CN103172789A - Method for preparing nickel series low-mooney high cis-1,4-polybutadiene rubber - Google Patents
Method for preparing nickel series low-mooney high cis-1,4-polybutadiene rubber Download PDFInfo
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- CN103172789A CN103172789A CN2012105407528A CN201210540752A CN103172789A CN 103172789 A CN103172789 A CN 103172789A CN 2012105407528 A CN2012105407528 A CN 2012105407528A CN 201210540752 A CN201210540752 A CN 201210540752A CN 103172789 A CN103172789 A CN 103172789A
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Abstract
The invention provides a method for preparing nickel series low-mooney high cis-1,4-polybutadiene rubber. A solution polymerization reaction is performed by 1,3-butadiene in a polymerization solvent. The preparation method has the beneficial effect that a low-mooney cis rubber with the mooney viscosity between 25 and 40 can be prepared stably, and the prepared low-mooney cis rubber can be kept in a higher tensile strength, achieves the same strength as that of butadiene rubber with mooney viscosity between 40 and 50, and has a low gel content which is less than 0.5 percent.
Description
Technical field
The invention belongs to the synthetic field of rubber, relate to a kind of preparation method of low Mooney point high-cis 1，4-polybutadiene rubber.
Background technology
high-cis 1, the preparation technology of 4-polybutadiene rubber (referred to as cis-1,4-polybutadiene rubber) generally adopts solution polymerization process, with cobalt be, titanium system, nickel system, rare earth is that catalyst system makes 1, 3-divinyl (being called for short Bd) polymerization, the nickel catalyst that industrial production adopts is-the Ni-AL-B three-way catalyst, Ni refers to nickel naphthenate, nickel acetate, the carboxylic acid nickel salts such as nickel octoate, AL refers to triisobutyl aluminium or triethyl aluminum, B refers to boron trifluoride ethyl ether complex or boron trifluoride ether complex, the aliphatic saturated hydrocarbon that polymer solvent is in a liquid state when being polymerization, aromatic hydrocarbons, naphthenic hydrocarbon or its mixture, as refine oil the intensity of Mooney cis-1,4-polybutadiene rubber and can not descend.Low-mooney polybutadiene rubber is domestic does not have manufacturer and patented technology.Factory raffinates oil, hexane, heptane, benzene or toluene.The mooney viscosity of prepared cis-1,4-polybutadiene rubber is generally 40-50, and the processing characteristics of cis-1,4-polybutadiene rubber is relatively poor, and tackiness is bad.
China's nickel polymerized BR production is adopted take nickel naphthenate-triisobutyl aluminium-boron trifluoride ethyl ether complex as catalyzer, to raffinate oil as the catalyst system of solvent, the mooney viscosity of the cis-1,4-polybutadiene rubber of preparation is 40-50, adopt and regulate the AL-B ratio or add appropriate water to regulate the molecular weight of cis-1,4-polybutadiene rubber, but because the scope of application of nickle catalyst system AL/B ratio is narrower, and system is very responsive to water, therefore, under existence conditions by regulate AL/B than or add appropriate water can only trace to regulate the molecular weight of cis-1,4-polybutadiene rubber, existing system is not suitable for preparing the cis-1,4-polybutadiene rubber that mooney viscosity is 25-40.
Add the molecular weight regulator molecular weight of telomerized polymer easily in polymerization system, the clear 46-7708 report of Japan's special permission, the conditioning agent that can reduce molecular weight has alkynes, as propylacetylene, ethylacetylene, vinylacetylene, phenylacetylene etc., and the alkene such as divinyl dimer, hydrogen, ethene, propylene, cyclooctadiene also can reduce molecular weight.U.S. Goodyear company has studied halogenated phenols and had the effect that reduces cis 1，4-polybutadiene molecular weight and widen its molecular weight distribution in the Ni catalyst system in patent U.S5100982 (1992).The control method of the molecular weight of the high-cis 1，4-polybutadiene that U.S. Goodyear company reports in patent EP0093073 (1983) is to adopt with the organic nickel compound in the solvent of aliphatics or cycloaliphatic.The catalyzer that the complex compound that organo-aluminium compound and HF are combined with ketone, ester, aldehyde, ether, alcohol, phenol, water forms carries out polymericular weight and regulates under a-alkene such as ethene, propylene exist on a small quantity.And Japan special permission clear 40-13072, clear 41-3640, clear 44-27824, clear 42-4985, clear 44-19260 and U.S.Pat, 3487063 (1970) reports add alcohol, naphthalene, phenols in polymerization system.CS
2, CO
2, water and chelate compound etc., the effect of the molecular weight that is improved.
