CN103951776B - Catalyst charge method in neodymium polymerized butadiene rubber polymerization process - Google Patents
Catalyst charge method in neodymium polymerized butadiene rubber polymerization process Download PDFInfo
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- CN103951776B CN103951776B CN201410147143.5A CN201410147143A CN103951776B CN 103951776 B CN103951776 B CN 103951776B CN 201410147143 A CN201410147143 A CN 201410147143A CN 103951776 B CN103951776 B CN 103951776B
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Abstract
Catalyst charge method in the neodymium polymerized butadiene rubber polymerization process of the present invention, comprise the following steps: mixed catalyst i.e. sesquialter ethylmercury chloride aluminum, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium are mixed and carry out ternary ageing by static mixer by (1) according to a certain percentage, digestion time 25 35min, temperature 25 DEG C 35 DEG C；(2) mixed catalyst after ageing enters polymeric kettle after entering premix still buffering together with fourth oil and participates in polyreaction, polymeric kettle pressure 0.35 0.45MPa, first polymeric kettle temperature 60 C 75 DEG C；(3) simultaneously, by the most aged for part diisobutylaluminium hydride directly from the middle and lower part addition of premix still, enter polymeric kettle polyreaction together with the material in step (2) and produce polybutadiene rubber.The invention has the beneficial effects as follows, stable reaction, activity stabilized, temperature stabilization, be conducive to Mooney to control, polybutadiene rubber constant product quality.
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
During existing method prepares neodymium polymerized butadiene rubber, catalyst uses ternary ageing catalyst the most all to add reaction, and reaction temperature fluctuation is big, 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, it is provided that a kind of catalyst charge method in stable reaction, neodymium polymerized butadiene rubber polymerization process activity stabilized, that beneficially Mooney controls.
The present invention is achieved through the following technical solutions:
Catalyst charge method in the neodymium polymerized butadiene rubber polymerization process of the present invention, it is characterised in that: comprise the following steps:
(1) mixed catalyst i.e. sesquialter ethylmercury chloride aluminum, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium are mixed according to a certain percentage carry out ternary ageing, digestion time 25-35min, temperature 25 DEG C-35 DEG C by static mixer；
(2) entrance polymeric kettle participation polyreaction after the mixed catalyst after ageing enters premix still buffering together with fourth oil, polymeric kettle pressure 0.35-0.45MPa,
First polymeric kettle temperature 60 C-75 DEG C；Fourth oil includes butadiene and solvent naphtha, and solvent naphtha is normal hexane；
(3) simultaneously, by the most aged for part diisobutylaluminium hydride directly from the middle and lower part addition of premix still, enter polymeric kettle polyreaction together with the material in step (2) and produce polybutadiene rubber.
Prioritization scheme is, in ternary ageing, diisobutylaluminium hydride is 7:1-2:1 with the part by weight of the diisobutylaluminium hydride singly added.
Single plus hydrogenated diisobutyl aluminum and ratio HAL/Nd(of new certain herbaceous plants with big flowers acid neodymium
Mol/mol) control to be adjusted between 2-5.
Sesquialter ethylmercury chloride aluminum, 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.
Butadiene is 1:5 5.5 with the volume ratio of solvent naphtha.
The ratio (mol/mol) of neodymium caprate and butadiene is (6 ± 0.5) × 10-5: 1.
Reaction scheme: diisobutylaluminium hydride divides two parts add paradigmatic system, first the diisobutylaluminium hydride of ＞ 2/3 amount carries out ageing reaction 1-3min with sesquialter ethylmercury chloride aluminum (sesquialter aluminum), reacted into ageing liquid again carry out with neodymium caprate ageing reaction, total digestion time 25-35min, ageing reaction enters premix still after completing；Additionally have≤diisobutylaluminium hydride of 1/3 amount is directly entered premix still and carries out polyreaction.
The invention has the beneficial effects as follows, stable reaction, activity stabilized, temperature stabilization, be conducive to Mooney to control, polybutadiene rubber constant product quality.
Accompanying drawing explanation
Fig. 1 is the material charging schematic flow sheet of prior art.Fig. 2 is the material charging schematic flow sheet of the present invention.
Detailed description of the invention
Accompanying drawing is a kind of specific embodiment of the present invention.
