CN114920865A - Synthesis method of butyl rubber - Google Patents
Synthesis method of butyl rubber Download PDFInfo
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- CN114920865A CN114920865A CN202210633361.4A CN202210633361A CN114920865A CN 114920865 A CN114920865 A CN 114920865A CN 202210633361 A CN202210633361 A CN 202210633361A CN 114920865 A CN114920865 A CN 114920865A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
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- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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Abstract
The invention provides a synthesis method of butyl rubber, which comprises the steps of mixing a polymerization monomer with a mixed solvent to obtain a polymerization monomer solution; the mixed solvent comprises a polarity regulator and a polymerization solvent, wherein the polarity regulator has a general formula: c x H y F z (ii) a x is 1-10, y is 1-20, and z is 1-8; reacting the polymerization monomer solution under an initiation system to obtain a glue solution; and removing the solvent from the glue solution, adding an alcohol compound to terminate, separating out a product, and drying to obtain the butyl rubber. The method improves the reaction activity of the polyene hydrocarbon by adopting the polarity regulator, thereby increasing the double bond content in the molecular chain of the butyl rubber and leading the butyl rubber to have higher unsaturation degree. The polymerization method does not reduce the activity of a catalytic system, has no adverse effect on the conversion rate and the molecular weight, and the obtained product basically has no gel. Polarity of the reaction systemThe viscosity of the reaction system is reduced, the heat transfer efficiency of the system is improved, the adhesive hanging is reduced, and the aims of saving energy and reducing consumption are fulfilled.
Description
Technical Field
The invention belongs to the technical field of butyl rubber preparation, and particularly relates to a synthesis method of butyl rubber.
Background
The traditional butyl Rubber (IIR) is a linear polymer which takes Isobutene (IB) and a small amount of Isoprene (IP) as monomers and is combined end to end, wherein the Isoprene mainly takes a trans-1, 4 structure to participate in polymerization, and the content of the Isoprene only accounts for 0.6 to 2.5 percent of a main chain. In addition to isoprene, other types of conjugated dienes and cyclic dienes may be employed as isobutylene comonomers. Due to the structural characteristics, the butyl rubber has good chemical stability and thermal stability and outstanding air tightness, and is also widely applied to the fields of steam hoses, conveying belts used at high temperature, liners of chemical equipment, cable insulation layers, waterproof coiled materials and the like. However, the butyl rubber has low double bond content in molecular chains, so that the vulcanization speed is slow, the adhesion with other unsaturated diene rubbers (such as natural rubber, butadiene rubber, styrene-butadiene rubber and the like) is poor, blending and co-vulcanization are difficult, and the compatibility with fillers and the like is poor, so that the application of the butyl rubber is limited, and therefore, the improvement of the unsaturation degree of the butyl rubber becomes an effective means for solving the problems. However, since polyene monomers, such as isoprene, are potent chain transfer agents and catalyst poisons, and with a significant increase in reactive unsaturation sites in the polymer chain, the likelihood of crosslinking during polymerization is greatly increased. In addition, the mechanism of chain growth and chain transfer of isobutylene cationic polymerization is very complex, the activity of carbocation is high, and side reactions such as isomerization, rearrangement and the like can occur in the chain growth process. High unsaturation butyl rubbers are often not suitable for use because of the low molecular weight or high gel content of the polymer product.
Exxon, U.S. Pat. No. 4, 4031300A, discloses a process for the synthesis of high molecular weight, highly unsaturated isobutylene-cyclopentadiene copolymers by initiating the copolymerization of isobutylene-cyclopentadiene and the terpolymerization of isobutylene-isoprene-cyclopentadiene in a mixed solution of chlorinated alkane and cycloalkanes using aluminum halide or alkyl aluminum halide initiators to obtain essentially gel-free butyl rubber having a number average molecular weight Mn of greater than 90kg/mol and an unsaturation of greater than 5 mol%, but using a lower polymerization temperature of-120 ℃ and higher energy consumption in the temperature control process.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for synthesizing butyl rubber, wherein the butyl rubber prepared by the method has high unsaturation degree.
