CN1324874A - Prepn. of cir-rich 1,4-polybutadine rubber for tyre - Google Patents
Prepn. of cir-rich 1,4-polybutadine rubber for tyre Download PDFInfo
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- CN1324874A CN1324874A CN 00111053 CN00111053A CN1324874A CN 1324874 A CN1324874 A CN 1324874A CN 00111053 CN00111053 CN 00111053 CN 00111053 A CN00111053 A CN 00111053A CN 1324874 A CN1324874 A CN 1324874A
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Abstract
The preparation method of cis-rich, 1,4-polybutadiene ruber for tyre adopts the polymerization and microwater addition process, utilizes catalyst formulation, polymerization temp. and microwater for cooperation regulation in control, the said invented polymerization reaction is high in catalytic activity, sensitive in regulation and stable in polymerization process, and can make polymerization reaction be in the optimum state. Said invention can effectively regulate Mooney viscosity of rubber liquor and gel, and control molecular structure and molecular weight of polymer. Said invented product is a high-quality rubber for making tyre.
Description
The present invention relates to the preparation method of tire with high-cis 1 rubber.
High-cis 1, the 4-polybutadiene rubber is one of glue kind of preparation tire, development along with tire production and technology, for high-cis 1, the specification of quality of 4-polybutadiene rubber is more and more higher, and the molecular weight rubber that polymerization process determined, molecular weight distribution and gel content are the principal elements that influences the rubber inner quality.
High-cis 1, the preparation method of 4-polybutadiene rubber generally adopts solution method, catalyst system is divided into nickel system, titanium system, cobalt system, rare-earth system etc., the nickel catalyst that industrial production adopts is a Ni-Al-B ternary system catalyzer, Ni is meant carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound, carboxylic acid nickel salt such as nickel naphthenate, nickel acetate, nickel octoate; Al is meant alkylaluminium cpd such as triisobutyl aluminium or triethyl aluminum; B is meant boron trifluoride complex such as boron trifluoride ethyl ether complex or boron trifluoride ether complex.Carrying out solution polymerization by divinyl in Ni-Al-B ternary system catalyzer is the method for preparing high-cis 1 rubber.Polyreaction can be successive polymerization, also can be batchwise polymerization.Aliphatic saturated hydrocarbon, aromatic hydrocarbons, alkane aromatic hydrocarbons or its mixture that polymer solvent is in a liquid state during for polymerization.As refinery raffinate oil, hexane, heptane, benzene or toluene, or their mixture.In this preparation method, the effect of water is vital in the polymerization system, the deployment conditions that how much reaches water of the water content in the system directly influences polymerization activity and rubber quality, an amount of water does not only reduce polymerization rate, and can under the prerequisite that does not change micmstructure of polymer, regulate molecular weight, and make catalyst system more stable, but water number is too high in the system again can spent catalyst, destroy the active centre, reduce polymerisation conversion, can produce a large amount of gels simultaneously, influence rubber quality.
At high-cis 1, add water in the polymerization process of 4-polybutadiene rubber, report is all arranged both at home and abroad, the clear 56-24412 of Japanese Patent and Chinese patent 94102595.0 disclosed a kind of high-cis 1 that are applicable to the preparation high impact resistance polystyrene, the 4-polybutadiene rubber, though all be to adopt in the Ni-Al-B three-element catalytic system to add water, but the former is the preparation low molecular weight polybutadiene for its purpose, the latter is the high-cis 1 of preparation high impact resistance polystyrene, the 4-polyhutadiene, and water number is by dehydration or adds the method control of water, do not describe adding the water mode.Added the water mode adopts the water number of control solvent, divinyl refining system or add water in solvent, divinyl in the past, these shortcomings one that add the water mode are to the polyreaction control lag, the 2nd, water disperses inhomogeneous in system, and free water easily causes the polyreaction fluctuation and forms a large amount of gels.94102595.0 patent is strict for the limiting viscosity of solution, it is different with the purposes that the present invention relates to.
The performance and the quality instability of high-cis 1 rubber can not satisfy the requirement of tire with glue at present.
