CN1358776A - Process for polymerizing 1,3-butadiene - Google Patents
Process for polymerizing 1,3-butadiene Download PDFInfo
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- CN1358776A CN1358776A CN 00134073 CN00134073A CN1358776A CN 1358776 A CN1358776 A CN 1358776A CN 00134073 CN00134073 CN 00134073 CN 00134073 A CN00134073 A CN 00134073A CN 1358776 A CN1358776 A CN 1358776A
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Abstract
The polymerization method of 1,3-butadiene is characterized by that nickel carboxylate salt, alkylaluminium compound, boron trifluoride or its complex compound and water are used as catalyst system, the catalyst components are divided into two groups of Al-Ni and B-H2O according to specific ratio and respectively aged, then adding into the polymerization system to initiate buta diene to make 1,4-cis-polymerization. The mole ratio of aluminium to nickel is 1.0-10.0, mole ratio of water to boron is 0.1-3.0, mole ratio of aluminium to boron is 0.1-2.0, mole ratio of nickel to butadiene is 0.3-3.0X10 to the minus fifth power. Its obvious advantage lies in that on the basis of retaining and unchanging the structure and property of cis-1,4-polybutadiene its catalyst utilization rate is high, dosage is small, Mooney visocisty of polymer is easy to be regulated and controlled.
Description
The invention belongs to the 1,3-butadiene paradigmatic category, relate to the preparation method of polymeric core technology-catalyst activity kind.
The catalyst system of polymerizing butadiene is a lot, and catalyst system such as lithium, nickel, cobalt, titanium, rare earth are arranged, and wherein except that the lithium catalytic body was anionic polymerization, all the other all belonged to the negative ion coordination polymerization of multicomponent catalyst.Catalyst system for multicomponent catalyst forms must carry out ageing (preparation spike) between the catalyst component in some way, just can give full play to the coordinative role of each catalyst component.The mode difference of preparation spike, the activity of such catalysts difference.
The preparation method that nickel catalyst system causes the polymerizing butadiene spike is a lot, as ternary ageing, two binary ageing and Al-Ni ageing, modes such as rare B Dan Jia.Japan JSB company adopts Ni-B-Al ternary ageing mode to produce cis-1,4-polybutadiene rubber, and China generally adopts the Al-Ni ageing at present, the single add mode production of rare B.
In nickel polymerized BR research and development process, find with the operation initial stage, polymer raw water content height, polyreaction is difficult to carry out.Therefore thinking that water can destroy catalyzer, is detrimental impurity; Found again afterwards that polymerization activity descended when the solvent comprises water amount is extremely low.This proof water is detrimental impurity in nickel catalyst system butadiene solution polymerization process, can destroy catalyzer, kills spike, influences polyreaction; When the polymerization system water content was an amount of, water can improve the polymerization activity of catalyzer again.China's cis-1,4-polybutadiene rubber production equipment generally adopts in solvent or monomer and adds water at present, make the polymerization system water content be controlled at certain limit, to improve the polymerization activity of catalyzer, (referring to " Wang Songze etc. the effect of minor amount of water in the polymer solvent oil ", China Synthetic Rubber Industry, 1984:7 (2) sends to the press: 1).At this moment, the molar content of water and catalyzer all is in the 10-6 order of magnitude in the polymerization system, and collision difficulty mutually is difficult to give full play to water and participates in the active effect of spike generation and eliminate water destroys catalyzer as impurity negative influence as catalyzer.Day disclosure special permission clear 56-24412 of communique (A) (19810309) has reported the production method of catalyst system production lower molecular weight cis-polybutadiene of organometallic compound, boron trifluoride or its complex compound of employing organic carboxyl acid nickel salt (or organic nickel complex compound), basic metal, II and III-th family, emphasized that polymerization system must be moisture, but the ageing of water as catalyst component participation catalyzer, catalyst levels is not higher.Chinese patent ZL94102595.0 has reported a kind of high-cis 1 that is applicable to the preparation high impact resistance polystyrene, the preparation method of 4-polyhutadiene, use carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound to make catalyzer, water is made conditioning agent, the water content that reduces polymerization system is produced the polybutadiene rubber of low solution viscosity, also not the ageing of water as catalyzer participation catalyzer, catalyst levels is higher.
The objective of the invention is to avoid the weak point of above-mentioned technology, a kind of 1,3-butadiene polymerization process is provided, provide a kind of aging method that the four-way catalyst of water participation is arranged especially, preparation high-cis 1 rubber, to improve the utilization ratio of catalyzer, reduce its consumption.
