CN1347923A - Rare earth catalytic system and butadiene polymerizing process - Google Patents
Rare earth catalytic system and butadiene polymerizing process Download PDFInfo
- Publication number
- CN1347923A CN1347923A CN 01128284 CN01128284A CN1347923A CN 1347923 A CN1347923 A CN 1347923A CN 01128284 CN01128284 CN 01128284 CN 01128284 A CN01128284 A CN 01128284A CN 1347923 A CN1347923 A CN 1347923A
- Authority
- CN
- China
- Prior art keywords
- ageing
- room temperature
- catalyst system
- hours
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The catalytic rare earth system consists of: neodymium carboxylate compound, alkyl aluminium hydride or trialkyl aluminium, halide and conjugated diolefin in the molar ratio of 1 to 5-50 to 0.5-5 to 5-30. The aging temperature is 0-90 deg.c. The catalyst system may maintain its homogeneous phase at normal temperature for over 54 hr and may be used to obtain polybutadiene with a single-peak molecular weight distribution of distribution index Mw/Mn=3-3.5 and a cis form component content greater than 97 wt%.
Description
Technical field: the invention belongs to a kind of rare-earth catalysis system and butadiene polymerizing process.
Background technology: the phase of rare-earth catalysis system and phase stability thereof are most important to the production and the quality control of rare earth rubber.At first, the phase of catalyst system and phase thereof stability directly influences its stability of catalytic performance.The homogeneous catalysis system catalytic performance is stablized, and polymerization process is controlled easily, and heterogeneous catalysis system is owing to may exist many active centre, difficult control of catalytic performance and polymerization process and grasp.Second, its storage of the stability influence of catalyst system phase and transportation, the change of phase or the change of chemical property may take place in the storage of catalyzer and transportation, this is totally unfavorable to stablizing of the production of rare earth rubber and product performance, if the change of phase takes place in catalyzer in the polymerization reaction kettle transport process, both become heterogeneously, easily caused the generation of implode phenomenon in the polymeric kettle, the problems such as obstruction of catalyzer pipeline by homogeneous phase.The 3rd, the phase of catalyst system directly influences the production and the performance of rubber, catalyst system becomes heterogeneous meeting by homogeneous phase and directly causes the molecular weight distribution of rare earth rubber product to be widened, the increase of high molecular weight component, the negative effect of bringing thus has: (1) increases the polymerization system coefficient of dynamic viscosity, cause increasing of stir current, increase power consumption; (2) make the postprocessing working procedures such as transmission, cohesion of glue that difficulty take place, limited the raising of monomer concentration, increased energy consumption, reduced production efficiency; (3) processing characteristics of giving rubber especially the behavior of extruding bring disadvantageous effect.
For the problem and the wide problem of synthetic rubber molecular weight distribution that solve rare-earth catalysis system phase stability, people have carried out extensive studies, at EP Pat.375, adopt tert-butyl chloride t-C as Italian EnichemElastomers Ltd in 421 patents
4H
9Cl adopts the feed way of (Nd+Al)+Cl and-30 ℃～40 ℃ ageing temperature as the chloride component of catalyzer, to guarantee the homogeneous state of catalyzer, makes the rare earth polybutadiene rubber of production have narrower and unimodal molecular weight distribution.Japan has delivered many pieces and has changed patent such as the flat 4-142308 of flat 3-185008 that the rare earth element part prepares narrow distribution rare earth cis-butadiene cement.
The method of the control homogeneous phase rare earth catalyst phase of above-mentioned proposition is to realize under the condition of specific feed way, temperature, time and low Cl/Nd ratio, be relative, with good conditionsi, this is unmanageable in process of production, more cannot say for sure to demonstrate,prove the homogeneity and the stability of product.
Summary of the invention: the purpose of this invention is to provide a kind of rare-earth catalysis system and butadiene polymerizing process.The invention provides rare-earth catalysis system and have the height homogeneous stability.
The composition of rare-earth catalysis system provided by the invention is:
A. the carboxylic acid neodymium compound is specially neodymium naphthenate, and the neodecanoic acid neodymium with branched structure that contains 8-10 carbon atom.
