CN1063189C - Preparation of low molecular 1, 2 -polybutadiene - Google Patents
Preparation of low molecular 1, 2 -polybutadiene Download PDFInfo
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- CN1063189C CN1063189C CN96120729A CN96120729A CN1063189C CN 1063189 C CN1063189 C CN 1063189C CN 96120729 A CN96120729 A CN 96120729A CN 96120729 A CN96120729 A CN 96120729A CN 1063189 C CN1063189 C CN 1063189C
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- divinol
- sodium
- naphthalene
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- divinyl
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Abstract
The present invention relates to a method for preparing 1, 2-divinol. In the method, the In Site technology is introduced into the process of preparing polybutadiene, and the process adopts a sodium-naphthalene catalytic system and toluene as chain transfer agents. Therefore, the In Site technology is combined with batch polymerization, which greatly increases the concentration of monomer butadiene in polymerizing solution, obviously enhances the production capacity, greatly reduces solvent dosages and equipment investment, and effectively lowers energy consumption and raw material consumption.
Description
The present invention relates to the diene polymer preparing technical field.
Low molecular 1,2-polyhutadiene (claiming polyhutadiene oil again) is a kind of important petrochemicals.It is the important intermediates of coating, spices, tensio-active agent, in field of fine chemical purposes is widely arranged.In addition, also can be used for preparing insulating material, electronic encapsulation material, lubricating oil and tackiness agent etc.
Low molecule 1, the 2-polyhutadiene can prepare with all different initiating systems.These initiating systems have free fundamental mode, cationic, anionic and Ziegler one Natta type.The structure of products obtained therefrom has 1,2 type, 1,4 type and middle vinyl-type.
The anionic polymerization system is these two kinds of different initiating speciess of branch active polymerization system and the basic metal initiator system that has chain-transfer agent again.Active polymerization system needs-78 ℃ low temperature, needs expensive refrigeration system, is difficult for starting.
In the basic metal that uses, lithium, sodium, potassium etc. are arranged.The direct use sodium sand that has, the organic compound of the use sodium that has.DD 265 903 A1 (89.03.15) directly use sodium sand to make promoting agent.GB 1 417 002 (75.12.10) has used organolithium and organosiloxane compound to prepare divinol.
The preparation divinol commonly adopts the batchwise polymerization mode.Common batchwise polymerization is once divinyl all to be added, but such divinyl feed way, the concentration of divinyl can only reach about 20% in the polymerization system.
The objective of the invention is to overcome in the batch polymerization process, the shortcoming that the monomer butadiene concentration is low increases substantially the concentration of divinyl, reduces the solvent usage quantity, reduces facility investment, cuts down the consumption of energy and raw materials consumption, thereby reduces production costs greatly.
Purpose of the present invention realizes by following technical scheme:
Preparation 1, the 2-divinol, employing is the sodium-naphthalene catalyst system of solvent with tetrahydrofuran (THF) (THF), with toluene is chain-transfer agent, make 1, the 3-divinyl carries out the negatively charged ion telomerization, In Site technology is introduced 1 of employing sodium-naphthalene catalyst system, and 2-divinol preparation process makes In Site technology combine with batchwise polymerization, promptly at first in polymeric kettle, add quantitative toluene and be the sodium-naphthalene catalyzer of solvent with the tetrahydrofuran (THF), add the 1,3-butadiene monomer then continuously, be reacted to specified rate, stop to add divinyl, polymer fluid is pressed into washing still stopped reaction.
The volume ratio of toluene and tetrahydrofuran (THF) is 12～1, and preferred value is 10～2; The mol ratio of sodium-naphthalene and divinyl is 0.3 * 10
-3～8.0 * 10
-3, preferred value is 0.5 * 10
-3～5.0 * 10
-3Polymeric reaction temperature is-50 ℃～100 ℃, and preferred value is 0 ℃～80 ℃.
The volumetric concentration of divinyl in polymeric solution is 20%～70%.
Product 1, the molecular-weight average of 2-divinol (Mn) are that 500～1500,1,2 structural content is 65%～75%.