The purpose of this invention is to provide the preparation method of a kind of tire, make the product inner quality satisfy tire glue requirement with high-cis 1 rubber.High-cis 1 rubber has stable molecular structure, suitable molecular weight and molecular weight distribution,
Tire of the present invention is to adopt Ni-Al-B ternary system catalyzer to carry out solution polymerization by divinyl with the preparation method of high-cis 1 rubber, it is characterized in that:
Ni to the mol ratio of divinyl is: (0.8～3.0) * 10
-5
Al to the mol ratio of divinyl is: (0.2～1.5) * 10
-4
B to the mol ratio of divinyl is: (0.6～3.0) * 10
-4
Al to the mol ratio of B is: 0.2～0.8
Water to the mol ratio of divinyl is: (0～15.0) * 10
-5
Polymeric reaction temperature: 50～120 ℃.
The optimum condition of above-mentioned each index is:
Ni to the mol ratio of divinyl is: (1.0～2.0) * 10
-5
Al to the mol ratio of divinyl is: (0.25～0.8) * 10
-4
B to the mol ratio of divinyl is: (0.7～1.8) * 10
-4
Al to the mol ratio of B is: 0.3～0.6
Water to the mol ratio of divinyl is: (0～12.0) * 10
-5
Polymeric reaction temperature: 65～120 ℃.
The present invention selects above-mentioned polymerization process condition, and by changing catalyst proportion and regulating minor amount of water and polymeric reaction temperature, the controlled polymerization reaction makes the high-cis 1 rubber product that obtains satisfy the requirement of tire with glue.
The present invention selects the water of suitable trace to improve the catalytic activity of polyreaction.The water of polymerization system is mainly from solvent and divinyl, can control by solvent and divinyl dehydration or the mode that adds water.Solvent and divinyl all carry out processed by refining plant before polymerization.Add water owing to many-sided reason, the mode that adds water is also different in the polymeric performance, until the quality of impact polymer.The invention provides a kind of water mode that adds, with mode telo merization and polymericular weight by part divinyl band saturation water, mode is to add water in divinyl preferably, adds water in the mode that forms the divinyl saturated aqueous solution.Divinyl and solvent process refining plant processed before the polymerization, the water number≤25ppm of divinyl, polymer solvent water number≤25ppm, above-mentioned water is outer amount of water to the mol ratio of divinyl.The flow of the divinyl of accommodation zone saturation water can realize regulating the water yield that enters polymerization system.
The present invention adds the mode of water and technology of the present invention flow process as shown in Figure 1.
The divinyl separated into two parts, the small portion divinyl mixes in container 1 with water, water intermittently adds, the divinyl of band saturation water carries out polyreaction through mixing after container 2 enters polymeric kettle with most of divinyl and solvent streams through metering by container 1 top, and its operation and catalyzer add mode with the prior art mode.
The water mode that adds of the present invention can be regulated arbitrarily and entered the outer amount of water of polymeric, and is easy to operate, the tolerance range height, regulate in time, because of forming the saturated aqueous solution of divinyl, water is uniformly dispersed in system, the water number of controlled polymerization system mixed solution is implemented with minor amount of water polymerization to be regulated effectively.Amount of water outside can in time regulating in water yield scope of the present invention according to response situation makes polyreaction be in optimum regime.
Polymer solvent of the present invention and catalyzer still adopt the product of prior art.The aliphatic saturated hydrocarbon that is in a liquid state when polymer solvent is polymerization, aromatic hydrocarbons, alkane aromatic hydrocarbons or its mixture.As refinery raffinate oil, hexane, heptane, benzene or toluene, or its mixture.Catalyzer is a Ni-Al-B ternary system catalyzer, is carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound.The carboxylic acid nickel salt can be nickel naphthenate, nickel acetate, nickel octoate; Alkylaluminium cpd can be triisobutyl aluminium or triethyl aluminum; Boron trifluoride complex can be boron trifluoride ethyl ether complex or boron trifluoride ether complex.