B. alkyl-al hydride or trialkylaluminium specifically are triisobutyl aluminium Al (i-C
4H
9)
3, triethyl aluminum AlEt
3Perhaps diisobutyl aluminium hydride AlH (i-C
4H
9)
2
C. halogen contained compound specifically is tert-butyl chloride t-C
4H
9Cl, sesquialter aluminium Al
2R
3Cl
3, dialkylaluminum chloride AlR
2Cl or chloro methyl-monosilane Me
4-nSiCl
n, wherein R is ethyl-C
2H
5And isobutyl--i-C
4H
9, n is 1,2 or 3.
D. conjugated diolefin specifically is divinyl and isoprene.
Mol ratio is between each component of catalyst system: B: A=5-50: 1, and C: A=0.5-5: 1 and D: A=5-30: 1; Layoutprocedure is pressed following order:
1) .A+B+D adds C then 0-90 ℃ of ageing, continues ageing at 0-90 ℃;
2) .B+C+D adds A then 0-20 ℃ of ageing, continues ageing at 0-20 ℃;
3) .B+C ageing adds A and D then and continues ageing, and the ageing temperature is 0-90 ℃ when D is divinyl; The ageing temperature is 0-20 ℃ when D is isoprene;
Catalyst system by above method configuration can keep homogeneous phase more than 54 hours at normal temperatures, and the molecular weight of gained polyhutadiene is unimodal distribution, dispersion index Mw/Mn=3-3.5, and cis-content is greater than 97wt%.
Embodiment:
Embodiment 1.
Under nitrogen protection, in the dry long-neck ampere of 10ml bottle, add neodecanoic acid neodymium 0.112mmol and AlH (i-C
4H
9)
23.37mmol ageing added MeSiCl after 10 minutes in 11 ℃ of water-baths
30.092mmol ageing was put in room temperature after 6 hours in 11 ℃ of water-baths again.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 2:
Replace the neodecanoic acid neodymium with neodymium naphthenate, with Me
3SiCl replaces MeSiCl
3, simultaneously the ageing temperature being increased to 50 ℃ by 11 ℃, other conditions are with embodiment 1.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 3:
Under nitrogen protection, in the dry long-neck ampere of 10ml bottle, add AlH (i-C
4H
9)
22.24mmol and Me
2SiCl
20.056mmol ageing adds neodecanoic acid neodymium 0.112mmol after 10 minutes in 11 ℃ of water-baths, ageing was put in room temperature after 6 hours in 11 ℃ of water-baths again.More than Pei Zhi catalyst system at room temperature keeps homogeneous phase can reach more than 54 hours, below three months.
Embodiment 4:
The ageing temperature is increased to 50 ℃ by 11 ℃, and other conditions are with embodiment 3.The catalyst system of being prepared at room temperature keeps homogeneous phase can reach more than 54 hours, below three months.
Comparative example 1:
Under nitrogen protection, in the dry long-neck ampere of 10ml bottle, add neodecanoic acid neodymium 0.112mmol and MeSiCl
30.092mmol ageing added AlH (i-C after 10 minutes in 11 ℃ of water-baths
4H
9)
23.37mmol ageing was put in room temperature after 6 hours in 11 ℃ of water-baths again.More than Pei Zhi catalyst system precipitation occurs at room temperature 10 hours.
Comparative example 2:
The ageing temperature is increased to 50 ℃ by 11 ℃, and other conditions are with comparative example 1.The catalyst system of being prepared precipitation occurs at room temperature 10 hours.
Embodiment 5:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, divinyl hexane solution 1.08mmol and AlH (i-C
4H
9)
23.37mmol ageing added MeSiCl after 10 minutes in 10 ℃ of water-baths
30.092mmol, in 20 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 6:
The tertiary monocarboxylic acid neodymium with branched structure with 8-10 carbon atom replaces the neodecanoic acid neodymium, with t-C
4H
9Cl replaces MeSiCl
3, and the ageing temperature is increased to 50 ℃, other conditions are with embodiment 5.The catalyst system of being prepared is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 7:
The hexane solution 2.24mmol that under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, adds divinyl, AlH (i-C
4H
9)
24.48mmol, and Al (i-C
4H
9)
2Cl 0.092mmol, ageing adds neodecanoic acid neodymium 0.112mmol after 10 minutes in 10 ℃ of water-baths, continues ageing again and be put in room temperature after 6 hours in 10 ℃ of water-baths.More than Pei Zhi catalyst system is at room temperature placed and can be kept homogeneous phase more than three months, below 16 months.
