinyl structure content in polymer increases, if desired the polymer of high-vinyl structure or medium vinyl structure,
Then need quantitative addition polar additive.Further, polar additive includes diethylene glycol dimethyl ether, ether, tetrahydrochysene furan
Mutter or dioxane.When noticeable, in embodiment provided by the invention, pole can also be directly used in step sl
Property larger organic solvent dissolve divinylic monomer, achieving the purpose that to adjust polymer medium vinyl structure, but this side
The shortcomings that formula, is that the content of prepared polymer medium vinyl structure is difficult to control, and financial cost is high, is unfavorable for industry
Big production.
More preferable, polar additive is diethylene glycol dimethyl ether.Diethylene glycol dimethyl ether is in the reaction system at the same time
Acted on both sides, be specially:1. it is used as and kills miscellaneous color developing agent:Diethylene glycol dimethyl ether can be shown with n-BuLi reaction
Color, the amount of the impurity such as water oxygen in reaction system is can determine that by the change of color;2. being used as polar additive, polymer is adjusted
Structure, the structure of polybutadiene and the addition of diethylene glycol dimethyl ether have certain relation, and what can be adjusted as needed is poly-
The addition of diethylene glycol dimethyl ether is adjusted in butadiene structure value.
Further, which adds terminator when terminating reaction.Terminator include ethanol, methanol, hydrochloric acid,
Water or isopropanol equal solvent.
Present embodiment also provides a kind of epoxidized liquid polybutadiene rubber, and its preparation method includes:
The glue of the liquid polybutadiene rubber of above-mentioned preparation is mixed with organic acid, hydrogen peroxide, it is anti-to carry out epoxidation
Should.
Further, the molar ratio of hydrogen peroxide and organic acid is 1.0~1.5:1, or be 1.1~1.4:1, Huo Zhewei
1.1~1.3:1, or be 1.2:1.Preferably, hydrogen peroxide by the way of being slowly added to and contains polybutadiene rubber glue
The solution of liquid and organic acid mixes, and avoids reaction excessively violent.
Further, the reaction temperature of epoxidation reaction is 30~60 DEG C, is either 33~50 DEG C or is 38~45
DEG C, or for 40 DEG C;Reaction time is 3~5h, is either 3.5~4.5h or is 4h.
Further, the molar ratio of organic acid and polybutadiene double bond is 0.3~0.5:1, or be 0.4:1.
Further, the last handling process of reaction is further included, such as including epoxidized liquid will be obtained after epoxidation reaction
Liquid polybutadiene glue, after alkali cleaning, washing regulation system pH=7, stratification, removes solvent through distillation, obtains epoxy
Change liquid polybutadiene rubber.
The feature and performance of the present invention are described in further detail with reference to embodiments:
Embodiment 1
The present embodiment provides a kind of liquid polybutadiene rubber, its preparation method includes:
After anhydrous and oxygen-free is handled, the dimethylbenzene of 1500mL and the butadiene of polymer grade are added in the flask of 3000mL
Monomer 180g, starts stirring, 40 DEG C is preheated in constant water bath box, obtains divinylic monomer solution.
In divinylic monomer solution, add diethylene glycol dimethyl ether 2.4mL and (polar modifier and kill miscellaneous color developing agent, press
The addition of diethylene glycol dimethyl ether is determined according to molar ratio=10 of diethylene glycol dimethyl ether and Li), during the micro- yellow of solution
The initiator n-BuLi 0.8mL needed for design molecular weight is added, and (molar ratio according to K and Li is potassium tert-butoxide 2.0mL
1.0, determine the addition of telogen), continue at 40 DEG C and react 4h, use ethanol to be reacted for terminator to terminate, up to liquid
Body polybutadiene rubber.
After sampling removing solvent, using the microstructure of infrared test characterization polymer.Using gel permeation chromatograph table
Levy molecular weight and the distribution of polymer.As a result it is as follows:
The content of 1,2- butadiene:The content of 55.65%, cis-1,4- butadiene:1.32%, Trans-1,4- butadiene
Content:56.97%, molecular weight (Mn):3200, polymer dispersity index (PDI):1.79.
Embodiment 2
The present embodiment provides a kind of liquid polybutadiene rubber, its preparation method includes:
After anhydrous and oxygen-free is handled, the xylene solution of 1500mL and the fourth of polymer grade are added in the flask of 3000mL
Diene monomers 180g, starts stirring, 40 DEG C is preheated in constant water bath box, obtains divinylic monomer solution.