Purpose of the present invention can reach by following technical solution:
Adopt carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound as catalyst system, stable hydrocarbon is a solvent, cause divinyl and carry out 1, and 4-cis polyreaction, wherein:
(1) water participates in the reaction mechanism that the catalyst activity kind generates as the 4th kind of catalyst component in the above-mentioned catalyst system;
(2) catalyst component is divided into aluminium (Al)-nickel (Ni), boron (B)-water (H
2O) two groups of ageings respectively generate spike initiation divinyl then and carry out 1, the polymerization of 4-cis in polymerization system; Proportioning between the catalyst component is as follows:
A. aluminium is 1.0～10.0 to the mol ratio of nickel;
B. water is 0.1～3.0 to the mol ratio of boron;
C. aluminium is 0.1～2.0 to the mol ratio of boron;
D. nickel is 0.3～3.0 * 10 to the mol ratio of divinyl
-5
1,3-butadiene polymerization process of the present invention adopts carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound, water to make catalyzer, catalyst component is divided into Al-Ni, B-H
2O carries out ageing at intermittence or ageing continuously respectively for two groups, and digestion time and ageing temperature do not have strict especially restriction, and generally speaking, digestion time is controlled at 0.5～50min, and the ageing temperature is controlled at 0～50 ℃.Join then in the polymerization system and to generate spike and cause divinyl and carry out solution polymerization.
The carboxylic acid nickel salt can be solubility organic nickel compounds such as nickel naphthenate, nickel acetate, nickel octoate.
Alkylaluminium cpd can be the organic compound of aluminium such as triisobutyl aluminium, triethyl aluminum, aluminium diethyl monochloride or ethyl aluminum dichloride.
Boron trifluoride complex can be boron trifluoride ethyl ether complex or boron trifluoride ether complex.
Solvent can be raffinate oil, one-component or its mixture of hexane, heptane, hexanaphthene, benzene, toluene etc., the blending ratio of mixture does not have special restriction.
In Al-Ni ageing liquid, Al is 1.0～10.0 to the mol ratio of Ni, and preferred value is 1.5～6.0.
At B-H
2In the O ageing liquid, H
2O is 0.1～3.0 to the mol ratio of B, and preferred value is 0.4～1.0.
Al is 0.1～2.0 to the mol ratio of B, and preferred value is 0.2～0.6.
Ni is 0.3～3.0 * 10 to the mol ratio of divinyl
-5, preferred value is 0.5～1.0 * 10
-5
Add in the paradigmatic system down the collaborative of above-mentioned condition, can cause divinyl fast and carry out 1, the polymerization of 4-cis, polymerization temperature generally is controlled at 40～120 ℃, and preferred value is 60～100 ℃.
Special feature of the present invention is: recognizing that suitable quantity of water can improve on the basis of polymerization activity of nickel catalyst system, water as the monobasic catalyst component in this catalyst system, and with the ageing of B catalyst component, the participation spike generates, like this, the polymerization activity of the more effective raising catalyzer of ability reduces catalyst consumption.In catalyzer ageing mode in the past, no matter be ternary, two binary or B singly adds, all not water as catalyzer, allow it participate in catalyzer ageing, but keep containing suitable quantity of water in the polymerization system.In the spike generative process, water and Ni be inoperative, can reduce it to the reducing power of Ni with destroy Al-Ni product, influence the generation of spike with the Al reaction, has only the effect of water and B to belong to the reaction mechanism of spike generation.No matter be by that way water to be added polymerization system, the molar content of water and catalyst component is 10 in polymeric kettle
-6Level, the collision difficulty is difficult to give full play to active effect, but spent catalyst, " killing " spike in polymerization process between them when spike forms.
Based on above-mentioned viewpoint, with the inventive method water is added among the B, can further improve the utilization ratio of catalyzer, reduce catalyst levels.
Because water is participated in B-H as catalyst component
2The O ageing improves catalyst activity, and therefore, polymerization system needn't specially add water again, thereby has reduced the water content of polymerization system, and the life-span of spike is prolonged.
The present invention is applicable to 1,3-butadiene batchwise polymerization or continuous polymerization technique.Divinyl is under the varsol dilution, adopt nickel-aluminium-boron-water catalyst system and the inventive method, use a spot of catalyzer, the polymerizing butadiene transformation efficiency is reached about 85%, the polymkeric substance mooney viscosity is regulated and control easily, can prepare mooney viscosity and be 30～100, the high-quality polybutadiene rubber of gel content＜0.1%, cis-content＞96%, to satisfy doughnut and other rubber item needs.