Embodiment 8:
The ageing temperature is become 0 ℃, and other conditions are with embodiment 7.The catalyst system of being prepared is at room temperature placed and can be kept homogeneous phase more than three months, below 16 months.
Embodiment 9:
The ageing temperature is become 20 ℃, and other conditions are with embodiment 7.The catalyst system of being prepared is at room temperature placed and can be kept homogeneous phase more than three months, below 16 months.
Comparative example 3:
The ageing temperature is increased to 50 ℃, and other conditions are with embodiment 7.The catalyst system of being prepared precipitation occurs at room temperature 10 hours.
Comparative example 4:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, the hexane solution 1.08mmol of divinyl, and MeSiCl
30.092mmol ageing adds AlH (i-C after 10 minutes in 11 ℃ of water-baths
4H
9)
23.37mmol, in 11 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system precipitation occurs at room temperature 10 hours.
Comparative example 5:
The ageing temperature is increased to 50 ℃ by 11 ℃, and other conditions are with comparative example 4.The catalyst system of being prepared precipitation occurs at room temperature 10 hours.
Embodiment 10:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add AlH (i-C
4H
9)
23.37mmol and Al
2(i-C
4H
9)
3Cl
30.224mmol ageing adds the n-heptane solution 1.08mmol of neodecanoic acid neodymium 0.112mmol and divinyl after 10 minutes in 20 ℃ of water-baths, continues ageing again and be put in room temperature after 6 hours in 20 ℃ of water-baths.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 11:
The ageing temperature is become 0 ℃, and other conditions are with embodiment 10.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 12:
The ageing temperature is increased to 50 ℃, and other conditions are with embodiment 10.The catalyst system of being prepared is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 13:
The ageing temperature is increased to 90 ℃, and other conditions are with embodiment 10.The catalyst system of being prepared is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 14:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, isoprene hexane solution 1.08mmol and AlH (i-C
4H
9)
23.37mmol ageing adds Al (C after 10 minutes in 0 ℃ of water-bath
2H
5)
2Cl 0.092mmol continues ageing again and is put in room temperature after 6 hours in 10 ℃ of water-baths.More than Pei Zhi catalyst system is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 15:
The ageing temperature is increased to 60 ℃, and other conditions are with embodiment 14.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 3 months, below 16 months.
Embodiment 16
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add AlH (i-C
4H
9)
23.37mmol and MeSiCl
30.092mmol ageing adds the hexane solution 1.08mmol of neodecanoic acid neodymium 0.112mmol and isoprene after 10 minutes in 10 ℃ of water-baths, continues ageing again and be put in room temperature after 6 hours in 10 ℃ of water-baths.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 17:
The ageing temperature is become 0 ℃, and other conditions are with embodiment 16.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 18:
The ageing temperature is become 20 ℃, and other conditions are with embodiment 16.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Comparative example 6:
The ageing temperature is increased to 50 ℃, and other conditions are with embodiment 16.The catalyst system of being prepared precipitation occurs at room temperature 10 hours.
Embodiment 19:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, divinyl n-heptane solution 3.36mmol and Al (i-C
4H
9)
30.56mmol ageing added Al after 10 minutes in 0 ℃ of water-bath
2(C
2H
5)
3Cl
30.336mmol, in 10 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than three months, below 16 months.
Embodiment 20:
The ageing temperature is increased to 70 ℃, and other conditions are with embodiment 19.The catalyst system of being prepared is at room temperature placed and is still kept homogeneous phase more than 2 years.
Embodiment 21:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, isoprene hexane solution 1.08mmol and Al (i-C
4H
9)
33.37mmol ageing added MeSiCl after 10 minutes in 11 ℃ of water-baths
30.092mmol, in 11 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than three months, below 16 months.
Embodiment 22:
The ageing temperature is increased to 50 ℃ by 11 ℃, and other conditions are with embodiment 21.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 3 months, below 16 months.