The invention provides a synthesis method of butyl rubber, which comprises the following steps:
mixing a polymerization monomer with a mixed solvent to obtain a polymerization monomer solution; the mixed solvent comprises a polarity regulator and a polymerization solvent, wherein the polarity regulator has a general formula shown in a formula I:
C x H y F z the formula I is shown in the specification;
the value of x is 1-10, the value of y is 1-20, the value of z is 1-8, and x, y and z are integers;
reacting the polymerization monomer solution under an initiation system to obtain a glue solution; the polymerization monomer is selected from isomonoolefin and polyene hydrocarbon of C4-C16 with the molar ratio of (98:2) - (80: 20);
and (3) removing the solvent from the glue solution, adding an alcohol compound to terminate, precipitating a product, and drying to obtain the butyl rubber.
In the invention, the value of x is 1-6, the value of y is 1-10, and the value of z is 1-6.
In the present invention, the polarity modifier is selected from difluoromethane, 1, 1-difluoromethane, 1,1, 1-trifluoromethane, 1,1,1, 2-tetrafluoroethane, 1,1,2, 2-tetrafluoroethane, 1,1,1,2, 2-pentafluoroethane, 1, 2-difluoroethylene, 1,1, 2-trifluoroethylene, 1-fluoropropene, 1, 1-difluoropropene, 1, 2-difluoropropene, 1, 3-difluoropropene, 2, 3-difluoropropene, 3, 3-difluoropropene, 1, 2-trifluoropropene, 1, 3-trifluoropropene, 1,2, 3-trifluoropropene, 2,3, 3-trifluoropropene, and 2,3,3, 3-tetrafluoro-1-propene. The adopted polarity regulator has high purity, does not need refining, has simple polymerization operation and saves the process cost. The polar regulator has low toxicity, no harm and no environmental pollution.
In the present invention, the mass ratio of the polarity modifier to the polymerization solvent is (1:99) to (50: 50).
In the invention, the temperature of the polymerization monomer solution reacting under the initiation system is-70 to-90 ℃.
In the invention, the polymerization monomer is selected from isomonoolefin and polyene with the molar ratio of (98:2) to (80:20) and C4-C16;
the polyene is selected from conjugated diene of C4-C14 and/or cyclic diene of C5-C8. In particular embodiments, the isomonoolefin is selected from isobutylene; the multiolefin is preferably selected from isoprene.
In the present invention, the initiator includes a main initiator, a co-initiator, and a polymerization solvent; the molar ratio of the polymerized monomer to the main initiator is 1500-1000; the molar ratio of the main initiator to the auxiliary initiator is 10-5: 1. In specific embodiments, the primary initiator is a 20% wt polymerization solvent solution; the coinitiator is a 0.025% wt solution in the polymerization solvent.
The main initiator is selected from one or more of aluminum trichloride, ethyl aluminum dichloride, diethyl aluminum monochloride, butyl aluminum dichloride, dibutyl aluminum monochloride, boron trifluoride, titanium tetrachloride and aluminum sesqui-chloride; the coinitiator is selected from H 2 O or HCl. The invention does not introduce nucleophilic substances containing nitrogen, oxygen, sulfur and phosphorus, does not reduce the activity of the initiator, has no adverse effect on the conversion rate and the molecular weight, and the obtained product basically has no gel.
In the present invention, the unsaturation degree of the butyl rubber is 5 to 15 mol%.
In the present invention, the polymerization solvent is a nonpolar solvent.
In the present invention, the non-polar solvent is selected from one or more of n-pentane, isopentane, cyclopentane, n-hexane, isohexane, cyclohexane and methylcyclohexane.
The invention provides a synthesis method of butyl rubber, which comprises the following steps: polymerizing monomers andmixing the mixed solvents to obtain a polymerization monomer solution; the mixed solvent comprises a polarity regulator and a polymerization solvent, wherein the polarity regulator has a general formula shown in a formula I: c x H y F z The formula I is shown in the specification; the value of x is 1-10, the value of y is 1-20, the value of z is 1-8, and x, y and z are integers; reacting the polymerization monomer solution under an initiation system to obtain a glue solution; the polymerization monomer is selected from isomonoolefin and polyene with the molar ratio of (98:2) to (80:20) and the molar ratio of C4-C16; and (3) removing the solvent from the glue solution, adding an alcohol compound to terminate, precipitating a product, and drying to obtain the butyl rubber. The method improves the reaction activity of polyene hydrocarbon in the polymerization monomer by adopting the polarity regulator, thereby increasing the double bond content in the molecular chain of the butyl rubber and leading the prepared butyl rubber to have higher unsaturation degree. The polymerization method does not reduce the activity of the initiator, has no adverse effect on the conversion rate and the molecular weight, and the obtained product has no gel basically. The increase of the polarity of the reaction system reduces the viscosity of the reaction system, improves the heat transfer efficiency of the system, reduces the hanging glue and achieves the purposes of energy conservation and consumption reduction. The experimental results show that: the method has the conversion rate of more than 70 percent, the gel content of less than 1.5, the unsaturation degree of more than 7mol percent, the Mooney viscosity ML (1+8) at 125 ℃ of more than 35, and the weight-average molecular weight M w Greater than 30 x 10 4g /mol。
Detailed Description
For further illustration of the present invention, the synthesis of a butyl rubber provided by the present invention is described in detail below with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The examples are all carried out in a low-temperature glove box, the oxygen content of water is less than 10ppm, the purity of a polymerization solvent is more than or equal to 99.5 percent, the purity of a solvent polarity regulator is more than or equal to 99.5 percent, the purity of isoolefine is more than or equal to 99.5 percent, and the purity of dialkene is more than or equal to 99.8 percent in an inert gas atmosphere.
