CN1635004A - Process for producing high cis-polybutadiene rubber - Google Patents
Process for producing high cis-polybutadiene rubber Download PDFInfo
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Abstract
A production process of cis-rich polybutadiene is to polymerize 1,3-butadiene under the temperature of 40-120DEG C in hydrogenated gasoline. The process is characterized in that the initiation system is composed of nickel naphthenate, triisobutylaluminum, boron trifluoride D complex, wherein, D is a C6-C18 alcohol, an ester composed of C2-C4 alkyl acid and C4-C6 alkyl alcohol, or a R3N tertiary amine substance wherein the R is a C4-C8 alkyl. By regulating the content of boron trifluoride D complex, a cis-rich polybutadiene with 25-100 Mooney viscosity, less than 0.05% gel can be synthesized. The cis-rich polybutadiene has improved processing properties and stress at definite elongation, lower Mooney viscosity by 10 Mooney unit than that of general cis-1,4-polybutadiene rubber BR900 with the same molecular weight. The invention has advantages of low energy consumption, simple operation, steady production, long running period, and high conversion rate.
Description
Technical field
The invention belongs to China Synthetic Rubber Industry, relate to the technology that polymerizing butadiene is produced cis-1,4-polybutadiene rubber.
Background technology
Nickel is that general cis-1,4-polybutadiene rubber production is at a certain temperature, in hydrogenated gasoline or hexane, hexanaphthene, toluene, benzene equal solvent, 1, the 3-divinyl is polymerized under the nickel catalyst effect, the nickel catalyst that industrial production adopts is the Ni-Al-B three-way catalyst, Ni is meant carboxylic acid nickel salts such as nickel naphthenate, nickel acetate, nickel octoate, and Al is meant triisobutyl aluminium or triethyl aluminum, and B is meant boron trifluoride ethyl ether complex or boron trifluoride ether complex.At the bottom of the cis-1,4-polybutadiene rubber of producing can be used for producing doughnut, motorcycle tyre, hand cart tyre, sebific duct, rubber overshoes, sealing-ring etc., have snappiness, wear resistance good, give birth to series of advantages such as the low and dynamic property of heat is better, but its gel content height, anti-cold flow properties is poor, especially in process of production because boron trifluoride solvability in solvent is bad, cause and can not effectively regulate the molecular weight size, the polymerization unit kiss-coating is serious etc., has limited its use range.
It is catalyzer that the patent CN1080295 of Yanshan Petrochemical company adopts nickel naphthenate, triisobutyl aluminium, boron trifluoride ethyl ether complex, the gel content of controlling cis-1,4-polybutadiene rubber by minor amount of water consumption in the regulation system and polymerization temperature.Because boron trifluoride solvability in solvent is bad in the system, difficult control in rubber production.
In nickel-aluminium-boron catalyst system, add alcohols, Ester as the 4th component,, can regulate mooney viscosity significantly by regulating catalyst proportion.But when producing high Mooney glue, soltion viscosity is bigger, easy kiss-coating, and the equipment operation cycle is short.
The patent JP02091105 of Japan SYnthetic Rubber Co. Ltd adopts the Ni-Al-B catalyst system, is solvent with toluene or toluene and 20% other hydrocarbon compound, regulates catalyst proportion and regulates mooney viscosity.But toluene toxicity is big, and the cost height.The single aluminium agent that the patent US5412045 of Polysar rubber company adopts triethyl aluminum and trioctylaluminum to replace tradition to use, hexanaphthene is a solvent, improves catalyst formulation, can produce the product of low-gel content.But hexanaphthene price height, and use two kinds of aluminium agent complicated operations, so the production cost height.
Summary of the invention
The production technique of the cis-rich polybutadiene rubber that technical problem to be solved by this invention provides can reduce gel content in the cis-1,4-polybutadiene rubber, alleviates the equipment kiss-coating, prolongs the cycle of operation; Reduce soltion viscosity; Regulate mooney viscosity significantly.