Product 1, the final structure of 2-divinol is:
Wherein, m, n are natural number.
Of the present invention 1,2-divinol preparation method has outstanding feature and advantage:
1, monomer butadiene concentration height, its volumetric concentration can be up to 50～70%.Therefore, can improve 2.5～3.5 times of throughput, solvent for use is 25～40% of a common batchwise polymerization, can reduce facility investment, therefore can significantly reduce production costs.
2, polymeric reaction temperature is easy to control.By the feed rate of control divinyl, can control reaction heat effectively and emit, to reach the purpose of effective control reaction temperature.Product molecular-weight average and quality all can be effectively controlled.
3, polymerization rate is fast.
Further specify the present invention below in conjunction with embodiment, but do not limit the scope of the invention.
Embodiment 1
Under nitrogen protection, be to add 100mlTHF in the catalyst preparation bottle of 250ml toward volume, 28mmol sodium Metal 99.5 bits, the 25.2mmol naphthalene starts and stirs, and reaction is 6 hours under room temperature, makes cyan sodium-naphthalene solution.Through acid base titration, recording Na ion concentration is 0.189mol/l.
Under nitrogen protection, be to add above-mentioned sodium-naphthalene solution 4.9ml in the polymerization bottle of 250ml toward volume, toluene 19.6ml under agitation slowly feeds polymerization-grade 1,3-butadiene 50 grams (80.6ml), and temperature of reaction is 28 ℃, and the reinforced time is 40 minutes.Reinforced finishing stops to stir, and adds 2ml methyl alcohol termination reaction, and the divinyl volumetric concentration is 70% in the polymeric solution, and reaction soln washs with 3% hydrochloric acid soln 200ml, removes catalyst residue.Evaporate organic solvent, under vacuum, remove the oligopolymer of divinyl then, obtain lurid oily matter 49.6g.Press instrument to measure through the gas-phase permeation of KNAVER type, this low molecular polyhutadiene is 927; Measure with the 260-50 of Hitachi type infrared spectrophotometer, its 1,2 structural content is 74.4%; Trans 1,4 structural content is 16.1%, and cis 1,4 structural content is 9.2%.
Embodiment 2
Sodium Metal 99.5 bits 70mmol.Naphthalene 63mmol, THF250ml, the preparation Na ion concentration is sodium-naphthalene solution of 0.259mol/l.
Be to add above-mentioned sodium-naphthalene solution 20ml in the polymerization bottle of 500ml toward volume, toluene 160ml slowly feeds polymerization-grade 1,3-butadiene 50g (80.6ml), and temperature of reaction is 20.5 ℃, and the reinforced time is 47 minutes.The divinyl volumetric concentration is 67.4% in the polymeric solution.
All the other are with embodiment 1.
Obtain lurid oily matter 50g.This divinol Mn is 620, and its 1,2 structural content is 70.8%, and trans 1,4 structural content is 10.6%, and cis 1,4 structural content is 18.6%.
Embodiment 3
Sodium Metal 99.5 bits 45mmol, naphthalene 40.5mmol, THF100ml, the preparation Na ion concentration is sodium-naphthalene solution of 0.433mol/l.
Is volume that to place temperature be-34.5 ℃ cryostat for the polymerization bottle of 500ml.Feed above-mentioned sodium-naphthalene solution 17.9ml in polymerization bottle, add toluene 108ml, under agitation slowly feed polymerization-grade 1,3-butadiene 60g (96.8ml), the reinforced time is 55 minutes.The divinyl volumetric concentration is 65.6%.
All the other are with embodiment 1.
Obtain the 61.3g light yellow oil.This divinol is 749, and its 1,2 structural content is 69.9%, and trans 1,4 structural content is 12.2%, and cis 1,4 structural content is 15.4%.
Embodiment 4
Sodium Metal 99.5 bits 28mmol, naphthalene 25.2mmol, THF100ml, the preparation Na ion concentration is sodium-naphthalene catalyst solution of 0.189mol/l.