The specification of quality of catalyzer, compound concentration and polymerization feed way are that cis-butadiene cement is identical with the universal nickel of preparation.
Advantage of the present invention:
1, adopted polymerization to add the method for minor amount of water, control with catalyst formulation, the collaborative adjusting of minor amount of water, polyreaction catalytic activity height, regulate sensitive, polymerization technique is stable, can keep polyreaction to be in optimum regime, regulate the mooney viscosity and the gel of glue effectively, the molecular structure of controlling polymers, molecular weight and molecular weight distribution.
2, add the water conservancy project skill simply, easy to operate, metering is easy, and minor amount of water is uniformly dispersed in polymerization system, and water number is stable.
3, polymerisation conversion obviously improves.Because adding the water conservancy project skill is that minor amount of water is added in the divinyl, amount of water can in time be regulated according to response situation, makes activity of such catalysts maintain good order and condition all the time, and therefore, the transformation efficiency of reaction can obviously improve.With do not add water or other and add the water conservancy project skill and compare, transformation efficiency can improve more than 6%.
4, can reduce catalyst consumption, catalyst levels reduces, and has alleviated the kiss-coating of polymeric kettle, glue pipeline greatly, and the reduction of boron agent consumption has reduced the acid content in the system, has reduced the corrosion to equipment, has prolonged the running period of equipment.
5, the high-cis 1 rubber that obtains of the present invention, its products molecule structure, molecular weight and molecular weight distribution are suitable stable, and gel content is low, can be controlled at effectively in the claimed range, is the high-quality glue of making tire.Salient features, test result is as follows:
Table 1
| Index name | Indication range | Analytical procedure | |
| General value | Preferred value | ||
| High-cis 1 rubber content % | ＞93 | ＞96 | Infrared analysis |
| M WMolecular weight (ten thousand) | 30～45 | 30～40 | Gpc analysis |
| M W/ M N | 2.0～5.5 | 2.5～4.0 | Gpc analysis |
| 100 ℃ of mooney viscosities | 38-52 | 42-48 | ?GB/T1232-92 |
| Gel content % | ＜1.0 | ＜0.5 | ?SH/T1050-91 |
| Color | Colourless or light | ||
In the table: M
wBe weight-average molecular weight, M
NBe number-average molecular weight.
Embodiment 1:
Adopting 5 liters of polymeric kettles, is catalyzer with nickel naphthenate, triisobutyl aluminium, boron trifluoride ethyl ether complex, and solvent oil is a solvent, carries out the 1,3-butadiene batchwise polymerization.
At first, with clean solvent oil wash still, in the polymeric kettle after the vacuum nitrogen filling gas disposal, add the divinyl that contains 245.4 parts of solvent oils and 54.6 parts prepare, solvent oil and divinyl are the raw material through the retrieving arrangement dehydration, water number≤25PPM (Ka Er. Fei Xiufa) adopts in the divinyl of the present invention to add the water mode, makes in the divinyl moisture 2.86 * 10
-3Get 1.76 * 10
-3Part nickel naphthenate and 5.4 * 10
-3Part triisobutyl aluminium preparation ageing liquid, 4.26 * 10
-2Part boron trifluoride ethyl ether complex dilutes with 11 parts of solvent oils, joins in the polymeric kettle respectively then.Under 70 ℃ of temperature, make 1,3-butadiene reaction 3 hours, in the glue of emitting, add ethanol 2.64 * 10
-3Part, 0.43 part of antioxidant 264 (2,6 di tert butyl 4 methyl phenol), water steam boiling then, the product of the present invention of hot roller drying.Butadiene conversion 89%.More than each material be parts by weight.
Reaction conditions and product test the results are shown in Table 2.
Comparative Examples 1: divinyl moisture 4 * 10
-3Part (weight part), butadiene conversion is 79%.
All the other are with embodiment 1.
Comparative Examples 2: adopt the mode in solvent oil, add water, make in the divinyl moisture 2.86 * 10
-3Part (weight part).Butadiene conversion is 65%.
All the other are with embodiment 1.