Embodiment 23:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, divinyl n-heptane solution 0.56mmol and Al (C
2H
5)
35.6mmol ageing added MeSiCl after 10 minutes in 10 ℃ of water-baths
30.56mmol, in 20 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 24:
The ageing temperature is increased to 90 ℃, and other conditions are with embodiment 23.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 25:
Under nitrogen protection, in exsiccant 10ml long-neck ampere bottle, add neodecanoic acid neodymium 0.112mmol, isoprene hexane solution 1.08mmol and Al (C
2H
5)
33.37mmol ageing added MeSiCl after 10 minutes in 11 ℃ of water-baths
30.092mmol, in 11 ℃ of water-baths, continue ageing again and be put in room temperature after 6 hours.More than Pei Zhi catalyst system at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 26:
The ageing temperature is increased to 50 ℃ by 11 ℃, and other conditions are with embodiment 25.The catalyst system of being prepared at room temperature can keep homogeneous phase more than 54 hours, below three months.
Embodiment 27:
Under nitrogen protection, in 100ml exsiccant single port glass reaction bottle, add dry hexane 84ml and dry divinyl 10g, add the homogeneous catalyst solution 4.55 * 10 of embodiment 5 preparations then
-6Mol, polymerization is 5 hours in 50 ℃ of waters bath with thermostatic control.Add the ethanolic soln that contains 2,6,4 anti-aging agent, polymkeric substance is dried to constant weight through the washing with alcohol final vacuum.Polymerisation conversion is 95%, and polyhutadiene is 97.9% along 1,4 content.Polymerisate is a unimodal distribution through the gpc analysis molecular weight, Mw=343,000, Mw/Mn=3.05.
Comparative example 7:
Use the heterogeneous catalyst of comparative example 4 preparations, other polymerizing conditions are with embodiment 27.Polymerisation conversion is 94%, and polyhutadiene is 96.6% along 1,4 content.Polymerisate is a bimodal distribution through the gpc analysis molecular weight, Mw=953,000, Mw/Mn=7.50.
Embodiment 28:
Use the homogeneous catalyst of embodiment 5 configurations of placing after 2 years, other polymerizing conditions are with embodiment 27.Polymerisation conversion is 97%, and polyhutadiene is 97.6% along 1,4 content.Polymerisate is a unimodal distribution through the gpc analysis molecular weight, Mw=365,000, Mw/Mn=3.02.
Embodiment 29:
Use the homogeneous catalyst of embodiment 7 configurations, other polymerizing conditions are with embodiment 27.Polymerisation conversion is 93%, and polyhutadiene is 97.2% along 1,4 content.Polymerisate is a unimodal distribution through the gpc analysis molecular weight, Mw=358,000, Mw/Mn=3.25.
Embodiment 30:
Use the homogeneous catalyst of embodiment 12 configurations, other polymerizing conditions are with embodiment 27.Polymerisation conversion is 96%, and polyhutadiene is 97.8% along 1,4 content.Polymerisate is a unimodal distribution through the gpc analysis molecular weight, Mw=323,000, Mw/Mn=3.10.
Embodiment 31:
Use the homogeneous catalyst of embodiment 16 configurations, other polymerizing conditions are with embodiment 27.Polymerisation conversion is 91%, and polyhutadiene is 97.0% along 1,4 content.Polymerisate is a unimodal distribution through the gpc analysis molecular weight, Mw=345,000, Mw/Mn=3.42.