The production technique of cis-rich polybutadiene rubber of the present invention, be by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent is characterized in that the initiator system that polyreaction adopts is made up of nickel naphthenate, triisobutyl aluminium, boron trifluoride D complex compound, and wherein D is C
6～C
18Alcohol, by C
2～C
4Alkyl acid and C
4～C
6The alkyl alcohol ester or the R that form
3N tertiary amines material, wherein R is C
4～C
8Alkyl, the mol ratio of boron trifluoride D complex compound and divinyl is 0.2～3.5 * 10
-4, the mol ratio of Ni and divinyl is 0.5～8.0 * 10
-5, the mol ratio of Al and divinyl is 0.1～8.0 * 10
-4
It is initiator system that the present invention has adopted new nickel, produces the cis-1,4-polybutadiene rubber of different mooney viscosities by regulating boron trifluoride D complex compound consumption.The mol ratio of initiator and divinyl is preferably: boron trifluoride D complex compound and divinyl mol ratio are 0.3～2.5 * 10
-4, the mol ratio of Ni and divinyl is 2.1～6.0 * 10
-5, the mol ratio of Al and divinyl is 2.1～6.0 * 10
-4
The polyreaction preheating temperature is 40 ℃, 80～120 ℃ of reaction top temperatures, and the preferred value of temperature of reaction is 40～120 ℃.Fourth oil concentration (divinyl/solvent) is 5～18g/100ml solvent oil, is preferably 8～15g/100ml solvent oil.This reaction conditions and novel initiation system adapt, and the product that makes, cis-1,4-polybutadiene rubber mooney viscosity are 25～100, and gel content is compared with BR9000 (general cis-1,4-polybutadiene rubber) less than 0.05%, low 10 mooney units of mooney viscosity during the same molecular amount.
Boron trifluoride D complex compound be by boron trifluoride and D material in the container of airtight, withstand voltage 0.5Mpa, fully react at 200～400 ℃ and to make.Boron trifluoride in the boron trifluoride D complex compound accounts for 15～30% of this complex compound quality.
D is preferably C in the boron trifluoride D complex compound
6～C
9Alcohol (as hexanol, n-Octanol, isooctyl alcohol, nonyl alcohol) or by C
2～C
4Alkyl acid and C
4～C
6The alkyl alcohol ester (as butylacetate, hexyl acetate, n-butyl propionate, isobutyl propionate, n-hexyl propionate, butyl butyrate, n-hexyl butyrate) or the R that form
3N tertiary amines material, wherein R is C
4～C
8Alkyl (as Tributylamine, trihexylamine, trioctylamine etc.).
The material that polymer solvent of the present invention can adopt prior art to use usually is preferably hydrogenated gasoline, and toxicity is low, and cost is low.
According to method of the present invention, utilize existing cis-1,4-polybutadiene rubber production equipment, produce the cis-1,4-polybutadiene rubber of different mooney viscosities, gel content is low, and processing characteristics is improved greatly, and stress at definite elongation improves.In the production process, can produce mooney viscosity 25～40,40～50,55～100 different trade mark products according to different needs.Compare with former BR9000, under the same molecular amount, mooney viscosity can hang down 10 mooney units.High molecular rubber can be used for producing oil-extended butadiene rubber, to satisfy different purposes.Polymerization technique energy consumption of the present invention is low, and polymeric kettle and pipeline kiss-coating are light, easy to operate, produces and stablizes, and running period is long, the transformation efficiency height.The mooney viscosity that adopts the present invention's preparation is 25～35 low-mooney polybutadiene rubber, and 300% stress at definite elongation and tensile strength all can reach BR9000 quality level.The mooney viscosity that adopts the present invention's preparation is that 5% styrene solution viscosity of 35～40 cis-1,4-polybutadiene rubber product is 60～120mPa.s, and gel content can be used to prepare HIPS less than 0.05%.The mooney viscosity that adopts the present invention's preparation is that the gelatin viscosity of 70～90 cis-1,4-polybutadiene rubber product is 20000～45000mPa.s, can produce contamination type oil-extended butadiene rubber BR9073 and without pollution oil-extended butadiene rubber BR9053 according to demand.