The size of the molecular weight of polymkeric substance directly affects the tensile strength of polymkeric substance, and general polymerization thing molecular weight reduces to make polymkeric substance to draw refreshing strength decreased.The low molecular weight polybutadiene weak point that adopts above-mentioned technology to prepare causes the decline of polymer strength when being the polyhutadiene molecular weight is reduced, and all publications are all reported the intensity that how to improve low-mooney polybutadiene rubber.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the low Mooney high-cis 1，4-polybutadiene rubber of a kind of nickel system.
the technical solution used in the present invention is: the low Mooney high-cis 1 of nickel system, the preparation method of 4-polybutadiene rubber, by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent, the employing catalyzer is nickel catalyst, this nickel catalyst is the Ni-AL-B three-way catalyst, Ni refers to nickel naphthenate, nickel acetate, the carboxylic acid nickel salts such as nickel octoate, AL refers to triisobutyl aluminium or triethyl aluminum, B refers to boron trifluoride ethyl ether complex or boron trifluoride ether complex, add molecular weight regulator D in polymerization system, but the compound of D hydroxyl or olefines, polymerizing condition is:
A. the mol ratio of Ni/Bd is (1.0-6.0) * 10
-5
B. the mol ratio of AL/Bd is (3.0-6.0) * 10
-5
C. the mol ratio of B/Bd is (1.0-10.0) * 10
-4
D. the mol ratio of D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（0.5-10.0）×10
-4
When D is olefines:
D/Bd=0.01-1.0
E. polymeric reaction temperature is 30-120 ℃,
Wherein Bd represents 1,3-butadiene,
Ni in Ni/Bd refers to contain in the carboxylic acid nickel salt mole number of Ni;
AL in AL/Bd refers to contain in organo-aluminium compound the mole number of AL;
B in B/Bd refers to the mole number of boron compound.
Molecular weight regulator is the compound of specific hydroxyl, and as alcohols, phenols, commonly used have a C
4～C
12Fatty Alcohol(C12-C14 and C12-C18), wherein preferred amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, certain herbaceous plants with big flowers alcohol, the preferred cresols of alkylphenol, also olefines, commonly used by butene-1, butene-2, iso-butylene, described polymerizing condition preferred value is:
A. the mol ratio of Ni/Bd is (2.5-4.0) * 10
-5
B. the mol ratio of AL/Bd is (4.0-7.0) * 10
-5
C. the mol ratio of B/Bd is (2.0-7.0) * 10
-4
D. the mol ratio of D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（1.0-7.0）×10
-4
When D is olefines:
D/Bd=0.05-0.5
Polymeric reaction temperature is 40-100 ℃.
Also added coupling agent C in polymerization system, coupling agent C selects divinyl compound, and its add-on is: the mol ratio of C/Bd is 0.01-10.0, preferred 0.05-5.
Beneficial effect of the present invention, can be stable prepare the low-mooney polybutadiene rubber that mooney viscosity is 25-40, and make the low-mooney polybutadiene rubber of preparation keep higher tensile strength, reach the intensity identical with the cis-1,4-polybutadiene rubber of mooney viscosity 40-50, has simultaneously lower gel content, less than 0.5%.
Embodiment
Technical problem to be solved by this invention is to provide the low Mooney high-cis 1 of nickel system, the preparation technology of 4-polybutadiene rubber, in the catalyst system take Ni-AL-B as catalyzer by adding molecular weight regulator D, regulate the add-on of D, the preparation low-mooney polybutadiene rubber, and add appropriate coupling agent to make molecular chain appropriateness branching, thereby make low your cis-1,4-polybutadiene rubber of door of preparation have higher intensity.