Comparative Examples 3: 40 ℃ of butadiene polymerization temperature.Butadiene conversion is 77%.
All the other are with embodiment 1.Comparative Examples 4: nickel naphthenate 1.76 * 10
-3Part (weight), boron trifluoride ethyl ether complex 2.63 * 10
-2Part (weight), triisobutyl aluminium 4.5 * 10
-3Part (weight).Butadiene conversion is 85%.All the other are with embodiment 1.
Comparative Examples 5: nickel naphthenate 1.76 * 10
-3Part (weight), boron trifluoride ethyl ether complex 2.63 * 10
-2Part (weight), triisobutyl aluminium 4.5 * 10
-3Part (weight) is adopted the water mode that adds in solvent oil.Butadiene conversion is 45%.
All the other are with embodiment 1.
Embodiment 2:
12 cubic metres polymeric kettle with having stirring, chuck, temperature, pressure indication makes 1,3-butadiene carry out successive polymerization.
Charge proportion: 14m
3/ h raffinates oil and 4m
3/ h divinyl, divinyl passes through the retrieving arrangement processed in advance with raffinating oil.Nickel naphthenate Ni/ divinyl=1.8 * 10
-5(mol ratio), triisobutyl aluminium Al/ divinyl=0.5 * 10
-4(mol ratio), boron trifluoride ethyl ether complex B/ divinyl=1.4 * 10
-4(mol ratio).The catalyst charge mode, aluminium, nickel catalyzator mix, and enter polymeric kettle with the boron component again, add minor amount of water, and water is 5.0 * 10 to the mol ratio of divinyl
-5, 60～120 ℃ of polymerization temperatures make 1,3-butadiene reaction 3 hours, add antioxidant 264 (2,6 di tert butyl 4 methyl phenol), then glue are taken out, and the water steam boiling is extruded drying and is obtained product of the present invention.Butadiene conversion 88.1%.
Comparative Examples 6:
Water is 0 to the mol ratio of divinyl, does not promptly add water.Butadiene conversion is 79.1%.
All the other are with embodiment 2.
Embodiment 3:
Nickel naphthenate Ni/ divinyl=1.0 * 10
-5(mol ratio), triisobutyl aluminium Al/ divinyl=0.3 * 10
-4(mol ratio), boron trifluoride B/ divinyl=0.8 * 10
-4(mol ratio) adds minor amount of water, and water is 7.0 * 10 to the mol ratio of divinyl
-5, butadiene conversion is 87.5%.
All the other are with embodiment 2.
Comparative Examples 7:
Triisobutyl aluminium Al/ divinyl=0.42 * 10
-4(mol ratio), butadiene conversion are 84.7%.
All the other are with embodiment 3.Table 2: high-cis 1 rubber product test result sequence number mooney viscosity cis 1,4-gathers fourth M
w* 10
4M
N* 10
4M
w/ M
NGel content
Diene content, % (%) embodiment 1 46 96.3 37.1 13.10 2.83 0.3 Comparative Examples 1 54 95.6 43.9 8.91 4.93 0.6 Comparative Examples 2 57 95.2 45.2 8.86 5.10 1.0 Comparative Examples 3 50 96.4 41.8 13.10 3.18 0.8 Comparative Examples 4 48 95.9 39.6 13.60 2.91 0.7 Comparative Examples 63 94.8 49.4 9.55 5.17 1.3 embodiment 47 96.3 36.7 12.57 2.92 0.4 Comparative Examples 6 58 98.0 42.3 8.81 4.80 0.9 embodiment 3 40 95.8 35.7 12.48 2.86 0.2 Comparative Examples 7 52 96.1 38.1 12.02 3.17 1.2
Claims (11)
1, a kind of tire is to adopt Ni-Al-B ternary system catalyzer to carry out solution polymerization by divinyl with the preparation method of high-cis 1 rubber, it is characterized in that:
Ni to the mol ratio of divinyl is: (0.8～3.0) * 10
-5
Al to the mol ratio of divinyl is: (0.2～1.5) * 10
-4
B to the mol ratio of divinyl is: (0.6～3.0) * 10
-4
Al to the mol ratio of B is: 0.2～0.8
Water to the mol ratio of divinyl is: (0～15.0) * 10
-5
Polymeric reaction temperature: 50～120 ℃.