Major advantage of the present invention is to add the water conservancy project preface by what save polymerization system, water as catalyst component, participate in the preparation of spike in mode of the present invention, reduced the consumption of water, improve the utilization ratio and the polymerization activity of catalyzer, prolonged the life-span of spike, reduced catalyst consumption, and the mooney viscosity of telomerized polymer, relative molecular mass etc. can be produced the fine cis-rich polybutadiene rubber neatly.
In the text, transformation efficiency is the mass percent that polymerizing butadiene is converted into polybutadiene rubber, and the usefulness amount of shaking is the quality that the electronic balance of 0.01g weighs up the polymerization glue, weighs up dry glue quality after the drying, calculates transformation efficiency; Refer in particular to inductive phase after polymerization feeds intake, the polymerization temperature in the kettle surpasses the needed time of jacket temperature, measures with temperature test instrument and clock; The mooney viscosity day automatic Mooney viscometer determining of island proper Tianjin company production (value was rotated 4 minutes in preheating 1 minute down at 100 ℃); The microtexture of polymkeric substance is measured with the 260-50 of Hitachi type infrared spectrophotometer; Molecular weight of polymer is measured with the GPC instrument that Waters company produces.
Further specify the present invention below in conjunction with embodiment, but do not limit the scope of the invention.Embodiment 1
The solution of raffinating oil, the triisobutyl aluminium that nickel naphthenate is made into 0.1mol/L be made into 0.2mol/L the solution of raffinating oil, be ready to boron trifluoride ethyl ether complex, tap water, standby.
With 100ml clean, oven dry, with the brown narrow-mouthed bottle of rubber stopper seal, through vacuumize, N
2After the displacement, be sequentially added into the above-mentioned solution of raffinating oil (down with) of 20ml raffinating oil after refining, 4.16ml triisobutyl aluminium and 1.40ml nickel naphthenate respectively, shake up room temperature ageing 30 minutes standby.
With 500ml clean, oven dry, with the ampere bottle of vacuum emulsion tube sealing, through vacuumize, N
2After the displacement, be sequentially added into respectively that 300ml raffinates oil, 20.0 μ l water, 174 μ l boron trifluoride ethyl ether complexs, shake up, standby room temperature ageing 30 minutes.
The polymerization formula proportioning: the Ni consumption of every 100g divinyl is 2.78 * 10
-5Mol, triisobutyl aluminium/nickel naphthenate/boron trifluoride diethyl etherate compound/water (Al/Ni/B/H
2O, mol ratio, down together) be 6/1/10/8.
Carry out batchwise polymerization with 5 liters of polymeric kettles.At first, strictness is washed still with clean the bubble still of raffinating oil, intensification, with high-purity nitrogen extrude wash still and raffinate oil after, add the solution of raffinating oil that 4L contains the 500g divinyl, be preheated to 30 ℃, add above-mentioned catalyzer ageing liquid respectively, start and stir, the jacket temperature of controlled polymerization still reacted 2.5 hours at 50 ± 1 ℃, press 0.5% of divinyl amount then and add antideteriorant BHT, experimental result is as shown in table 1.Comparative example 1A
With 100ml clean, oven dry, with the brown narrow-mouthed bottle of rubber stopper seal, through vacuumize, N
2After the displacement, be sequentially added into 20ml raffinating oil after refining, 6.9ml triisobutyl aluminium and 2.3ml nickel naphthenate respectively and shake up, standby room temperature ageing 30 minutes.
With 500ml clean, oven dry, with the ampere bottle of vacuum emulsion tube sealing, through vacuumize, N
2After the displacement, add that 300ml raffinates oil, 290 μ l boron trifluoride diethyl etherate compounds, shake up, standby room temperature ageing 30 minutes.
The polymerization formula proportioning: the Ni consumption by every 100g divinyl is 4.63 * 10
-5Mol, Al/Ni/B/H
2The O mol ratio is 6/1/10/0, and other experiment conditions are with embodiment 1, and experimental result is as shown in table 1.Comparative example 1B
Except the catalyzer ageing do not add water, polymer solvent add water make its moisture 12 * 10
-6Outward, other experiment conditions are with embodiment 1, and experimental result is as shown in table 1.Embodiment 2
With 100ml clean, oven dry, with the brown narrow-mouthed bottle of rubber stopper seal, through vacuumize, N
2After the displacement, be sequentially added into 20ml raffinating oil after refining, 1.38ml triisobutyl aluminium and 0.93ml nickel naphthenate respectively, shake up, standby room temperature ageing 10 minutes.