The low Mooney high-cis 1 of nickel system of the present invention, the preparation technology of 4-polybutadiene rubber, by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent, the employing catalyzer is nickel catalyst, this nickel catalyst is the Ni-AL-B three-way catalyst, Ni refers to the carboxylic acid nickel salts such as nickel naphthenate, nickel acetate, nickel octoate, AL refers to triisobutyl aluminium or triethyl aluminum, B refers to boron trifluoride ethyl ether complex or boron trifluoride ether complex, add molecular weight regulator D in polymerization system, but the compound of D hydroxyl or olefines, and polymerizing condition is:
A. the mol ratio of Ni/Bd is (1.0-6.0) * 10
-5
B. the mol ratio of AL/Bd is (3.0-6.0) * 10
-5
C. the mol ratio of B/Bd is (1.0-10.0) * 10
-4
D. the mol ratio of D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（0.5-10.0）×10
-4
When D is olefines:
D/Bd=0.01-1.0
E. polymeric reaction temperature is 30-120 ℃,
Wherein Bd represents 1,3-butadiene,
Ni in Ni/Bd refers to contain in the carboxylic acid nickel salt mole number of Ni;
AL in AL/Bd refers to contain in organo-aluminium compound the mole number of AL;
B in B/Bd refers to the mole number of boron compound.
The present invention selects the molecular weight regulator with good result, regulates add-on and AL/B ratio, can reduce the mooney viscosity of cis-1,4-polybutadiene rubber to 25-40.The present invention still adopts solution polymerization, the nickel catalyst system has technology with oneself, polymer solvent has technology with oneself, the aliphatic saturated hydrocarbon that is in a liquid state during for polymerization, aromatic hydrocarbons, naphthenic hydrocarbon or its mixture, as refinery raffinate oil, hexane, heptane, benzene or toluene.Other polymerizing conditions have technology with oneself.Molecular weight regulator is the compound of specific hydroxyl, and as alcohols, phenols, commonly used have a C
4～C
12Fatty Alcohol(C12-C14 and C12-C18), wherein preferred amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, certain herbaceous plants with big flowers alcohol, the preferred cresols of alkylphenol, also olefines, commonly used by butene-1, butene-2, iso-butylene, described polymerizing condition preferred value is:
A. the mol ratio of Ni/Bd is (2.5-4.0) * 10
-5
B. the mol ratio of AL/Bd is (4.0-7.0) * 10
-5
C. the mol ratio of B/Bd is (2.0-7.0) * 10
-4
D. the mol ratio of D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（1.0-7.0）×10
-4
When D is olefines:
D/Bd=0.05-0.5
Polymeric reaction temperature is 40-100 ℃.
The present invention has reduced mooney viscosity by molecular weight regulator, for the intensity that keeps cis-1,4-polybutadiene rubber and have lower gel content, also added coupling agent C in polymerization system, coupling agent C selects divinyl compound, its add-on is: the mol ratio of C/Bd is 0.01-10.0, preferred 0.05-5.Divinyl compound commonly used by Vinylstyrene.Divinyl naphthalene, 1,5 hexadiene.
Embodiment 1
Use 50 living polymeric kettles with ribbon stirring, chuck, temperature, pressure indication, make the 1.3-divinyl carry out batchwise polymerization.First wash still with clean raffinating oil; with nitrogen extrude wash still and raffinate oil after; under nitrogen protection; add raffinate oil 54 parts of 282.5 parts, divinyl in the polymeric kettle; stir; add respectively nickel naphthenate 0.0102mol, triisobutyl aluminium 0.235mol, boron trifluoride ethyl ether complex 0.0286mol, isooctyl alcohol 0.0304mol, Vinylstyrene 0.122mol; at 80 ℃ of temperature; the polyase 13 lab scale; add ethanol, anti-aging agent takes out glue; use the water vapour boiling, hot roller drying obtains product of the present invention.
Diene conversion rate is 91.4%.Reaction conditions and product test the results are shown in Table 1.
Embodiment 2
Replace isooctyl alcohol with butene-1, add 1-butylene 3.7mol in 54 parts of divinyl, nickel naphthenate 0.118mol, triisobutyl aluminium 0.384mol, boron trifluoride ethyl ether complex 0.0358mol, transformation efficiency are 90.2%.All the other are with embodiment 1.
