CN103951776A - Catalyst charging method in neodymium polybutadiene rubber polymerization processes - Google Patents
Catalyst charging method in neodymium polybutadiene rubber polymerization processes Download PDFInfo
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- CN103951776A CN103951776A CN201410147143.5A CN201410147143A CN103951776A CN 103951776 A CN103951776 A CN 103951776A CN 201410147143 A CN201410147143 A CN 201410147143A CN 103951776 A CN103951776 A CN 103951776A
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Abstract
The invention discloses a catalyst charging method in neodymium polybutadiene rubber polymerization processes. The catalyst charging method comprises following steps: (1) ethylaluminum sesquichloride, diisobutylaluminum hydride, and neodymium neodecanoate are mixed according to a certain ratio so as to obtain a mixed catalyst, the mixed catalyst is delivered into a static mixer for ternary aging, wherein aging time ranges from 25 to 35min, and aging temperature ranges from 25 to 35 DEG C; (2) the mixed catalyst obtained via aging is delivered into a premixing kettle with a mixture of butadiene and a solvent oil for buffer treatment, and then an obtained mixed material is delivered into a polymerization kettle for polymerization, wherein pressure of the polymerization kettle ranges from 0.35 to 0.45 MPa, a first polymerization kettle temperature ranges from 60 to 75 DEG C; and (3) a part of diisobutylaluminum hydride is directly added through the middle-lower part of the premixing kettle into the polymerization kettle without aging, and is reacted with the mixed material obtained via step (2) for polymerization so as to prepare polybutadiene rubber. Beneficial effects of the catalyst charging method are that: reaction is stable; activity is stable; temperature is stable; the catalyst charging method is beneficial for Mooney viscosity control; and polybutadiene rubber product quality is stable.
Description
Technical field
The invention belongs to rubber production field, relate to a kind of catalyst charge method in neodymium polymerized butadiene rubber polymerization process.
Background technology
Existing method is prepared in the process of neodymium polymerized butadiene rubber, and catalyzer adopts that ternary ageing catalyzer is disposable all adds reaction, and temperature of reaction fluctuation is large, and Mooney is high, and reaction effect is undesirable.
Summary of the invention
The present invention is in order to make up the deficiencies in the prior art, provide a kind of stable reaction, activity stabilized, be conducive to catalyst charge method in neodymium polymerized butadiene rubber polymerization process that Mooney controls.
The present invention is achieved through the following technical solutions:
Catalyst charge method in neodymium polymerized butadiene rubber polymerization process of the present invention, is characterized in that: comprise the following steps:
(1) by mixed catalyst, be that sesquialter ethyl aluminum chloride, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium mix according to a certain percentage by static mixer and carry out ternary ageing, digestion time 25-35min, 25 ℃-35 ℃ of temperature;
(2) mixed catalyst after ageing enters polymeric kettle participation polyreaction, polymeric kettle pressure 0.35-0.45MPa, first polymeric kettle temperature 60 C-75 ℃ enter premix still buffering together with fourth oil after; Fourth oil comprises divinyl and solvent oil, and solvent oil is normal hexane;
(3), partial hydrogenation diisobutyl aluminum is directly added from the middle and lower part of premix still without ageing simultaneously, and together with material in step (2), enter polymeric kettle polyreaction and produce polybutadiene rubber.
Prioritization scheme is that in ternary ageing, diisobutylaluminium hydride is 7:1-2:1 with the part by weight of the diisobutylaluminium hydride singly adding.
The ratio HAL/Nd(mol/mol that singly adds diisobutylaluminium hydride and new certain herbaceous plants with big flowers acid neodymium) be controlled between 2-5 and adjust.
Sesquialter ethyl aluminum chloride, total diisobutylaluminium hydride, the ratio (mol/mol/mol) of new certain herbaceous plants with big flowers acid neodymium are 1.6-2.1:9-15:1.
The volume ratio of divinyl and solvent oil is 1:5-5.5.