Embodiment 1(out-of-date methods):
Use ternary aging, it is aged 25-35 minute after three kinds of catalyst of sesquialter ethylmercury chloride aluminum, diisobutylaluminium hydride, new certain herbaceous plants with big flowers acid neodymium etc. being mixed by certain formula successively by certain proportioning, Aging Temperature 25 DEG C-35 DEG C, react in being then fed into polymeric kettle, polymeric kettle pressure 0.35-0.45MPa
First polymeric kettle temperature 60 C-75 DEG C, remaining polymeric kettle temperature is 60-90 DEG C.Now, diisobutylaluminium hydride and neodymium caprate formula: HAL/Nd(mol/mol) 15, through chemical examination, Mooney is 58, and reflects bigger 60 DEG C-80 DEG C of temperature fluctuation, and effect is undesirable.
Embodiment 2(new method):
(1) sesquialter ethylmercury chloride aluminum (be called for short sesquialter aluminum), diisobutylaluminium hydride (abbreviation aluminum hydride), the mixed catalyst of new certain herbaceous plants with big flowers acid neodymium composition are mixed according to a certain percentage carry out ternary ageing by static mixer, digestion time 25-35min, temperature 25 DEG C-35 DEG C；(2) entrance polymeric kettle participation polyreaction after the mixed catalyst after ageing enters premix still buffering together with fourth oil, polymeric kettle pressure 0.35-0.45MPa,
First polymeric kettle temperature 60 C-75 DEG C, remaining polymeric kettle temperature is 60-90 DEG C；Fourth oil includes butadiene and solvent naphtha, and solvent naphtha is normal hexane；(3) simultaneously, entering polymeric kettle polyreaction by the most aged for part diisobutylaluminium hydride (be called for short and singly add aluminum) produce polybutadiene rubber directly from the middle and lower part addition of premix still together with the material in step (2), sample examination judges whether reaction terminates.
The diisobutylaluminium hydride (being called for short ageing aluminum) being aged is 7:1-2:1 with single plus hydrogenated diisobutyl aluminum (be called for short and singly add aluminum) ratio.
All catalyst overall formulation are less than 20, and three kinds of catalyst ratio scopes are as follows:
| Diisobutylaluminium hydride total amount and the ratio of neodymium caprate | mol/mol | 9-15:1 |
| Sesquialter aluminum and the ratio of neodymium caprate | mol/mol | 1.6-2.1:1 |
Fourth oil formula:
| Butadiene and the ratio of solvent naphtha | Volume ratio | 1:5—5.5 |
Major catalyst and the ratio of butadiene:
| Neodymium caprate and the ratio of butadiene | mol/mol | (6 ± 0.5) × 10-5: 1 |
Single plus hydrogenated diisobutyl aluminum has just started temporarily to be set to neodymium caprate formula adjustment scope: 1:1≤HAL/Nd(mol/mol) ＜ 2:1, and be depending on circumstances adjusted, and regulate Mooney mainly based on the single plus hydrogenated diisobutyl aluminum of temporarily regulation, and note reflection activity and Mooney fluctuation at any time.Being 49 through chemical examination Mooney, temperature fluctuation is between 62 DEG C-80 DEG C, and Mooney, temperature all develop towards preferable direction, and reflection temperature fluctuation also tends to plateau temperature.
Embodiment 3(new method):
The mixed catalyst consumption of ternary ageing is constant, and single plus hydrogenated diisobutyl aluminum (be called for short and singly add aluminum) is HAL/Nd(mol/mol with neodymium caprate formula adjustment) 1.8:1, remaining is same as in Example 2.Being 47 through chemical examination Mooney, temperature fluctuation is between 66 DEG C-75 DEG C.
Embodiment 4(new method):
The mixed catalyst consumption of ternary ageing is constant, and single plus hydrogenated diisobutyl aluminum (be called for short and singly add aluminum) is HAL/Nd(mol/mol with neodymium caprate formula adjustment) 4:1, remaining is same as in Example 2.Reflection trend tends to be steady substantially, and temperature fluctuation is between 70 DEG C ± 2 DEG C.Mooney 44, reactive state tends to be steady, and fluctuates the least.