Example 1
In a cold bath at the temperature of minus 80 ℃, 110.5g of n-hexane and 5.82g of 1,1, 1-trifluoromethane are taken into a reactor;
then adding 19.5g of isobutene and 1.25g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a-80 deg.C cold bath for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
12.07g of butyl rubber was obtained, the conversion was 58.2%, the gel content was 1.2%, and by conducting nuclear magnetic resonance analysis, Mooney viscosity analysis, and GPC measurement, the obtained butyl rubber had a degree of conversion unsaturation of 2.9 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 45, and a weight average molecular weight M w Is 18 x 10 4 g/mol。
Example 2
In a cold bath at the temperature of minus 80 ℃, 110.5g of normal hexane and 5.82g of 1,1,1, 2-tetrafluoroethane are put into a reactor;
then adding 19.5g of isobutene and 1.25g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a cold bath at-80 deg.C for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
17.68g of butyl rubber was obtained, the conversion was 85.2%, the gel content was 1.5%, and the conversion of the butyl rubber was 4.7 mol%, the Mooney viscosity ML (1+8) at 125 ℃ was 47, and the weight-average molecular weight M was measured by nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC w Is 45 x 10 4 g/mol。
Example 3
In a cold bath at the temperature of minus 80 ℃, 110.5g of normal hexane, 5.82g of 2,3,3, 3-tetrafluoro-1-propylene are taken to be arranged in a reactor;
then adding 19.5g of isobutene and 1.25g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a cold bath at-80 deg.C for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
9.4g of butyl rubber were obtained, the conversion was 45.3%, the gel content was 1.7%, and a nuclear magnetic resonance analysis, a Mooney viscosity analysis and a GPC test were carried out, whereby the conversion of the butyl rubber was 3.2 mol%, the Mooney viscosity ML (1+8) at 125 ℃ was 38, and the weight-average molecular weight M was measured w Is 27X 10 4 g/mol。
Example 4
In a cold bath at the temperature of minus 80 ℃, 110.5g of normal hexane and 19.5g of 1,1,1, 2-tetrafluoroethane are put into a reactor;
then adding 19.5g of isobutene and 2.06g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a-80 deg.C cold bath for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
16.21g of butyl rubber was obtained, the conversion was 75.2%, the gel content was 1.3%, and by conducting nuclear magnetic resonance analysis, Mooney viscosity analysis, and GPC measurement, the obtained butyl rubber had a degree of conversion unsaturation of 7.3 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of 43, and a weight-average molecular weight M w Is 42X 10 4 g/mol。
Example 5
In a cold bath at the temperature of minus 80 ℃, 110.5g of n-hexane and 27.6g of 1,1,1, 2-tetrafluoroethane are put into a reactor;
then adding 19.5g of isobutene and 4.18g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a-80 deg.C cold bath for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
16.83g of butyl rubber were obtained, the conversion was 71.07%, the gel content was 1.6%, and the conversion of the butyl rubber was 15 mol%, the Mooney viscosity ML (1+8) at 125 ℃ was 35, and the weight-average molecular weight M was determined by nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement w Is 38 multiplied by 10 4 g/mol。
Example 6
In a cooling bath at the temperature of-85 ℃, 110.5g of n-hexane and 19.5g of 1,1,1, 2-tetrafluoroethane are put into a reactor;
then adding 19.5g of isobutene and 2.06g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a cooling bath at-85 deg.C for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction flask was removed from the glove box and 50g of ethanol was added to terminate and precipitate the product;
the product was dried in a vacuum oven.