Claims (1)
1. rare-earth catalysis system and butadiene polymerizing process is characterized in that the composition of the rare-earth catalysis system selected is:
E. the carboxylic acid neodymium compound is specially neodymium naphthenate, and the neodecanoic acid neodymium with branched structure that contains 8-10 carbon atom;
F. alkyl-al hydride or trialkylaluminium specifically are triisobutyl aluminium Al (i-C
4H
9)
3, triethyl aluminum AlEt
3Or diisobutyl aluminium hydride AlH (i-C
4H
9)
2
G. halogen contained compound specifically is tert-butyl chloride t-C
4H
9Cl, sesquialter aluminium Al
2R
3Cl
3, dialkylaluminum chloride AlR
2Cl or chloro methyl-monosilane Me
4-nSiCl
n, wherein R is ethyl-C
2H
5And isobutyl--i-C
4H
9, n is 1,2 or 3;
H. conjugated diolefin specifically is divinyl and isoprene;
Mol ratio is between each component of catalyst system: B: A=5-50: 1, and C: A=0.5-5: 1 and D: A=5-30: 1; Layoutprocedure is pressed following order:
1) .A+B+D adds C then 0-90 ℃ of ageing, continues ageing at 0-90 ℃;
2) .B+C+D adds A then 0-20 ℃ of ageing, continues ageing at 0-20 ℃;
3) .B+C ageing adds A and D then and continues ageing, and the ageing temperature is 0-90 ℃ when D is divinyl; The ageing temperature is 0-20 ℃ when D is isoprene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011282843A CN1176121C (en) | 2001-10-12 | 2001-10-12 | Rare earth catalytic system and butadiene polymerizing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011282843A CN1176121C (en) | 2001-10-12 | 2001-10-12 | Rare earth catalytic system and butadiene polymerizing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1347923A true CN1347923A (en) | 2002-05-08 |
| CN1176121C CN1176121C (en) | 2004-11-17 |
Family
ID=4668158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011282843A Expired - Lifetime CN1176121C (en) | 2001-10-12 | 2001-10-12 | Rare earth catalytic system and butadiene polymerizing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1176121C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007021215A1 (en) | 2005-08-12 | 2007-02-22 | Otkrytoe Aktsionernoe Obschestvo 'efremovsky Zavod Sinteticheskogo Kauchuka' | Method for producing cis-1,4 diene rubber, catalyst, rubber |
| US7288611B2 (en) | 2003-09-25 | 2007-10-30 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Methods for preparing a rare-earth cis-1,4-polybutadiene rubber with a controlled molecular weight distribution |
| CN100365030C (en) * | 2002-10-21 | 2008-01-30 | 米其林技术公司 | Synthetic branched polyisoprenes and process for obtaining them |
| CN101906110A (en) * | 2010-08-18 | 2010-12-08 | 中国科学院长春应用化学研究所 | Phthalate neodymium electron donor complex, preparing method and rare earth catalyst thereof |
| CN101735364B (en) * | 2009-12-11 | 2012-05-16 | 中国科学院长春应用化学研究所 | Method for preparing liquid polybutadiene rubber by sulfoacid rare earth catalyst |
| WO2012075964A1 (en) | 2010-12-09 | 2012-06-14 | 中国石油化工股份有限公司 | Neodymium based homogeneous phase rare earth catalyst and use thereof |
| CN102532365A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN102532353A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| CN102603940A (en) * | 2012-03-28 | 2012-07-25 | 中国科学院长春应用化学研究所 | Catalyst composition for preparing polyisoprene, preparation method of catalyst composition and preparation method of polyisoprene |
| CN102887966A (en) * | 2012-10-30 | 2013-01-23 | 中国科学院长春应用化学研究所 | Rare earth catalysis system and application thereof in preparation of conjugated diene liquid rubber |
| CN102911298A (en) * | 2011-08-03 | 2013-02-06 | 中国石油化工集团公司 | Catalyzing system for isoprene polymerization and preparation and application method of catalyzing system |
| CN103951776A (en) * | 2014-04-14 | 2014-07-30 | 山东玉皇化工有限公司 | Catalyst charging method in neodymium polybutadiene rubber polymerization processes |
| TWI488867B (en) * | 2009-10-16 | 2015-06-21 | Lanxess Deutschland Gmbh | Neodymium-catalysed polybutadienes |
-
2001
- 2001-10-12 CN CNB011282843A patent/CN1176121C/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365030C (en) * | 2002-10-21 | 2008-01-30 | 米其林技术公司 | Synthetic branched polyisoprenes and process for obtaining them |
| US7288611B2 (en) | 2003-09-25 | 2007-10-30 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Methods for preparing a rare-earth cis-1,4-polybutadiene rubber with a controlled molecular weight distribution |
| WO2007021215A1 (en) | 2005-08-12 | 2007-02-22 | Otkrytoe Aktsionernoe Obschestvo 'efremovsky Zavod Sinteticheskogo Kauchuka' | Method for producing cis-1,4 diene rubber, catalyst, rubber |