Embodiment 3
Replace isooctyl alcohol with meta-cresol, add meta-cresol 0.0494mol, butadiene conversion 90.8%.All the other are with embodiment 1.
Embodiment 4
Add Vinylstyrene 1.22mol, transformation efficiency is 89.8%.All the other are with embodiment 1.
Comparative Examples 1
Add isooctyl alcohol 0mol, Vinylstyrene 0mol, butadiene conversion is 89.3%.All the other are with embodiment 1.
Comparative Examples 2
Add isooctyl alcohol 0.0304mol, butadiene conversion is 92.3%, and all the other are with embodiment 1.
Comparative Examples 3
In former catalyst system, regulate the AL/B ratio, add triisobutyl aluminium 0.313mol, boron trifluoride diethyl etherate compound 0.0358mol, butadiene conversion is 72.4%.All the other are in proportion 1 years old.
Claims (3)
1. nickel is low Mooney high-cis 1, the preparation method of 4-polybutadiene rubber, it is characterized in that: be by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent, the employing catalyzer is nickel catalyst, this nickel catalyst is the Ni-AL-B three-way catalyst, Ni refers to the carboxylic acid nickel salts such as nickel naphthenate, nickel acetate, nickel octoate, AL refers to triisobutyl aluminium or triethyl aluminum, B refers to boron trifluoride ethyl ether complex or boron trifluoride ether complex, add molecular weight regulator D in polymerization system, but the compound of D hydroxyl or olefines, and polymerizing condition is:
The mol ratio of a.Ni/Bd is (1.0-6.0) * 10
-5
The mol ratio of b.AL/Bd is (3.0-6.0) * 10
-5
The mol ratio of c.B/Bd is (1.0-10.0) * 10
-4
The mol ratio of d.D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（0.5-10.0）×10
-4
When D is olefines:
D/Bd=0.01-1.0
E. polymeric reaction temperature is 30-120 ℃,
Wherein Bd represents 1,3-butadiene,
Ni in Ni/Bd refers to contain in the carboxylic acid nickel salt mole number of Ni;
AL in AL/Bd refers to contain in organo-aluminium compound the mole number of AL;
B in B/Bd refers to the mole number of boron compound.
2. the preparation method of the low Mooney high-cis 1，4-polybutadiene rubber of nickel according to claim 1 system is characterized in that: the compound of the specific hydroxyl of molecular weight regulator, as alcohols, phenols, commonly used have a C
4～C
12Fatty Alcohol(C12-C14 and C12-C18), wherein preferred amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, certain herbaceous plants with big flowers alcohol, the preferred cresols of alkylphenol, also olefines, commonly used by butene-1, butene-2, iso-butylene, described polymerizing condition preferred value is:
The mol ratio of a.Ni/Bd is (2.5-4.0) * 10
-5
The mol ratio of b.AL/Bd is (4.0-7.0) * 10
-5
The mol ratio of c.B/Bd is (2.0-7.0) * 10
-4
The mol ratio of d.D/Bd is
When D is hydroxy-containing compounds:
D/Bd=（1.0-7.0）×10
-4
When D is olefines:
D/Bd=0.05-0.5
Polymeric reaction temperature is 40-100 ℃.
3. nickel according to claim 1 is low Mooney high-cis 1, the preparation method of 4-polybutadiene rubber is characterized in that: also added coupling agent C in polymerization system, coupling agent C selects divinyl compound, its add-on is: the mol ratio of C/Bd is 0.01-10.0, preferred 0.05-5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3932958A1 (en) * | 2020-07-01 | 2022-01-05 | Zhejiang Transfar Synthetic Material Co., Ltd. | Method for continuously preparing nickel catalysed cis-polybutadiene and rare earth catalysed cis-polybutadiene |
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| CN101580560A (en) * | 2008-05-16 | 2009-11-18 | 中国石油化工股份有限公司 | Catalyst system and method for polymerizing butadiene |
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2012
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Patent Citations (3)
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|---|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3932958A1 (en) * | 2020-07-01 | 2022-01-05 | Zhejiang Transfar Synthetic Material Co., Ltd. | Method for continuously preparing nickel catalysed cis-polybutadiene and rare earth catalysed cis-polybutadiene |
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Application publication date: 20130626 |