Neodymium caprate is (6 ± 0.5) * 10 with the ratio (mol/mol) of divinyl
-5: 1.
Reaction scheme: divide two portions to add paradigmatic system diisobutylaluminium hydride, first the diisobutylaluminium hydride of > 2/3 amount carries out ageing with sesquialter ethyl aluminum chloride (sesquialter aluminium) and reacts 1-3min, reacted into ageing liquid carry out ageing reaction with neodymium caprate again, total digestion time 25-35min, ageing enters premix still after having reacted; The diisobutylaluminium hydride of have in addition≤1/3 amount directly enters premix still and carries out polyreaction.
The invention has the beneficial effects as follows, stable reaction, activity stabilized, temperature-stable, be conducive to Mooney and control, polybutadiene rubber constant product quality.
Accompanying drawing explanation
Fig. 1 is the material feeding schematic flow sheet of prior art.Fig. 2 is material feeding schematic flow sheet of the present invention.
embodiment
Accompanying drawing is a kind of specific embodiment of the present invention.
Embodiment 1(out-of-date methods):
Adopt ternary aging, ageing 25-35 minute after three kinds of catalyzer of sesquialter ethyl aluminum chloride, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium etc. being mixed by certain formula successively by certain proportioning, 25 ℃-35 ℃ of Aging Temperatures, then be sent in polymeric kettle and react, polymeric kettle pressure 0.35-0.45MPa, first polymeric kettle temperature 60 C-75 ℃, all the other polymeric kettle temperature are 60-90 ℃.Now, diisobutylaluminium hydride and neodymium caprate formula: HAL/Nd(mol/mol) 15, through chemical examination, Mooney is 58, and reflects larger 60 ℃-80 ℃ of temperature fluctuation, effect is undesirable.
Embodiment 2(novel method):
(1) mixed catalyst of sesquialter ethyl aluminum chloride (being called for short sesquialter aluminium), diisobutylaluminium hydride (abbreviation aluminum hydride), new certain herbaceous plants with big flowers acid neodymium composition is mixed according to a certain percentage by static mixer and carries out ternary ageing, digestion time 25-35min, 25 ℃-35 ℃ of temperature; (2) mixed catalyst after ageing enters polymeric kettle participation polyreaction enter premix still buffering together with fourth oil after, polymeric kettle pressure 0.35-0.45MPa, and first polymeric kettle temperature 60 C-75 ℃, all the other polymeric kettle temperature are 60-90 ℃; Fourth oil comprises divinyl and solvent oil, and solvent oil is normal hexane; (3) simultaneously, partial hydrogenation diisobutyl aluminum (be called for short and singly add aluminium) is directly added from the middle and lower part of premix still without ageing, produce polybutadiene rubber with entering polymeric kettle polyreaction together with material in step (2), whether sample examination judgement reaction finishes.
The diisobutylaluminium hydride of ageing (being called for short ageing aluminium) is 7:1-2:1 with singly adding diisobutylaluminium hydride (be called for short and singly add aluminium) ratio.
It is as follows that the overall formula of all catalyzer is no more than 20, three kinds of catalyst ratio scopes:
| The ratio of diisobutylaluminium hydride total amount and neodymium caprate | mol/mol | 9-15：1 |
| The ratio of sesquialter aluminium and neodymium caprate | mol/mol | 1.6-2.1：1 |
Fourth oil formula:
| The ratio of divinyl and solvent oil | Volume ratio | 1:5—5.5 |
The ratio of Primary Catalysts and divinyl:
| The ratio of neodymium caprate and divinyl | mol/mol | （6±0.5）×10 -5：1 |
Singly add diisobutylaluminium hydride and neodymium caprate formula adjustment scope has just started to be temporarily decided to be: 1:1≤HAL/Nd(mol/mol) < 2:1, and depending on circumstances regulate, and regulate Mooney mainly to take temporarily to regulate and singly add diisobutylaluminium hydride as main, and note at any time reflection activity and Mooney fluctuation.Through chemical examination Mooney, be 49, temperature fluctuation is between 62 ℃-80 ℃, and Mooney, temperature be all towards better future development, the reflection temperature fluctuation temperature that also tends to be steady.