| TWI488867B (en) * | 2009-10-16 | 2015-06-21 | Lanxess Deutschland Gmbh | Neodymium-catalysed polybutadienes |
| CN101735364B (en) * | 2009-12-11 | 2012-05-16 | 中国科学院长春应用化学研究所 | Method for preparing liquid polybutadiene rubber by sulfoacid rare earth catalyst |
| CN101906110B (en) * | 2010-08-18 | 2014-03-05 | 中国科学院长春应用化学研究所 | Phthalate neodymium electron donor complex, preparing method and rare earth catalyst thereof |
| CN101906110A (en) * | 2010-08-18 | 2010-12-08 | 中国科学院长春应用化学研究所 | Phthalate neodymium electron donor complex, preparing method and rare earth catalyst thereof |
| CN102532365A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN102532353A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| CN102532353B (en) * | 2010-12-09 | 2014-01-29 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| WO2012075964A1 (en) | 2010-12-09 | 2012-06-14 | 中国石油化工股份有限公司 | Neodymium based homogeneous phase rare earth catalyst and use thereof |
| CN102532365B (en) * | 2010-12-09 | 2014-07-02 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN102911298A (en) * | 2011-08-03 | 2013-02-06 | 中国石油化工集团公司 | Catalyzing system for isoprene polymerization and preparation and application method of catalyzing system |
| CN102911298B (en) * | 2011-08-03 | 2014-10-15 | 中国石油化工集团公司 | Catalyzing system for isoprene polymerization and preparation and application method of catalyzing system |
| CN102603940A (en) * | 2012-03-28 | 2012-07-25 | 中国科学院长春应用化学研究所 | Catalyst composition for preparing polyisoprene, preparation method of catalyst composition and preparation method of polyisoprene |
| CN102887966A (en) * | 2012-10-30 | 2013-01-23 | 中国科学院长春应用化学研究所 | Rare earth catalysis system and application thereof in preparation of conjugated diene liquid rubber |
| CN103951776A (en) * | 2014-04-14 | 2014-07-30 | 山东玉皇化工有限公司 | Catalyst charging method in neodymium polybutadiene rubber polymerization processes |
| CN103951776B (en) * | 2014-04-14 | 2016-08-17 | 华宇橡胶有限责任公司 | Catalyst charge method in neodymium polymerized butadiene rubber polymerization process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176121C (en) | 2004-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1176121C (en) | Rare earth catalytic system and butadiene polymerizing process | |
| CN1528794A (en) | Rare-earth cis-1,4-polybutadiene rubber molecular mass distribution regulating method. | |
| CN1342719A (en) | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene | |
| KR101628356B1 (en) | Bulk polymerization process for producing polydienes | |
| CN101045768A (en) | Rare earth catalyst for preparing polyisoprene and preparation method and method for preparing polyisoprene | |
| CN1008822B (en) | Improving one's methods of polymerizing butadiene and copolymerization | |
| EP0375421A1 (en) | Polymerization of butadiene | |
| CN1654541A (en) | Process for in-situ polymerization preparation of poly-lactic acid/montmorillonite nano composite materials | |
| CN114075307B (en) | Rare earth catalyst and preparation method and application thereof | |
| CN102532365B (en) | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof | |
| CN1814627A (en) | Catalyst active constituent and catalyst containing same | |
| CN1153790C (en) | Rare-earch catalyst for polymerization and copolymerization of diolefin | |
| CN117050218B (en) | Rare earth catalyst containing Nd-MIL-103 and method for preparing cis-polybutadiene based on catalyst | |
| CN1084337C (en) | Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst | |
| CN1207312C (en) | Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same | |
| CN1130398C (en) | Improved cationic polymerization process and catalyst system therefor | |
| CN1671750A (en) | Process for manufacturing crystalline 1,2-polybutadiene | |
| CN1861649A (en) | Preparation process of rare earth catalyst for diolefines polymerizing copolymerizing | |
| CN1485351A (en) | Adjusting process for molecular weight distribution of rare earth polybutadiene rubber | |
| CN107652381B (en) | Preparation method of high cis-diene polymer | |
| CN105330773A (en) | Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof | |
| CN1148390C (en) | Process for polymerizing 1,3-butadiene | |
| CN105777963B (en) | The polymerization of high Mooney rare earth polybutadiene rubber | |
| CN1544492A (en) | Technology for heat-insulated polymerization producing rare earth polybutadiene rubber | |
| CN1267464C (en) | Catalyst for copolymerization of ethylene and styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041117 |