With 300ml clean, oven dry, with the ampere bottle of vacuum emulsion tube sealing, through vacuumize, N
2After the displacement, be sequentially added into respectively that 150ml raffinates oil, 8.3 μ l water, 76.6 μ l boron trifluoride ethyl ether complexs, shake up, standby room temperature ageing 10 minutes.
The polymerization formula proportioning: every 100g monomer nickel naphthenate consumption is 1.85 * 10
-5Mol, Al/Ni/B/H
2O is 3/1/6.6/5.Other experiment conditions are with embodiment 1, and experimental result is as shown in table 1.Comparative example 2
Remove the spike preparation process and do not add water, Al/Ni/B/H
2O is outside 3/1/6.6/0, and other experiment conditions are with embodiment 2, and experimental result is as shown in table 1.
The preparation method of table 1 spike and polymerization activity
Embodiment 3
| Ni consumption mol/100g monomer | ????Al/Ni/B/H 2O mol ratio | Inductive phase/min | Transformation efficiency/% | Relative molecular mass/* 10 4 | |
| Embodiment 1 | ??2.78×10 -5 | ????6/1/10/8 | ????12.8 | ????86.6 | ?????26.3 |
| Comparative example 1A | ??4.63×10 -5 | ????6/1/10/0 | ????22.3 | ????80.1 | ?????27.2 |
| Comparative example 1B | ??2.78×10 -5 | 6/1/10/0 solvent comprises water 12 * 10 -6 | ????25.3 | ????83.2 | ?????29.5 |
| Embodiment 2 | ??1.85×10 -5 | ????3/1/6.6/5 | ????15.6 | ????83.6 | ?????32.3 |
| Comparative example 2 | ??1.85×10 -5 | ????3/1/6.6/0 | ????38.5 | ????41.1 | ?????39.1 |
Except polymerization formula: every 100g monomer Ni consumption is 9.26 * 10
-5Mol, other catalyst levelss are undertaken outside the corresponding change by the experiment proportioning, and other experiment conditions are with embodiment 1, and experimental result is as shown in table 2.
Table 2
Embodiment 4
| ????Al/Ni/B/H 2O mol ratio | Transformation efficiency/% | Relative molecular mass/* 10 4 | ??ML(1+4) ???100℃ | Cis 1.4 content/% |
| ????10/1/6/1 | ??79.6 | ????42.3 | ????82 | ?????96.1 |
| ????8/1/8/3 | ??80.5 | ????36.4 | ????68 | ?????96.6 |
| ????6/1/6/5 | ??83.1 | ????32.1 | ????57 | ?????96.9 |
| ????4/1/8/7 | ??85.8 | ????24.1 | ????45 | ?????97.1 |
| ????5/1/10/9 | ??87.1 | ????22.0 | ????38 | ?????96.8 |
| ????3/1/6/12 | ??85.2 | ????23.6 | ????42 | ?????96.9 |
| ????3/1/6/15 | ??80.5 | ????26.1 | ????54 | ?????96.5 |
| ????3/1/6/2 | ??83.6 | ????38.4 | ????72 | ?????96.3 |
| ????2/1/4/1 | ??80.3 | ????43.1 | ????85 | ?????96.1 |
Change hexanaphthene, nickel naphthenate except that raffinating oil into and change that nickel octoate, triisobutyl aluminium change triethyl aluminum into, boron trifluoride ethyl ether complex changes into the boron trifluoride ether complex into, other experiment conditions are with embodiment 1, and experimental result is as shown in table 3.Embodiment 5
Nickel naphthenate changes nickel acetate into to the mixture that will change benzene, toluene into except that raffinating oil (mass ratio of benzene/methylbenzene is 1.2/1), triisobutyl aluminium changes into the triethyl aluminum, and other experiment conditions are with embodiment 1, and experimental result is as shown in table 3.Embodiment 6
Triisobutyl aluminium changes triethyl aluminum into to the mixture that will change hexane, heptane into except that raffinating oil (mass ratio of hexane/heptane is 2/1), boron trifluoride ethyl ether complex changes into the boron trifluoride ether complex, other experiment conditions are with embodiment 1, and experimental result is as shown in table 3.