16.64g of butyl rubber was obtained, the conversion was 77.2%, the gel content was 1.1%, and the conversion of the butyl rubber was 8 mol%, the Mooney viscosity ML (1+8) at 125 ℃ was 48, and the weight averageMolecular weight M w 44X 104 g/mol.
Example 7
In a cold bath at the temperature of-85 ℃, 110.5g of n-hexane and 27.6g of 1,1,1, 2-tetrafluoroethane are put into a reactor;
then adding 19.5g of isobutene and 4.18g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a cooling bath at-85 deg.C for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction flask was removed from the glove box and 50g of ethanol was added to terminate and precipitate the product;
the product was dried in a vacuum oven.
16.58g of butyl rubber were obtained, the conversion was 70%, the gel content was 1.4%, and the conversion of the butyl rubber, the Mooney viscosity and the GPC measurement were carried out to obtain 15 mol% of unsaturation, a Mooney viscosity ML (1+8) at 125 ℃ of 40 and a weight average molecular weight M w Is 41X 10 4 g/mol。
Comparative example 1
In a cold bath at the temperature of minus 80 ℃, 110.5g of normal hexane is taken to be put in a reactor;
then adding 19.5g of isobutene and 2.06g of isoprene to obtain a polymerization monomer solution, and starting stirring;
mixing 20 wt% ethyl aluminum dichloride n-hexane solution 0.22g with HCl 0.025 wt% n-hexane solution 10g to obtain catalyst solution, and aging in a-80 deg.C cold bath for 10 min;
adding the catalyst solution into the polymerization monomer solution, and reacting for 10min to obtain a polymer glue solution;
the reaction bottle is removed from the glove box, 50g of ethanol is added to terminate and precipitate a product;
the product was dried in a vacuum oven.
7.65g of butyl rubber was obtained, the conversion was 35.5%, the gel content was 5%, and the butyl rubber was subjected to nuclear magnetic resonance analysis, Mooney viscosity analysis and GPC measurement to obtainThe rubber conversion is 3.2 mol% of unsaturation, the Mooney viscosity ML (1+8) is 30 at 125 ℃, and the weight-average molecular weight M w Is 12 x 10 4 g/mol。
In comparison with examples 1-7, in comparative example 1, no solvent polarity modifier fluoroalkane was added, and the obtained product had lower unsaturation degree and lower Mooney viscosity and molecular weight than in the examples, which proves that the addition of the solvent polarity modifier fluoroalkane serves to improve the reaction activity of the polyene hydrocarbon in the butyl polymerization process.
In summary, preference is given to a conversion of greater than 70%, a gel content of less than 1.5, an unsaturation of greater than 7 mol%, a Mooney viscosity ML (1+8) at 125 ℃ of greater than 35, and a weight-average molecular weight M w Greater than 30 x 10 4g The parameter/mol is used for the synthesis of highly unsaturated butyl rubbers.
From the above examples, the present invention provides a method for synthesizing butyl rubber, comprising the following steps: mixing a polymerization monomer with a mixed solvent to obtain a polymerization monomer solution; the mixed solvent comprises a polarity regulator and a polymerization solvent, wherein the polarity regulator has a general formula shown in a formula I: c x H y F z The formula I is shown in the specification; the value of x is 1-10, the value of y is 1-20, the value of z is 1-8, and x, y and z are integers; reacting the polymerization monomer solution under an initiation system to obtain a glue solution; and (3) removing the solvent from the glue solution, adding an alcohol compound to terminate, precipitating a product, and drying to obtain the butyl rubber. The method improves the reaction activity of polyene hydrocarbon in the polymerization monomer by adopting the polarity regulator, thereby increasing the double bond content in the molecular chain of the butyl rubber and leading the prepared butyl rubber to have higher unsaturation degree. The polymerization method does not reduce the activity of the initiator, has no adverse effect on the conversion rate and the molecular weight, and the obtained product has no gel basically. The increase of the polarity of the reaction system reduces the viscosity of the reaction system, improves the heat transfer efficiency of the system, reduces the hanging glue and achieves the purposes of energy conservation and consumption reduction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A synthesis method of butyl rubber comprises the following steps:
mixing a polymerization monomer with a mixed solvent to obtain a polymerization monomer solution; the mixed solvent comprises a polarity regulator and a polymerization solvent, wherein the polarity regulator has a general formula shown in a formula I:
C x H y F z formula I;
the value of x is 1-10, the value of y is 1-20, the value of z is 1-8, and x, y and z are integers;
reacting the polymerization monomer solution under an initiation system to obtain a glue solution; the polymerization monomer is selected from isomonoolefin and polyene hydrocarbon of C4-C16 with the molar ratio of (98:2) - (80: 20);
and (3) removing the solvent from the glue solution, adding an alcohol compound to terminate, precipitating a product, and drying to obtain the butyl rubber.