Embodiment 3(novel method):
The mixed catalyst consumption of ternary ageing is constant, and singly adding diisobutylaluminium hydride (be called for short and singly add aluminium) is HAL/Nd(mol/mol with neodymium caprate formula adjustment) 1.8:1, all the other are identical with embodiment 2.Through chemical examination Mooney, be 47, temperature fluctuation is between 66 ℃-75 ℃.
Embodiment 4(novel method):
The mixed catalyst consumption of ternary ageing is constant, and singly adding diisobutylaluminium hydride (be called for short and singly add aluminium) is HAL/Nd(mol/mol with neodymium caprate formula adjustment) 4:1, all the other are identical with embodiment 2.Reflection trend tends to be steady substantially, and temperature fluctuation is between 70 ℃ ± 2 ℃.Mooney 44, response behaviour tends to be steady, and fluctuates very little.
Embodiment 5(novel method):
The mixed catalyst consumption of ternary ageing is constant, through repeatedly adjusting, singly adds diisobutylaluminium hydride (be called for short and singly add aluminium) and neodymium caprate formula (mol/mol) and is controlled between 2-5:1 and adjusts, and all the other are identical with embodiment 2.Reflection temperature is relatively stable, and temperature fluctuation is between 70 ℃ ± 3 ℃, and Mooney fluctuation remains between 45 ± 5 substantially, has reached completely to related request.
Guaranteeing under the prerequisite of raw materials quality, out-of-date methods generally can regulate Mooney by method below:
1, reactive behavior is low, and Mooney is low: improve neodymium caprate and accompany half aluminium consumption;
2, reactive behavior is low, and Mooney is high: improve diisobutylaluminium hydride consumption, or the whole formula that improves;
3, reactive behavior is high, and Mooney is low: reduce diisobutylaluminium hydride consumption, or the whole formula that reduces;
4, reactive behavior is high, and Mooney is high: reduce and accompany half aluminium consumption, or improve HAL/Nd and reduce integral formula simultaneously.
Through the present invention, can regulate by the following method Mooney:
1, reaction is normal, and Mooney is low: reduce diisobutylaluminium hydride consumption, or improve sesquialter aluminium consumption (take to regulate and singly add diisobutylaluminium hydride consumption as main);
2, reaction is normal, and Mooney is high: improve diisobutylaluminium hydride consumption, or reduce sesquialter aluminium consumption (take to regulate and singly add diisobutylaluminium hydride consumption as main);
3, reactive behavior is low, and Mooney is low: improve neodymium caprate and accompany half aluminium consumption;
4, reactive behavior is low, and Mooney is high: improve and singly add diisobutylaluminium hydride consumption, or the whole formula that improves;
5, reactive behavior is high, and Mooney is high: reduce sesquialter aluminium consumption;
6, reactive behavior is high, and Mooney is low: reduce and singly add diisobutylaluminium hydride consumption, or reduce the consumption of neodymium agent.
Claims (6)
1. a catalyst charge method in neodymium polymerized butadiene rubber polymerization process, is characterized in that: comprise the following steps:
(1) by mixed catalyst, be that sesquialter ethyl aluminum chloride, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium mix according to a certain percentage by static mixer and carry out ternary ageing, digestion time 25-35min, 25 ℃-35 ℃ of temperature;
(2) mixed catalyst after ageing enters polymeric kettle participation polyreaction, polymeric kettle pressure 0.35-0.45MPa, first polymeric kettle temperature 60 C-75 ℃ enter premix still buffering together with fourth oil after; Fourth oil comprises divinyl and solvent oil, and solvent oil is normal hexane;
(3), partial hydrogenation diisobutyl aluminum is directly added from the middle and lower part of premix still without ageing simultaneously, and together with material in step (2), enter polymeric kettle polyreaction and produce polybutadiene rubber.