Embodiment 5(new method):
The mixed catalyst consumption of ternary ageing is constant, through repeatedly adjusting, single plus hydrogenated diisobutyl aluminum (be called for short and singly add aluminum) and neodymium caprate formula (
Mol/mol) controlling to be adjusted between 2-5:1, remaining is same as in Example 2.Reflection temperature is the most stable, and temperature fluctuation is between 70 DEG C ± 3 DEG C, and Mooney fluctuation substantially remains between 45 ± 5, has reached completely to related request.
On the premise of ensureing raw materials quality, out-of-date methods typically can be by method below regulation Mooney:
1, reactivity is low, and Mooney is low: improves neodymium caprate and accompanies half aluminum consumption；
2, reactivity is low, and Mooney is high: improve diisobutylaluminium hydride consumption, or overall raising formula；
3, reactivity is high, and Mooney is low: reduce diisobutylaluminium hydride consumption, or overall reduction formula；
4, reactivity is high, and Mooney is high: reduces and accompanies half aluminum consumption, or raising HAL/Nd reduces integral formula simultaneously.
Through the present invention, Mooney can be regulated by the following method:
1, reaction is normal, and Mooney is low: reduces diisobutylaluminium hydride consumption, or improves sesquialter aluminum consumption (based on the single plus hydrogenated diisobutyl aluminum consumption of regulation)；
2, reaction is normal, and Mooney is high: improves diisobutylaluminium hydride consumption, or reduces sesquialter aluminum consumption (based on the single plus hydrogenated diisobutyl aluminum consumption of regulation)；
3, reactivity is low, and Mooney is low: improves neodymium caprate and accompanies half aluminum consumption；
4, reactivity is low, and Mooney is high: improve single plus hydrogenated diisobutyl aluminum consumption, or overall raising formula；
5, reactivity is high, and Mooney is high: reduce sesquialter aluminum consumption；
6, reactivity is high, and Mooney is low: reduces single plus hydrogenated diisobutyl aluminum consumption, or reduces the consumption of neodymium agent.
Claims (3)
1. catalyst charge method in a neodymium polymerized butadiene rubber polymerization process, it is characterised in that: comprise the following steps:
(1) mixed catalyst i.e. sesquialter ethylmercury chloride aluminum, diisobutylaluminium hydride, neodymium caprate is mixed according to a certain percentage carry out ternary ageing, digestion time 25-35min, temperature 25 DEG C-35 DEG C by static mixer；Sesquialter ethylmercury chloride aluminum, total diisobutylaluminium hydride, the ratio (mol/mol/mol) of neodymium caprate are 1.6-2.1:9-15:1；
(2) mixed catalyst after ageing enters polymeric kettle after entering premix still buffering together with fourth oil and participates in polyreaction, polymeric kettle pressure 0.35-0.45MPa, first polymeric kettle temperature 60 C-75 DEG C；Fourth oil includes butadiene and solvent naphtha, and solvent naphtha is normal hexane；
(3) simultaneously, by the most aged for part diisobutylaluminium hydride directly from the middle and lower part addition of premix still, enter polymeric kettle polyreaction together with the material in step (2) and produce polybutadiene rubber；In ternary ageing, diisobutylaluminium hydride is 7:1-2:1 with the part by weight of the diisobutylaluminium hydride singly added；Single plus hydrogenated diisobutyl aluminum and ratio HAL/Nd(mol/mol of neodymium caprate) control to be adjusted between 2-5.
Catalyst charge method in neodymium polymerized butadiene rubber polymerization process the most according to claim 1, it is characterised in that: butadiene is 1:5 5.5 with the volume ratio of solvent naphtha.
Catalyst charge method in neodymium polymerized butadiene rubber polymerization process the most according to claim 1 and 2, it is characterised in that: the ratio (mol/mol) of neodymium caprate and butadiene is (6 ± 0.5) × 10-5: 1.
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| CN105713119B (en) * | 2014-12-05 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of neodymium series rare earth polybutadiene rubber polyplant and its feed system |
| CN112552441B (en) * | 2020-12-09 | 2021-09-07 | 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 |
| 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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| KR101010865B1 (en) * | 2002-05-16 | 2011-01-26 | 미쉐린 러쉐르슈 에 떼크니크 에스.에이. | Catalytic system for preparing polybutadienes and preparation method |
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| 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 |
| 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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| Title |
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| 合成顺丁橡胶用稀土催化剂的开发进展;赵世权等;《合成橡胶工业》;20080315;第31卷(第2期);p81-86 * |
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