Following table is the rubber of employing the inventive method production and the comparing result of BR9000:
| Sequence number | Project | General nickel is BR9000 | Cis-1,4-polybutadiene rubber of the present invention | High Mooney cis-1,4-polybutadiene rubber of the present invention |
| ?1 | 100 ℃ of mooney viscosity ML (1+4) | ?40～50 | ?25～40，40～50 | ?70～90 |
| ?2 | 300% stress at definite elongation MPa (35min) | ?7.2～8.5 | ?8.5～11.0 | ?8.5～11.0 |
| ?3 | Tensile strength/MPa | ?14.2 | ?13.0～15.0 | ?13.0～15.0 |
| ?4 | Elongation/% | ?450 | ?380～500 | ?400～500 |
| ?5 | Hardness/Shao A | ?60 | ?55～60 | ?60～70 |
| ?6 | Gel content/% | ?0.36 | ?0.04～0 | ?0.04～0 |
| ?7 | The processing banding characteristics | Difference | Good | Good |
| ?8 | Cis-1,4/% | ?94～96 | ?94～96 | ?94～96 |
| ?9 | Gelatin viscosity mPa.s | ?3000～4000 | ?2500～3500 | ?20000～45000 |
| ?10 | Polymerization kettle cleaning period/sky | ?7 | ?40 | ?40 |
Embodiment
Embodiment 1
In the 5L polymeric kettle, add 100 parts of hydrogenated gasolines, 15 parts of divinyl, logical nitrogen pressurize is opened and is stirred, and the preheating in chuck of logical hot water.The ageing liquid that adds nickel naphthenate and triisobutyl aluminium when preheating temperature reaches 40 ℃ successively, boron trifluoride nonyl alcohol complex compound.Catalyst levels Ni/Bd (mol ratio, together, Bd represents divinyl down)=6.0 * 10
-5, Al/Bd=3.6 * 10
-4, boron trifluoride nonyl alcohol complex compound/Bd=2.5 * 10-4 reacted 3 hours, and monomer conversion is greater than 97%, and the polyreaction top temperature is 85 ℃.The glue cohesion obtains product of the present invention after the drying, the gel content of product is 0.02%.The results are shown in Table 2.
Comparative Examples 1
Adopt the cis-1,4-polybutadiene rubber three-way catalyst, nickel naphthenate, triisobutyl aluminium, boron trifluoride ethyl ether complex are catalyzer, boron trifluoride ethyl ether complex/Bd=2.5 * 10
-4, other condition is with embodiment 1, monomer conversion 85%, and the polyreaction top temperature is 87 ℃.The mooney viscosity of gained cis-1,4-polybutadiene rubber is 40, and the gel content of product is 0.38%.
Embodiment 2
Ni/Bd=5.7 * 10
-5, Al/Bd=4.3 * 10
-4, boron trifluoride nonyl alcohol complex compound/Bd=3.5 * 10
-4, monomer conversion 95%, the polyreaction top temperature is 110 ℃.The gel content of product is 0.03%.Other condition is with embodiment 1.
Embodiment 3
Ni/Bd=5.1 * 10
-5, Al/Bd=3.6 * 10
-4, boron trifluoride nonyl alcohol complex compound/Bd=2.5 * 10
-4, monomer conversion 95%, the polyreaction top temperature is 110 ℃.The gel content of product is 0.03%.Other condition is with embodiment 1.
Embodiment 4
Ni/Bd=4.7 * 10
-5, Al/Bd=4.5 * 10
-4, boron trifluoride nonyl alcohol complex compound/Bd=2.2 * 10
-4, monomer conversion 95%, the polyreaction top temperature is 95 ℃.The gel content of product is 0.04%.Other condition is with embodiment 1.
Embodiment 5
Ni/Bd=4.7 * 10
-5, Al/Bd=5.1 * 10
-4, boron trifluoride nonyl alcohol complex compound/Bd=1.8 * 10
-4, monomer conversion 95%, the polyreaction top temperature is 100 ℃.The gel content of product is 0.04%.Other condition is with embodiment 1.
Embodiment 6
Ni/Bd=4.0 * 10
-5, Al/Bd=5.2 * 10
-4, boron trifluoride hexanol complex compound/Bd=1.0 * 10
-4, monomer conversion 94%, the polyreaction top temperature is 100 ℃.The gel content of product is 0.03%.Other condition is with embodiment 1.
