CN1425698A - Process for preparing nickel series low mooney viscosity high cis-1,4,-polybutadiene rubber - Google Patents
Process for preparing nickel series low mooney viscosity high cis-1,4,-polybutadiene rubber Download PDFInfo
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- CN1425698A CN1425698A CN 01135283 CN01135283A CN1425698A CN 1425698 A CN1425698 A CN 1425698A CN 01135283 CN01135283 CN 01135283 CN 01135283 A CN01135283 A CN 01135283A CN 1425698 A CN1425698 A CN 1425698A
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Abstract
The preparation process relates to the solution polymerizing reaction of 1,3-butadiene in polymerizing solvent in the presence of ternary nickel system Ni-Al-B catalyst. The main technological feature of the present invention is the addition of the molecular weight regulator D, which is hydroxy compound or olefin. By means of the regu9lation of D amount and Al/B ratio, cis-1,4-polybutadiene rubber with Mooney viscosity as low as 25-40 is prepared. In the same time, divinyl compound as cross-linking agent C is added into the polymerization system to make the cis-1,4-polybutadiene rubber with lower Mooney viscosity has relatively high tensile strength and low gel content, less than 0.5 %.
Description
Technical field
The invention belongs to the Polymer Synthesizing field, relate to a kind of preparation method of low Mooney point high-cis 1 rubber.
Background technology
High-cis 1, the preparation method of 4-polybutadiene rubber (abbreviating cis-1,4-polybutadiene rubber as) 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 is meant nickel naphthenate, nickel acetate, carboxylic acid nickel salts such as nickel octoate, Al is meant triisobutyl aluminium or triethyl aluminum, B is meant boron trifluoride ethyl ether complex or boron trifluoride ether complex, the aliphatic saturated hydrocarbon that polymer solvent is in a liquid state during for polymerization, aromatic hydrocarbons, naphthenic hydrocarbon or its mixture are raffinated oil as refinery, hexane, heptane, benzene or toluene.The mooney viscosity of prepared cis-1,4-polybutadiene rubber is generally 40～50, because the processing characteristics of cis-1,4-polybutadiene rubber is relatively poor, tackiness is bad, so the Rubber processing industry wishes to use the cis-1,4-polybutadiene rubber of low mooney viscosity (generally 25～40) that above-mentioned performance is improved, and requires the intensity of low-mooney polybutadiene rubber not descend simultaneously.Low-mooney polybutadiene rubber is domestic not to have manufacturer and patented technology.
As everyone knows, mooney viscosity is a kind of rotation viscosity, is the rubber sample that records with mooney's viscosimeter to the resistivity of adding moment (promptly shear force square) with one's hands behind one's back, and this value can characterize the size of molecular weight rubber.The cis-1,4-polybutadiene rubber for preparing different mooney viscosities is that the method by regulate polymer molecular weight in polymerization process realizes.
It is catalyzer that China's nickel polymerized BR production is adopted with nickel naphthenate-triisobutyl aluminium-boron trifluoride ethyl ether complex, to raffinate oil is 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 the molecular weight that an amount of water is regulated cis-1,4-polybutadiene rubber, but because that nickel is the scope of application of 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 the molecular weight that an amount of water can only trace be regulated cis-1,4-polybutadiene rubber, it is 25～40 cis-1,4-polybutadiene rubber that existing system is not suitable for preparing mooney viscosity.
In polymerization system, add the molecular weight regulator molecular weight of telomerized polymer easily, 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 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 molecular weight and widen its molecular weight distribution in the Ni catalyst system in patent U.S.5100982 (1992).The high-cis 1 that U.S. Goodyear company reports in patent EP0093073 (1983), the control method of the molecular weight of 4-polyhutadiene is to adopt the catalyzer of forming with organic nickel compound, organo-aluminium compound and HF or HF and ketone, ester, aldehyde, ether, alcohol, phenol, water bonded complex compound in the solvent of aliphatics or cycloaliphatic, is carrying out the polymericular weight adjusting in the presence of a small amount of alpha-olefin such as ethene, propylene.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, CS in polymerization system
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 is the tensile strength of impact polymer directly, and general polymerization thing molecular weight reduces to make the polymkeric substance tensile strength to reduce.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
Technical problem to be solved by this invention provides the low Mooney high-cis 1 of nickel system, the preparation technology of 4-polybutadiene rubber, in the catalyst system that with Ni-Al-B is catalyzer, pass through to add molecular weight regulator D, regulate the add-on of D, the preparation low-mooney polybutadiene rubber, and add an amount of coupling agent and make molecular chain appropriateness branching, thereby make the low-mooney polybutadiene rubber 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, be by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent, the employing catalyzer is a nickel catalyst, this nickel catalyst is the Ni-Al-B three-way catalyst, Ni is a nickel naphthenate, nickel acetate, carboxylic acid nickel salts such as nickel octoate, Al is triisobutyl aluminium or triethyl aluminum, B is boron trifluoride ethyl ether complex or boron trifluoride ether complex, it is characterized in that adding molecular weight regulator D in polymerization system, and D can be the compound of hydroxyl, also can be olefines, polymerizing condition be:
The mol ratio of a.Ni/Bd is (1.0-6.0) * 10
-5
The mol ratio of b.Al/Bd is (3.0-10.0) * 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 among the Ni/Bd is meant the mole number that contains Ni in the carboxylic acid nickel salt,
Al among the Al/Bd is meant the mole number that contains Al in the organo-aluminium compound
B among the B/Bd is meant the mole number of boron compound.