In divinylic monomer solution, add diethylene glycol dimethyl ether 1.2mL and (as polar modifier and kill miscellaneous colour developing
Agent, the addition of diethylene glycol dimethyl ether is determined according to molar ratio=5 of diethylene glycol dimethyl ether and Li), the micro- Huang of solution
The initiator n-BuLi 0.8mL needed for design molecular weight is added during color, and potassium tert-butoxide 2.0mL is (according to mole of K and Li
Than the addition for for 1.0, determining telogen), continue at 40 DEG C and react 4h, use methanol to terminate reaction for terminator, i.e.,
Obtain liquid polybutadiene rubber.
After sampling removing solvent, using the microstructure of infrared test characterization polymer, using gel permeation chromatograph table
Levy molecular weight and the distribution of polymer.As a result it is as follows:
The content of 1,2- butadiene:The content of 50.65%, cis-1,4- butadiene:4.52%, Trans-1,4- butadiene
Content:44.83%, molecular weight (Mn):3120, polymer dispersity index (PDI):1.65.
Embodiment 3
The present embodiment provides a kind of liquid polybutadiene rubber, its preparation method includes:
After anhydrous and oxygen-free is handled, the xylene solution of 1500mL and the fourth of polymer grade are added in the flask of 3000mL
Diene monomers 180g, starts stirring, 30 DEG C is preheated in constant water bath box, obtains divinylic monomer solution.
In divinylic monomer solution, ether is added, the initiator s-butyl lithium needed for design molecular weight is added after mixing
0.8mL, and tert-butyl alcohol lithium 2.0mL (are 1.0 according to the molar ratio of tert-butyl alcohol lithium and s-butyl lithium, determine the addition of telogen
Amount), continue at 30 DEG C and react 5h, adopt water as terminator to terminate reaction, i.e., liquid obtains polybutadiene rubber.
After sampling removing solvent, using the microstructure of infrared test characterization polymer, using gel permeation chromatograph table
Levy molecular weight and the distribution of polymer.As a result it is as follows:
The content of 1,2- butadiene:The content of 48.71%, cis-1,4- butadiene:3.98%, Trans-1,4- butadiene
Content:43.19%, molecular weight (Mn):3021, polymer dispersity index (PDI):1.57.
Embodiment 4
The present embodiment provides a kind of liquid polybutadiene rubber, its preparation method includes:
After anhydrous and oxygen-free is handled, the xylene solution of 1500mL and the fourth of polymer grade are added in the flask of 3000mL
Diene monomers 180g, starts stirring, 50 DEG C is preheated in constant water bath box, obtains divinylic monomer solution.
In divinylic monomer solution, tetrahydrofuran is added, the tertiary fourth of initiator needed for design molecular weight is added after mixing
Base lithium 0.8mL, and sodium tert-butoxide 2.0mL (being 1.0 according to the molar ratio of Na and Li, determine the addition of telogen), continue
3h is reacted at 50 DEG C, terminator is adopted water as to terminate reaction, obtains liquid polybutadiene rubber.
After sampling removing solvent, using the microstructure of infrared test characterization polymer, using gel permeation chromatograph table
Levy molecular weight and the distribution of polymer.As a result it is as follows:
The content of 1,2- butadiene:The content of 46.72%, cis-1,4- butadiene:3.78%, Trans-1,4- butadiene
Content:41.98%, molecular weight (Mn):3105, polymer dispersity index (PDI):1.52.
Embodiment 5
The present embodiment provides a kind of epoxidized liquid polybutadiene rubber, its preparation method includes:
By the poly- fourth of liquid that in the three-necked flask equipped with spherical condensating tube of 500mL cleanings prepared by addition 200mL embodiments 1
Diene rubber glue, is preheated to 40 DEG C in constant water bath box, is 0.4 according to the molar ratio of organic acid and polybutadiene double bond
Ratio, addition have formic acid 12.9mL and start stirring, rotating speed 200rpm/min, then by hydrogen peroxide and mole of organic acid
Hydrogen peroxide 45mL is added in 20min than the ratio for 1.2, reacts 4h.Epoxidized liquid polybutadiene glue is through alkali cleaning, water
After washing regulation system pH=7, stratification, removes solvent using the method for distillation, is dried in 40 DEG C of vacuum drying chambers to constant weight.
Gained epoxidized liquid polybutadiene rubber 20.5g, is 45.6% through hydrochloric acid-acetone method measure epoxy content.