2, preparation method according to claim 1 is characterized in that:
Ni to the mol ratio of divinyl is: (1.0～2.0) * 10
-5
Al to the mol ratio of divinyl is: (0.25～0.8) * 10
-4
B to the mol ratio of divinyl is: (0.7～1.8) * 10
-4
Al to the mol ratio of B is: 0.3～0.6
Water to the mol ratio of divinyl is: (0～12.0) * 10
-5
Polymeric reaction temperature: 65～120 ℃.
3, preparation method according to claim 1, the hydromining that it is characterized in that polyreaction is with adding the water mode, the water number≤25ppm of divinyl, polymer solvent water number≤25ppm, water is outer amount of water to the mol ratio of divinyl.
4, preparation method according to claim 3 is characterized in that the water mode that adds with water and divinyl formation saturated solution.
5, preparation method according to claim 4, it is characterized in that the small portion divinyl mixes in a container with required water, water intermittently adds, most of divinyl and solvent enter in another container, the mixed solution that water and small portion divinyl form enters in another container and most of divinyl and solvent continuously, enters poly-unit after the mixing and carries out polyreaction.
6,, it is characterized in that the aliphatic saturated hydrocarbon, aromatic hydrocarbons, alkane aromatic hydrocarbons or its mixture that are in a liquid state when polymer solvent is polymerization according to claim 1,2 described preparation methods.
7,, it is characterized in that described Ni-A1-B ternary system catalyzer is meant carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound according to claim 1,2 described preparation methods.
8, according to claim 1,3 or 5 described preparation methods, it is characterized in that polymer solvent is that refinery is raffinated oil, hexane, heptane, benzene or toluene, or its mixture.
9, preparation method according to claim 7 is characterized in that the carboxylic acid nickel salt is nickel naphthenate, nickel acetate, nickel octoate.
10, preparation method according to claim 7 is characterized in that alkylaluminium cpd is triisobutyl aluminium or triethyl aluminum.
11, preparation method according to claim 7 is characterized in that boron trifluoride complex is boron trifluoride ethyl ether complex or boron trifluoride ether complex.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00111053 CN1324874A (en) | 2000-05-19 | 2000-05-19 | Prepn. of cir-rich 1,4-polybutadine rubber for tyre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00111053 CN1324874A (en) | 2000-05-19 | 2000-05-19 | Prepn. of cir-rich 1,4-polybutadine rubber for tyre |
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|---|---|
| CN1324874A true CN1324874A (en) | 2001-12-05 |
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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 |
| CN100469831C (en) * | 2003-07-17 | 2009-03-18 | 株式会社普利司通 | Pneumatic tire |
| CN104961852A (en) * | 2015-07-03 | 2015-10-07 | 新疆蓝德精细石油化工股份有限公司 | Narrow molecular weight cis-polybutadiene rubber and preparation method thereof |
| CN106589194A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Cis-1,4-polybutadiene and preparation method thereof |
| CN108026331A (en) * | 2015-09-30 | 2018-05-11 | 住友橡胶工业株式会社 | Pneumatic tire |
-
2000
- 2000-05-19 CN CN 00111053 patent/CN1324874A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469831C (en) * | 2003-07-17 | 2009-03-18 | 株式会社普利司通 | Pneumatic tire |
| 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 |
| CN104961852A (en) * | 2015-07-03 | 2015-10-07 | 新疆蓝德精细石油化工股份有限公司 | Narrow molecular weight cis-polybutadiene rubber and preparation method thereof |
| CN108026331A (en) * | 2015-09-30 | 2018-05-11 | 住友橡胶工业株式会社 | Pneumatic tire |
| CN108026331B (en) * | 2015-09-30 | 2021-06-25 | 住友橡胶工业株式会社 | Pneumatic tire |
| CN106589194A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Cis-1,4-polybutadiene and preparation method thereof |
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