Embodiment 7
Ni/Bd=3.5 * 10
-5, Al/Bd=5.4 * 10
-4, boron trifluoride hexanol complex compound/Bd=0.8 * 10
-4, monomer conversion 94%, the polyreaction top temperature is 90 ℃.The gel content of product is 0.04%.Other condition is with embodiment 1.
Embodiment 8
Ni/Bd=3.3 * 10
-5, Al/Bd=5.7 * 10
-4, boron trifluoride butylacetate complex compound/Bd=0.6 * 10
-4, monomer conversion 93%, the polyreaction top temperature is 90 ℃.The gel content of product is 0.04%.Other condition together
Embodiment 1.
Embodiment 9
Ni/Bd=2.5 * 10
-5, Al/Bd=6.0 * 10
-4, boron trifluoride butylacetate complex compound/Bd=0.4 * 10
-4, monomer conversion 91%, the polyreaction top temperature is 80 ℃.The gel content of product is 0.04%.Other condition together
Embodiment 1.
Embodiment 10
Ni/Bd=2.1 * 10
-5, Al/Bd=6.2 * 10
-4, boron trifluoride butylacetate complex compound/Bd=0.3 * 10
-4, monomer conversion 91%, the polyreaction top temperature is 75 ℃.The gel content of product is 0.04%.Other condition together
Embodiment 1.
Embodiment 11
Add 1000 parts of 150 parts of divinyl and hydrogenated gasolines in the 50L polymeric kettle, logical nitrogen pressurize is opened and is stirred, logical hot water preheating in chuck.When reaching 40 ℃, preheating temperature adds nickel naphthenate, triisobutyl aluminium, boron trifluoride .D complex compound successively, catalyst levels Ni/Bd=4.0 * 10
-5, Al/Bd=4.5 * 10
-4, boron trifluoride butylacetate complex compound/Bd=2.2 * 10
-4, reacted 3 hours, monomer conversion 95%, the polyreaction top temperature is 130 ℃.The gel content of product is 0.04%.Obtain product of the present invention after glue cohesion, the drying.The results are shown in Table 2.
Comparative Examples 2
Add 1000 parts of 150 parts of divinyl and hydrogenated gasolines in the 50L polymeric kettle, logical nitrogen pressurize is opened and is stirred, logical hot water preheating in chuck.When reaching 40 ℃, preheating temperature adds catalyst levels successively, Ni/Bd=4.0 * 10
-5, Al/Bd=4.5 * 10
-4, boron trifluoride ethyl ether complex/Bd=2.2 * 10
-4, reacted 3 hours, monomer conversion 90%, the polyreaction top temperature is 130 ℃.The gel content of product is 0.33%.Obtain product after the drying.The results are shown in Table 2.
Embodiment 12
Ni/Bd=3.5 * 10
-5, Al/Bd=4.8 * 10
-4, boron trifluoride Tributylamine complex compound/Bd=1.0 * 10
-4, reacted 3 hours, monomer conversion 93%, the polyreaction top temperature is 110 ℃.Other condition is with embodiment 10.
Embodiment 13
Ni/Bd=2.3 * 10
-5, Al/Bd=5.2 * 10
-4, boron trifluoride Tributylamine complex compound/Bd=0.4 * 10
-4, reacted 3 hours, monomer conversion 92%, the polyreaction top temperature is 100 ℃.Other condition is with embodiment 10.