Add above-mentioned sodium-naphthalene catalyzer 2.5ml in the polymerization bottle of 250ml, toluene 25ml slowly feeds polymerization-grade 1,3-butadiene 80.6ml, and temperature of reaction is 80 ℃, and the reinforced time is 45 minutes.The volumetric concentration of divinyl is 58.9% in the polymeric solution.
All the other are with embodiment 1.
Obtain light yellow oil 46.5g.This divinol is 1360; Its 1,2 structural content is 66.3%, and trans 1,4 structural content is 15.1%, and cis 1,4 structural content is 18.6%.
Embodiment 5
Sodium Metal 99.5 bits 70mmol, naphthalene 63mmol, THF250ml, the preparation Na ion concentration is sodium-naphthalene solution of 0.259mol/l.
Be to add above-mentioned sodium-naphthalene catalyst solution 14.3ml in the polymerization bottle of 500ml toward volume, toluene 35.8ml slowly feeds polymerization-grade 1,3-butadiene 509 (80.6ml), and the reinforced time is 1 hour, and temperature of reaction is 65 ℃.The volumetric concentration of divinyl is 65.5% in the polymeric solution.
All the other are with embodiment 1.
Obtain light yellow with shape thing 51.59.This divinol is 602; Its 1,2 structural content is 75.1%, and trans 1,4 structural content is 16.1%, and cis 1,4 structural content is 9.2%.
Embodiment 6
Sodium Metal 99.5 bar 2533mmol, naphthalene 228mmol, THF1l, the preparation Na ion concentration is sodium-naphthalene solution of 0.171mol/l.
Be to add above-mentioned sodium-naphthalene catalyst solution 280ml in 51 the polymeric kettle toward volume, toluene 1100ml slowly feeds polymerization-grade 1,3-butadiene 13649 (2200ml), and the reinforced time is 30 minutes.Add 20ml methyl alcohol termination reaction.The volumetric concentration of divinyl is 61.5% in the polymeric solution.Hydrochloric acid soln 3580ml washing reaction thing with 3%.All the other are with embodiment 1.
Obtain light yellow oil 1350g.This divinol is 1031; Its 1,2 structural content is 72.4%, and trans 1,4 structural content is 12.2%, and cis 1,4 structural content is 15.4%.
Embodiment 7
Sodium Metal 99.5 bar 7.08mol, naphthalene 6.37mol, THF2O1, the preparation Na ion concentration is sodium-naphthalene solution of 0.239mol/l.
Be to add above-mentioned sodium-naphthalene catalyst solution 6l in the polymeric kettle of 300l toward volume, toluene 30l under 50 ℃ of temperature, slowly feeds polymerization-grade 1,3-butadiene 41.54K9 (67l), is all when reinforced 1.5 hours.Add 200ml methyl alcohol termination reaction, the volumetric concentration of divinyl is 66.5% in the polymeric solution.Hydrochloric acid soln 1031 washing reaction products with 3%.
Obtain light yellow oil 42.1Kg.This divinol Mn is 1096; Its 1,2 structural content is 70.77%.Trans 1,4 structural content is 14.26%, and cis 1,4 structural content is 14.97%.
Comparative Examples 1
Adding Na ion concentration is sodium-naphthalene catalyst solution 9.8ml of 0.189mol/l, and toluene 39.2ml all adds 6.2g (10ml) polymerization-grade 1,3-butadiene in the polymerization bottle quickly, and temperature of reaction rises to 85 ℃ immediately.The volumetric concentration of divinyl is 16.9% in the polymeric solution.
From the foregoing description and Comparative Examples as can be seen, adopt of the present inventionly 1,2-divinol preparation method can improve the concentration of monomer divinyl in the polymeric solution greatly, than common batchwise polymerization, can improve throughput 3-3.5 doubly.Simultaneously, owing to reduced solvent load significantly, thus significantly reduce facility investment, cut down the consumption of energy effectively and raw materials consumption.