2. The synthetic method according to claim 1, wherein x is 1-6, y is 1-10, and z is 1-6.
3. The method of synthesis according to claim 1, the polarity modifier is selected from one or more of difluoromethane, 1, 1-difluoromethane, 1,1, 1-trifluoromethane, 1,1,1, 2-tetrafluoroethane, 1,1,2, 2-tetrafluoroethane, 1,1,1,2, 2-pentafluoroethane, 1, 2-difluoroethylene, 1,1, 2-trifluoroethylene, 1-fluoropropene, 1, 1-difluoropropene, 1, 2-difluoropropene, 1, 3-difluoropropene, 2, 3-difluoropropene, 3, 3-difluoropropene, 1,1, 2-trifluoropropene, 1,1, 3-trifluoropropene, 1,2, 3-trifluoropropene, 2,3, 3-trifluoropropene, and 2,3,3, 3-tetrafluoro-1-propene.
4. The synthesis method according to claim 1, wherein the mass ratio of the polarity modifier to the polymerization solvent is (1:99) to (50: 50).
5. The synthesis method according to claim 1, characterized in that the temperature of the polymerization monomer solution under the initiation system is-70 to-90 ℃.
6. The process of claim 1, wherein the polyene is selected from the group consisting of conjugated dienes of C4 to C14 and/or cyclic dienes of C5 to C8.
7. The method of synthesis of claim 1, wherein the initiation system comprises a primary initiator, a co-initiator, and a polymerization solvent;
the main initiator is selected from one or more of aluminum trichloride, ethyl aluminum dichloride, diethyl aluminum monochloride, butyl aluminum dichloride, dibutyl aluminum monochloride, boron trifluoride, titanium tetrachloride and aluminum sesqui-chloride;
the coinitiator is selected from H 2 O or HCl;
the molar ratio of the polymerized monomer to the main initiator is 1500-1000; the molar ratio of the main initiator to the auxiliary initiator is 10-5: 1.
8. The method of claim 1, wherein the butyl rubber has an unsaturation of 5 to 15 mol%.
9. The method of synthesis according to claim 7, wherein the polymerization solvent is a non-polar solvent.
10. The method of claim 9, wherein the non-polar solvent is selected from one or more of n-pentane, isopentane, cyclopentane, n-hexane, isohexane, cyclohexane, and methylcyclohexane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
| CN116284530A (en) * | 2023-03-17 | 2023-06-23 | 山东京博中聚新材料有限公司 | Preparation method and application of butyl rubber |
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| CN106573996A (en) * | 2014-04-30 | 2017-04-19 | 阿朗新科新加坡私人有限公司 | Hydrofluorinated olefins (HFO's) as diluents for butyl rubber production |
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| WO2004058836A1 (en) * | 2002-12-20 | 2004-07-15 | Exxonmobil Chemical Patents Inc. | Polymers with new sequence distributions |
| CN106573996A (en) * | 2014-04-30 | 2017-04-19 | 阿朗新科新加坡私人有限公司 | Hydrofluorinated olefins (HFO's) as diluents for butyl rubber production |
| CN105646757A (en) * | 2014-11-27 | 2016-06-08 | 中国石油化工股份有限公司 | Cationic polymerization system and preparation method of high-unsaturation-degree isoolefin copolymer |
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| CN116284530A (en) * | 2023-03-17 | 2023-06-23 | 山东京博中聚新材料有限公司 | Preparation method and application of butyl rubber |
| CN116284530B (en) * | 2023-03-17 | 2024-06-07 | 山东京博中聚新材料有限公司 | Preparation method and application of butyl rubber |
| CN116217773A (en) * | 2023-03-29 | 2023-06-06 | 山东京博中聚新材料有限公司 | Butyl rubber with wide molecular weight distribution and synthetic method thereof |
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