The present invention selects the molecular weight regulator with good result for use, regulates add-on and Al/B ratio, mooney viscosity to 25～40 that can reduce cis-1,4-polybutadiene rubber.The present invention still adopts solution polymerization, the same prior art of nickel catalyst system, the same prior art of polymer solvent, 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.The same prior art of other polymerizing condition.Molecular weight regulator can be the compound of specific hydroxyl, and as alcohols, phenols, commonly used have a C
4～C
12Fatty Alcohol(C12-C14 and C12-C18) (preferred amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, certain herbaceous plants with big flowers alcohol), alkylphenol (preferred cresols) also can be olefines, and commonly used have butene-1, butene-2, an iso-butylene etc.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 ℃.
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, in polymerization system, also added coupling agent C, coupling agent C selects divinyl compound for use, its add-on is: the mol ratio of C/Bd is: 0.01～10.0, preferred 0.05～5.Divinyl compound is commonly used Vinylstyrene, divinyl naphthalene, 1,5 hexadiene.
Beneficial effect of the present invention: can stably prepare mooney viscosity and be 25～40 low-mooney polybutadiene rubber, and make the low-mooney polybutadiene rubber of preparation keep higher draw tensile strength, reach the intensity identical with the cis-1,4-polybutadiene rubber of mooney viscosity 40～50, has lower gel content simultaneously, less than 0.5%.The present invention does not influence the transformation efficiency of divinyl.
Embodiment
Further specify the present invention with comparative example in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
50 liters of polymeric kettles with having ribbon stirring, chuck, temperature, pressure indication make the 1.3-divinyl carry out batchwise polymerization.Earlier 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 nickel naphthenate 0.0102mol, triisobutyl aluminium 0.235mol, boron trifluoride ethyl ether complex 0.0286mol, isooctyl alcohol 0.0304mol, Vinylstyrene 0.122mol respectively; under 80 ℃ of temperature; polyase 13 hour; add ethanol, anti-aging agent takes out glue; the water steam boiling, hot roller drying obtains product of the present invention.
Butadiene conversion is 91.4%.Reaction conditions and product test the results are shown in Table 1.
Embodiment 2
Replace isooctyl alcohol with butene-1, in 54 parts of divinyl, add 1-butylene 3.7mol, 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%.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 ethyl ether complex 0.0358mol, butadiene conversion is 72.4%.All the other are with Comparative Examples 1.