Table 3
| Relative molecular mass/* 10 4 | Inductive phase/min | Transformation efficiency/% | ???ML(1+4) ???100℃ | |
| Embodiment 4 embodiment 5 embodiment 6 | ?????28.1 ?????29.6 ?????26.8 | ???16.3 ???17.2 ???15.3 | ????84.2 ????83.6 ????86.5 | ???45.4 ???49.7 ???43.1 |
As can be seen from the above Examples and Comparative Examples, polymerization process of the present invention can improve the utilization ratio of catalyzer, reduces catalyst consumption.Adopt the inventive method, use the ageing mode of four-way catalyst, improvement catalyzer, by changing polymerization process condition, mooney viscosity, the relative molecular mass of energy telomerized polymer are used to produce cis-1,4-polybutadiene rubber, can reach the object of the invention fully.
Claims (10)
1 one kinds of polymerization processs that are applicable to 1,3-butadiene adopt carboxylic acid nickel salt, alkylaluminium cpd, boron trifluoride or its complex compound as catalyst system, and stable hydrocarbon is a solvent, cause divinyl and carry out 1, and 4-cis polyreaction is characterized in that:
(1) water participates in the reaction mechanism that the catalyst activity kind generates as the 4th kind of catalyst component in the above-mentioned catalyst system;
(2) catalyst component is divided into aluminium (Al)-nickel (Ni), boron (B)-water (H
2O) two groups of respectively ageings add then and generate spike in the polymerization system, cause divinyl and carry out 1, the polymerization of 4-cis; Proportioning between the catalyst component is as follows:
A. aluminium is 1.0～10.0 to the mol ratio of nickel;
B. water is 0.1～3.0 to the mol ratio of boron;
C. aluminium is 0.1～2.0 to the mol ratio of boron;
D. nickel is 0.3～3.0 * 10 to the mol ratio of divinyl
-5
(3) Al-Ni, B-H
2During the O ageing, the ageing temperature generally is controlled at 0～50 ℃, and digestion time generally is controlled at 0.5～50min.
(4) polymerization temperature generally is controlled at 40～120 ℃.
2,, it is characterized in that described carboxylic acid nickel salt is nickel naphthenate, nickel acetate, nickel octoate according to the method for claim 1.
3,, it is characterized in that alkylaluminium cpd is triisobutyl aluminium, triethyl aluminum, aluminium diethyl monochloride or ethyl aluminum dichloride according to the method for claim 1.
4,, it is characterized in that described boron trifluoride or its complex compound are boron trifluoride ethyl ether complex or boron trifluoride ether complex according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that described saturated hydrocarbon solvent be raffinate oil, one-component or its mixture of hexane, heptane, hexanaphthene, benzene, toluene.
6,, it is characterized in that in the Al-Ni ageing liquid that Al is 1.5～6.0 to the mol ratio of Ni according to the method for claim 1.
7, according to the method for claim 1, it is characterized in that B-H
2In the O ageing liquid, H
2O is 0.4～1.0 to the mol ratio of B.
8,, it is characterized in that aluminium is 0.2～0.6 to the mol ratio of boron according to the method for claim 1.
9,, it is characterized in that nickel is 0.5～1.0 * 10 to the mol ratio of divinyl according to the method for claim 1
-5
10,, it is characterized in that polymerization temperature is controlled at 60～100 ℃ according to the method for claim 1.
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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 |
| 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 |
| US10066035B2 (en) | 2015-12-07 | 2018-09-04 | Bridgestone Corporation | Catalyst systems and methods for preparation of 1,4-polybutadiene rubber |
| CN114031698A (en) * | 2021-10-26 | 2022-02-11 | 中国石油化工股份有限公司 | Raw butadiene rubber and preparation method thereof |
-
2000
- 2000-12-12 CN CNB001340735A patent/CN1148390C/en not_active Expired - Lifetime
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 |
| 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 |
| US10066035B2 (en) | 2015-12-07 | 2018-09-04 | Bridgestone Corporation | Catalyst systems and methods for preparation of 1,4-polybutadiene rubber |
| CN114031698A (en) * | 2021-10-26 | 2022-02-11 | 中国石油化工股份有限公司 | Raw butadiene rubber and preparation method thereof |
| CN114031698B (en) * | 2021-10-26 | 2023-07-25 | 中国石油化工股份有限公司 | Butadiene rubber raw rubber and preparation method thereof |
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