Claims (5)
1. one kind 1,2-divinol preparation method, employing is the sodium-naphthalene catalyst system of solvent with the tetrahydrofuran (THF), with toluene is chain-transfer agent, make 1, the 3-divinyl carries out the negatively charged ion telomerization, it is characterized in that In Site technology is introduced 1 of employing sodium-naphthalene catalyst system, 2-divinol preparation process, In Site technology is combined with batchwise polymerization, promptly at first in polymeric kettle, add quantitative toluene and be the sodium-naphthalene catalyzer of solvent, add the 1,3-butadiene monomer then continuously with the tetrahydrofuran (THF), the volumetric concentration of divinyl in polymeric solution is 20%～70%, be reacted to specified rate, stop to add divinyl, polymer fluid is pressed into washing still stopped reaction; The volume ratio of toluene and tetrahydrofuran (THF) is 12～1, and the mol ratio of sodium-naphthalene and divinyl is 0.3 * 10
-3～8.0 * 10
-3, polymeric reaction temperature is-50 ℃～100 ℃.
2. according to 1 of claim 1,2-divinol preparation method, the volume ratio that it is characterized in that toluene and tetrahydrofuran (THF) is 10～2.
3. according to 1 of claim 1,2-divinol preparation method, the mol ratio that it is characterized in that sodium-naphthalene and divinyl is 0.5 * 10
-3～5.0 * 10
-3
4. according to 1 of claim 1,2-divinol preparation method is characterized in that polymeric reaction temperature is 0 ℃～80 ℃.
According to claim 1～5 each 1,2-divinol preparation method is characterized in that product 1, the molecular-weight average of 2-divinol (Mn) is that 500～1500,1,2 structural content is 65%～75%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120729A CN1063189C (en) | 1996-11-28 | 1996-11-28 | Preparation of low molecular 1, 2 -polybutadiene |
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|---|---|---|---|
| CN96120729A CN1063189C (en) | 1996-11-28 | 1996-11-28 | Preparation of low molecular 1, 2 -polybutadiene |
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| CN1184122A CN1184122A (en) | 1998-06-10 |
| CN1063189C true CN1063189C (en) | 2001-03-14 |
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| CN96120729A Expired - Lifetime CN1063189C (en) | 1996-11-28 | 1996-11-28 | Preparation of low molecular 1, 2 -polybutadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10312829A1 (en) * | 2002-06-29 | 2004-01-22 | Oxeno Olefinchemie Gmbh | Process for the telomerization of non-cyclic olefins |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD265903A1 (en) * | 1987-11-11 | 1989-03-15 | Buna Chem Werke Veb | METHOD FOR PRODUCING LOW-MOLECULAR POLYBUTADIENES |
| RU2017752C1 (en) * | 1991-04-17 | 1994-08-15 | Акционерное общество открытого типа "Ефремовский завод синтетического каучука" | Method of synthesis of low-molecular 1,2-polybutadiene |
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1996
- 1996-11-28 CN CN96120729A patent/CN1063189C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD265903A1 (en) * | 1987-11-11 | 1989-03-15 | Buna Chem Werke Veb | METHOD FOR PRODUCING LOW-MOLECULAR POLYBUTADIENES |
| RU2017752C1 (en) * | 1991-04-17 | 1994-08-15 | Акционерное общество открытого типа "Ефремовский завод синтетического каучука" | Method of synthesis of low-molecular 1,2-polybutadiene |
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| CN1184122A (en) | 1998-06-10 |
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Owner name: BEIJING YANHUA JILIAN PETROLEUM CHEMICAL CO., LTD. Free format text: FORMER OWNER: BEIJING YANHUA PETROLEUM CHEMICAL CO., LTD. SYNTHETIC RUBBER PLANT Effective date: 20100108 |
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Effective date of registration: 20100108 Address after: No. 26, Ding Dong Road, Yan Shandong Water Development Zone, Beijing, Fangshan District Patentee after: Beijing Yanshan Jilian Petroleum Chemical Co., Ltd. Address before: No. 4, Liyuan Road, Beijing, Fangshan District Patentee before: Synthetic Rubber Plant of Beijing Yanshan Petro-Chemical Industry Corp. |
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