Table 1 polymeric reaction condition and product test result
| Sequence number | Nickel component (mol) | Aluminium component (mol) | Boron component (mol) | Molecular weight regulator (mol) | Coupling agent (mol) | Mooney viscosity | Tensile strength (MPa) | 300% stretches (MPa) surely | Elongation % | Gel content % |
| Embodiment 1 | ?0.102 | ?0.235 | ?0.0286 | ?0.0304 | ?0.122 | ?32.5 | ?14.1 | ?10.0 | ?410 | ?0.36 |
| Embodiment 2 | ?0.118 | ?0.384 | ?0.0358 | ?3.7 | ?0.122 | ?26.5 | ?13.5 | ?8.7 | ?419 | ?0.17 |
| Embodiment 3 | ?0.102 | ?0.235 | ?0.0286 | ?0.0494 | ?0.122 | ?34.5 | ?14.5 | ?9.0 | ?430 | ?0.42 |
| Embodiment 4 | ?0.102 | ?0.235 | ?0.0286 | ?0.0304 | ?1.22 | ?35.0 | ?13.8 | ?9.7 | ?420 | ?0.30 |
| Comparative Examples 1 | ?0.102 | ?0.235 | ?0.0286 | ?0 | ?0 | ?45.0 | ?14.0 | ?10.2 | ?415 | ?0.45 |
| Comparative Examples 2 | ?0.102 | ?0.235 | ?0.0286 | ?0.0304 | ?0 | ?30.0 | ?12.0 | ?7.5 | ?424 | ?0.14 |
| Comparative Examples 3 | ?0.118 | ?0.313 | ?0.0358 | ?0 | ?0 | ?38.0 | ?12.9 | ?7.0 | ?440 | ?1.32 |
Claims (6)
1, the low Mooney high-cis 1 of nickel system, the preparation technology of 4-polybutadiene rubber, be by 1, the solution polymerization that the 3-divinyl carries out in polymer solvent, the employing catalyzer is a nickel catalyst, this nickel catalyst is the Ni-Al-B three-way catalyst, Ni is carboxylic acid nickel salts such as nickel naphthenate, nickel acetate, nickel octoate, Al is triisobutyl aluminium or triethyl aluminum, B is boron trifluoride ethyl ether complex or boron trifluoride ether complex, it is characterized in that adding molecular weight regulator D in polymerization system, D is the compound or the olefines of hydroxyl, 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 (3.0-10.0) * 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 among the Ni/Bd is meant the mole number that contains Ni in the carboxylic acid nickel salt,
Al among the Al/Bd is meant the mole number that contains Al in the organo-aluminium compound,
B among the B/Bd is meant the mole number of boron compound.
2, preparation technology according to claim 1 is characterized in that adding coupling agent C in polymerization process, and the mol ratio of C/Bd is: 0.01～10.0, and coupling agent is a divinyl compound.
3, preparation technology according to claim 1 is characterized in that polymerizing condition 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
E. polymeric reaction temperature is 40～100 ℃.
4, preparation technology according to claim 2 is characterized in that the mol ratio of C/Bd is: 0.05～5.
5, according to claim 1 or 3 described preparation technologies, it is characterized in that the employed hydroxy-containing compounds of described molecular weight regulator, be C
4～C
12Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol, employed alkenes compounds, commonly used have butene-1, butene-2, an iso-butylene.
6, according to claim 2 or 4 described preparation technologies, it is characterized in that described divinyl compound, commonly used have Vinylstyrene, divinyl naphthalene, 1,5 hexadiene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135283 CN1196723C (en) | 2001-12-14 | 2001-12-14 | Process for preparing nickel series low mooney viscosity high cis-1,4,-polybutadiene rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01135283 CN1196723C (en) | 2001-12-14 | 2001-12-14 | Process for preparing nickel series low mooney viscosity high cis-1,4,-polybutadiene rubber |
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| Publication Number | Publication Date |
|---|---|
| CN1425698A true CN1425698A (en) | 2003-06-25 |
| CN1196723C CN1196723C (en) | 2005-04-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335514C (en) * | 2005-04-28 | 2007-09-05 | 大连海事大学 | Process for preparing rubber of high cis 1,4 polybutadiene Ni-Mg-beta catalyzing system |
| 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 |
| CN103172789A (en) * | 2012-12-14 | 2013-06-26 | 万达集团股份有限公司 | Method for preparing nickel series low-mooney high cis-1,4-polybutadiene rubber |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
| CN108929400A (en) * | 2017-05-25 | 2018-12-04 | 北京化工大学 | A kind of nickel catalyst system, high-performance polybutadiene and preparation method thereof |
-
2001
- 2001-12-14 CN CN 01135283 patent/CN1196723C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335514C (en) * | 2005-04-28 | 2007-09-05 | 大连海事大学 | Process for preparing rubber of high cis 1,4 polybutadiene Ni-Mg-beta catalyzing system |
| 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 |
| CN103172789A (en) * | 2012-12-14 | 2013-06-26 | 万达集团股份有限公司 | Method for preparing nickel series low-mooney high cis-1,4-polybutadiene rubber |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
| CN108929400A (en) * | 2017-05-25 | 2018-12-04 | 北京化工大学 | A kind of nickel catalyst system, high-performance polybutadiene and preparation method thereof |
| CN108929400B (en) * | 2017-05-25 | 2023-03-14 | 北京化工大学 | Nickel catalyst system, high-performance polybutadiene and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1196723C (en) | 2005-04-13 |
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