Table 2 reaction conditions and product test result
| Sequence number | Reactor L | ?Ni ?×10 5 | ?Al ?×10 4 | Boron trifluoride D * 10 4 | Reaction top temperature ℃ | 100 ℃ of mooney viscosity ML (1+4) | Butadiene conversion % | Cis 1,4 structure % | Gel content % | Number-average molecular weight ten thousand |
| Embodiment 1 | ?5 | ?6.0 | ?3.6 | ?2.5 | ?85 | ?25 | ?96 | ?96 | ?0.02 | ?5.2 |
| Comparative Examples 1 | ?5 | ?6.0 | ?3.6 | Boron trifluoride diethyl etherate 2.5 | ?87 | ?40 | ?85 | ?96 | ?0.38 | ?10.2 |
| Embodiment 2 | ?5 | ?5.1 | ?4.5 | ?2.5 | ?110 | ?40 | ?95 | ?95 | ?0.03 | ?6.8 |
| Embodiment 3 | ?5 | ?4.7 | ?4.5 | ?2.2 | ?95 | ?43 | ?95 | ?96 | ?0.04 | ?7.8 |
| Embodiment 4 | ?5 | ?4.7 | ?5.1 | ?1.8 | ?100 | ?47 | ?95 | ?96 | ?0.04 | ?8.3 |
| Embodiment 5 | ?5 | ?4.0 | ?5.2 | ?1.0 | ?100 | ?54 | ?94 | ?97 | ?0.03 | ?9.5 |
| Embodiment 6 | ?5 | ?3.5 | ?5.4 | ?0.8 | ?90 | ?63 | ?94 | ?97 | ?0.04 | ?10.8 |
| Embodiment 7 | ?5 | ?3.3 | ?5.7 | ?0.6 | ?90 | ?75 | ?93 | ?95 | ?0.04 | ?11.7 |
| Embodiment 8 | ?5 | ?2.5 | ?6.0 | ?0.4 | ?80 | ?89 | ?91 | ?96 | ?0.04 | ?13.9 |
| Embodiment 9 | ?5 | ?2.1 | ?6.2 | ?0.3 | ?75 | ?93.5 | ?91 | ?97 | ?0.04 | ?16.7 |
| Embodiment 10 | ?50 | ?4.0 | ?4.5 | ?2.2 | ?130 | ?27 | ?95 | ?94 | ?0.04 | ?5.8 |
| Comparative Examples 2 | ?50 | ?4.0 | ?4.5 | Boron trifluoride diethyl etherate 2.2 | ?120 | ?45 | ?90 | ?95 | ?0.3 | ?9.7 |
| Embodiment 11 | ?50 | ?3.5 | ?4.8 | ?1.0 | ?110 | ?50 | ?93 | ?97 | ?0.03 | ?9.1 |
| Embodiment 12 | ?50 | ?2.3 | ?5.2 | ?0.4 | ?100 | ?90 | ?92 | ?96 | ?0.04 | ?14.3 |
Claims (7)
1, the production technique of cis-rich polybutadiene rubber, be by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent is characterized in that the initiator system that polyreaction adopts is made up of nickel naphthenate, triisobutyl aluminium, boron trifluoride D complex compound, and wherein D is C
6～C
18Alcohol, by C
2～C
4Alkyl acid and C
4～C
6The alkyl alcohol ester or the R that form
3N tertiary amines material, wherein R is C
4～C
8Alkyl, the mol ratio of boron trifluoride D complex compound and divinyl is 0.2～3.5 * 10
-4, the mol ratio of Ni and divinyl is 0.5～8.0 * 10
-5, the mol ratio of Al and divinyl is 0.1～8.0 * 10
-4
2, production technique according to claim 1 is characterized in that the polyreaction preheating temperature is 40 ℃, 80～120 ℃ of reaction top temperatures, and the fourth oil concentration is 5～18g/100ml solvent oil.
3, production technique according to claim 1 is characterized in that boron trifluoride D complex compound and divinyl mol ratio are 0.3～2.5 * 10
-4, the mol ratio of Ni and divinyl is 2.1～6.0 * 10
-5, the mol ratio of Al and divinyl is 2.1～6.0 * 10
-4
4, production technique according to claim 2 is characterized in that polymeric reaction temperature is 40～120 ℃, and the fourth oil concentration is 8～15g/100ml solvent oil.
5, production technique according to claim 1 is characterized in that described boron trifluoride D complex compound is fully to be reacted at 200～400 ℃ by boron trifluoride and D material to make.
6, production technique according to claim 5 is characterized in that the boron trifluoride in the described boron trifluoride D complex compound accounts for 15～30% of this complex compound total mass.