Embodiment 6
The present embodiment provides a kind of epoxidized liquid polybutadiene rubber, its preparation method includes:
By the poly- fourth of liquid that in the three-necked flask equipped with spherical condensating tube of 500mL cleanings prepared by addition 200mL embodiments 2
Diene rubber glue, is preheated to 60 DEG C in constant water bath box, is 0.4 according to the molar ratio of organic acid and polybutadiene double bond
Ratio, addition have formic acid 12.9mL and start stirring, rotating speed 200rpm/min, then by hydrogen peroxide and mole of organic acid
Hydrogen peroxide 45mL is added in 20min than the ratio for 1.2, reacts 4h.Epoxidized liquid polybutadiene glue is through alkali cleaning, water
After washing regulation system pH=7, stratification, removes solvent using the method for distillation, is dried in 40 DEG C of vacuum drying chambers to constant weight.
Gained epoxidized liquid polybutadiene rubber 20.0g, is 35.6% through hydrochloric acid-acetone method measure epoxy content.
Embodiment 7
The present embodiment provides a kind of epoxidized liquid polybutadiene rubber, its preparation method includes:
By the poly- fourth of liquid that in the three-necked flask equipped with spherical condensating tube of 500mL cleanings prepared by addition 200mL embodiments 3
Diene rubber glue, is preheated to 30 DEG C in constant water bath box, is 0.6 according to the molar ratio of organic acid and polybutadiene double bond
Ratio, addition have formic acid 19.4mL and start stirring, rotating speed 200rpm/min, then by hydrogen peroxide and mole of organic acid
Hydrogen peroxide 45mL is added in 20min than the ratio for 1.2, reacts 4h.Epoxidized liquid polybutadiene glue is through alkali cleaning, water
After washing regulation system pH=7, stratification, removes solvent using the method for distillation, is dried in 40 DEG C of vacuum drying chambers to constant weight.
Gained epoxidized liquid polybutadiene rubber 19.5g, is 32.0% through hydrochloric acid-acetone method measure epoxy content.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of liquid polybutadiene rubber, it is characterised in that it includes:
After the divinylic monomer of polymer grade is mixed with organic solvent, mixed at 30~50 DEG C with initiator and telogen, then
At 30~50 DEG C after 3~5h of polymerisation, reaction is terminated.
2. the preparation method of liquid polybutadiene rubber according to claim 1, it is characterised in that the initiator includes
At least one of n-BuLi, s-butyl lithium, tert-butyl lithium and isobutyl group lithium.
3. the preparation method of liquid polybutadiene rubber according to claim 1, it is characterised in that the telogen includes
At least one of potassium tert-butoxide, sodium tert-butoxide and tert-butyl alcohol lithium.
4. the preparation method of liquid polybutadiene rubber according to claim 1, it is characterised in that by the initiator
Before being mixed with the telogen with the solution dissolved with the divinylic monomer, further include:The divinylic monomer will be dissolved with
Solution mixed at 30~50 DEG C with killing miscellaneous color developing agent.
5. the preparation method of liquid polybutadiene rubber according to claim 4, it is characterised in that described to kill miscellaneous color developing agent
Including diethylene glycol dimethyl ether.
6. the preparation method of liquid polybutadiene rubber according to claim 1, it is characterised in that by the initiator
Before being mixed with the telogen with the solution dissolved with the divinylic monomer, further include:The divinylic monomer will be dissolved with
Solution mixed at 30~50 DEG C with polar additive.
7. according to the preparation method of claim 6 any one of them liquid polybutadiene rubber, it is characterised in that the polarity
Additive includes any one in diethylene glycol dimethyl ether, ether, tetrahydrofuran and dioxane.
A kind of 8. liquid polybutadiene rubber as described in any one of claim 1~7 obtained by preparation method.
9. a kind of preparation method of epoxidized liquid polybutadiene rubber, it is characterised in that it includes:Will as claim 8 institute
The glue for the liquid polybutadiene rubber stated, organic acid, hydrogen peroxide mixing, carry out epoxidation reaction.
A kind of 10. epoxidized liquid polybutadiene rubber obtained by preparation method as described in claim 9.
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CN109678991A (en) * | 2018-12-10 | 2019-04-26 | 浙江大学 | A method of epoxidation conjugated diene polymer is directly prepared with conjugated diene polymerisation in solution stoste |
JP7324877B2 (en) | 2020-05-22 | 2023-08-10 | エルジー・ケム・リミテッド | Method for producing liquid rubber and liquid rubber produced therefrom |
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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 |
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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 |
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CN109678991A (en) * | 2018-12-10 | 2019-04-26 | 浙江大学 | A method of epoxidation conjugated diene polymer is directly prepared with conjugated diene polymerisation in solution stoste |
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JP7324877B2 (en) | 2020-05-22 | 2023-08-10 | エルジー・ケム・リミテッド | Method for producing liquid rubber and liquid rubber produced therefrom |
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