2. catalyst charge method in neodymium polymerized butadiene rubber polymerization process according to claim 1, is characterized in that: in ternary ageing, diisobutylaluminium hydride is 7:1-2:1 with the part by weight of the diisobutylaluminium hydride singly adding.
3. catalyst charge method in neodymium polymerized butadiene rubber polymerization process according to claim 1 and 2, is characterized in that: the ratio HAL/Nd(mol/mol that singly adds diisobutylaluminium hydride and new certain herbaceous plants with big flowers acid neodymium) be controlled between 2-5 and adjust.
4. catalyst charge method in neodymium polymerized butadiene rubber polymerization process according to claim 1 and 2, is characterized in that: sesquialter ethyl aluminum chloride, total diisobutylaluminium hydride, the ratio (mol/mol/mol) of new certain herbaceous plants with big flowers acid neodymium are 1.6-2.1:9-15:1.
5. catalyst charge method in neodymium polymerized butadiene rubber polymerization process according to claim 1 and 2, is characterized in that: the volume ratio of divinyl and solvent oil is 1:5-5.5.
6. catalyst charge method in neodymium polymerized butadiene rubber polymerization process according to claim 1 and 2, is characterized in that: neodymium caprate is (6 ± 0.5) * 10 with the ratio (mol/mol) of divinyl
-5: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713119A (en) * | 2014-12-05 | 2016-06-29 | 中国石油天然气股份有限公司 | Neodymium-based rare earth butadiene rubber polymerization device and feeding system thereof |
| CN112552441A (en) * | 2020-12-09 | 2021-03-26 | 浙江传化合成材料有限公司 | Preparation method of neodymium rare earth rubber |
| CN116836318A (en) * | 2023-07-19 | 2023-10-03 | 浙江传化合成材料有限公司 | Rare earth butadiene rubber and preparation method thereof |
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| CN1347923A (en) * | 2001-10-12 | 2002-05-08 | 中国科学院长春应用化学研究所 | Rare earth catalytic system and butadiene polymerizing process |
| WO2003097708A1 (en) * | 2002-05-16 | 2003-11-27 | Societe De Technologie Michelin | Catalytic system for preparing polybutadienes and preparation method |
| CN1840552A (en) * | 2005-03-30 | 2006-10-04 | 中国石油化工股份有限公司 | Rare-earth catalyst and conjugated diene polymerization process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1347923A (en) * | 2001-10-12 | 2002-05-08 | 中国科学院长春应用化学研究所 | Rare earth catalytic system and butadiene polymerizing process |
| WO2003097708A1 (en) * | 2002-05-16 | 2003-11-27 | Societe De Technologie Michelin | Catalytic system for preparing polybutadienes and preparation method |
| CN1840552A (en) * | 2005-03-30 | 2006-10-04 | 中国石油化工股份有限公司 | Rare-earth catalyst and conjugated diene polymerization process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713119A (en) * | 2014-12-05 | 2016-06-29 | 中国石油天然气股份有限公司 | Neodymium-based rare earth butadiene rubber polymerization device and feeding system thereof |
| CN105713119B (en) * | 2014-12-05 | 2018-07-10 | 中国石油天然气股份有限公司 | Neodymium-based rare earth butadiene rubber polymerization device and feeding system thereof |
| CN112552441A (en) * | 2020-12-09 | 2021-03-26 | 浙江传化合成材料有限公司 | Preparation method of neodymium rare earth rubber |
| CN116836318A (en) * | 2023-07-19 | 2023-10-03 | 浙江传化合成材料有限公司 | Rare earth butadiene rubber and preparation method thereof |
| CN116836318B (en) * | 2023-07-19 | 2024-07-09 | 浙江传化合成材料股份有限公司 | Rare earth butadiene rubber and preparation method thereof |
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