7, production technique according to claim 1 is characterized in that described polymer solvent is a hydrogenated gasoline.
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|---|---|---|---|
| CN 200310114681 CN1247631C (en) | 2003-12-28 | 2003-12-28 | Process for producing high cis-polybutadiene rubber |
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|---|---|---|---|
| CN 200310114681 CN1247631C (en) | 2003-12-28 | 2003-12-28 | Process for producing high cis-polybutadiene rubber |
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| CN1247631C CN1247631C (en) | 2006-03-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580560B (en) * | 2008-05-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst system and method for polymerizing butadiene |
| CN106565879A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Antistatic oil-extended butadiene rubber for hydraulic breaking hammer high-pressure oil pipe and preparation method of antistatic oil-extended butadiene rubber |
| CN106565880A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Anti-bacterial oil-extended butadiene rubber used for high pressure oil pipe of hydraulic breaking hammer and preparation method thereof |
| CN106566024A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | High-toughness oil-extended cis-polybutadiene rubber for high-pressure oil pipe of hydraulic breaking hammer, and preparation method of rubber |
| CN106566025A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Anti-wear oil-extended butadiene rubber used for high pressure oil pipe of hydraulic breaking hammer and preparation method thereof |
| CN106589740A (en) * | 2016-11-10 | 2017-04-26 | 当涂县金龙机械有限公司 | Oil-extended 3-polybutadiene rubber for tensile hydraulic breaking hammer high-pressure oil pipe and preparation method thereof |
| CN106589739A (en) * | 2016-11-10 | 2017-04-26 | 当涂县金龙机械有限公司 | Good-gas-barrier-property oil-extended cis-polybutadiene rubber used for hydraulic hammer high pressure oil pipe and preparation method thereof |
| CN106750621A (en) * | 2016-11-10 | 2017-05-31 | 当涂县金龙机械有限公司 | A kind of High Strength Hydraulic quartering hammer high-pressure oil pipe oil-extended butadiene rubber and preparation method thereof |
| CN114031698A (en) * | 2021-10-26 | 2022-02-11 | 中国石油化工股份有限公司 | Raw butadiene rubber and preparation method thereof |
-
2003
- 2003-12-28 CN CN 200310114681 patent/CN1247631C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580560B (en) * | 2008-05-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst system and method for polymerizing butadiene |
| CN106565879A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Antistatic oil-extended butadiene rubber for hydraulic breaking hammer high-pressure oil pipe and preparation method of antistatic oil-extended butadiene rubber |
| CN106565880A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Anti-bacterial oil-extended butadiene rubber used for high pressure oil pipe of hydraulic breaking hammer and preparation method thereof |
| CN106566024A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | High-toughness oil-extended cis-polybutadiene rubber for high-pressure oil pipe of hydraulic breaking hammer, and preparation method of rubber |
| CN106566025A (en) * | 2016-11-10 | 2017-04-19 | 当涂县金龙机械有限公司 | Anti-wear oil-extended butadiene rubber used for high pressure oil pipe of hydraulic breaking hammer and preparation method thereof |
| CN106589740A (en) * | 2016-11-10 | 2017-04-26 | 当涂县金龙机械有限公司 | Oil-extended 3-polybutadiene rubber for tensile hydraulic breaking hammer high-pressure oil pipe and preparation method thereof |
| CN106589739A (en) * | 2016-11-10 | 2017-04-26 | 当涂县金龙机械有限公司 | Good-gas-barrier-property oil-extended cis-polybutadiene rubber used for hydraulic hammer high pressure oil pipe and preparation method thereof |
| CN106750621A (en) * | 2016-11-10 | 2017-05-31 | 当涂县金龙机械有限公司 | A kind of High Strength Hydraulic quartering hammer high-pressure oil pipe oil-extended butadiene rubber and preparation method thereof |
| CN114031698A (en) * | 2021-10-26 | 2022-02-11 | 中国石油化工股份有限公司 | Raw butadiene rubber and preparation method thereof |
| CN114031698B (en) * | 2021-10-26 | 2023-07-25 | 中国石油化工股份有限公司 | Butadiene rubber raw rubber and preparation method thereof |
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