CN1179988C - Optimized production process of terminal hydroxy liquid polybutadiene - Google Patents
Optimized production process of terminal hydroxy liquid polybutadiene Download PDFInfo
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- CN1179988C CN1179988C CNB021100950A CN02110095A CN1179988C CN 1179988 C CN1179988 C CN 1179988C CN B021100950 A CNB021100950 A CN B021100950A CN 02110095 A CN02110095 A CN 02110095A CN 1179988 C CN1179988 C CN 1179988C
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Abstract
The present invention relates to optimized production technology of hydroxy-terminated liquid polybutadiene, which uses oxydol as an initiating agent and butadiene as monomers to make a polymerization reaction in an organic solvent. The optimized production technology is mainly characterized in that the temperature of the product of the polymerization reaction is reduced to 60 to 85 DEG C; the product is degassed, filtered and deposited into layers; and the oil phase is washed by hot water; the product is finally obtained by dewatering and filtration. Before the reaction is carried out, the butadiene is washed by alkali solution having the concentration of 7 to 15% until the content of a polymerization inhibitor is less than 30 ppm, and then the solution is washed by water. The initiating agent of oxydol is added for once to a reaction system to initiate the butadiene to make a polymerization reaction. The optimized production technology optimizes reaction conditions and the post-processing process after the polymerization reaction and shortens the technological line by analyzing the existing technological line. The optimized production technology has the advantages of stable technology and high yield of the product, and furthermore, the quality of the product is greatly increased.
Description
Technical field
The present invention relates to the production technique of terminal hydroxy liquid polybutadiene.
Background technology
Terminal hydroxy liquid polybutadiene claims polybutadiene diol again, be called for short HTPB, it is a kind of liquid polymers that grows up in the sixties, by chain extension and crosslinking curing, can be made into the elastomerics of tridimensional network, because it has identical performance with solid rubber, also be called fluid rubber.U.S. ARCO had built up industrial production device in 1971, and USSR (Union of Soviet Socialist Republics), France, Japan also have corresponding industrialized unit to put into production then, and its purposes is as solid rocket propellant, rocket engine lining etc. the earliest.Except that military, many purposes are also arranged: the properties-correcting agent of (1) rubber plastic aspect civilian; (2) electrical equipment potting material; (3) sealing material; (4) caking agent; (5) a plurality of fields such as cast tyre and full capping.
China is from the begin one's study exploitation of HTPB of the seventies, mainly contain Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences, Liming chemical Inst, Qingtao Chemical Engineering College, research institute of Lan Hua company etc., through constantly research these years, technical had very big breakthrough, but do not enter the suitability for industrialized production stage yet.
The technology that prior art is taked is to be initiator with the hydrogen peroxide, and ethanol is solvent, the polyreaction that the monomer divinyl carries out.Aspect processing condition, mainly there is following problem:
1, unstable product quality, fluctuation is big;
2, the products production yield is low, the production cost height;
3, have emulsion in the production process, each link of production technique is not smooth;
4, prescription is unreasonable, and processing parameter control is unstable, does not have on the safety to ensure.
Summary of the invention
Technical problem to be solved by this invention is to overcome the problem that above-mentioned prior art exists, and the optimization production technology of terminal hydroxy liquid polybutadiene is provided, and optimizes processing condition, prepares up-to-standard stable terminal hydroxy liquid polybutadiene.
The optimization production technology of terminal hydroxy liquid polybutadiene of the present invention, be to be initiator with the hydrogen peroxide, divinyl is the polyreaction that monomer carries out under organic solvent, it is characterized in that product after the polyreaction is through being cooled to 60～85 ℃, the degassing, filtering, sedimentation layering then, the water washing of oil phase reusable heat, last dewatering and filtering obtains product.
Described hot wash is meant the hot water more than 60 ℃.Dehydrate and preferably adopt thin film evaporation, temperature is 120～200 ℃.
Divinyl is with 7～15% alkali liquid washing before the reaction, remove stopper (impurity in the divinyl) to level of inhibitor less than 30ppm, wash then.Washing is that alkali lye remaining in the divinyl is washed off, makes butadiene solution be neutral.
The initiator hydrogen peroxide is that disposable join in the reaction system caused divinyl and carried out polyreaction.
The weight ratio of divinyl, hydrogen peroxide, organic solvent is 1: (0.021～0.16): 0.5～1.5.
Temperature of reaction is 90～120 ℃, and the reaction times is 1.0～3.0 hours.
Organic solvent can be selected methyl alcohol, ethanol, Virahol or acetone etc., preferred alcohol for use.The concentration of initiator, monomer, solvent is ethanol mass concentration 〉=95% (other organic solvent adopts the high density product equally) preferably, hydrogen peroxide mass concentration 〉=27.5%, divinyl mass concentration 〉=99.5%, alkynes content＜50ppm in the divinyl.The proportional quantity of above-mentioned three kinds of materials is to calculate with the amount of pure substance.
Reaction conditions, post-reaction treatment process and initiator, solvent, monomeric amount that the present invention determines by a large amount of experiments are that the present invention produces qualified stable product more reasonable proportioning and reaction conditions.
Advantage of the present invention:
By careful analysis to the prior art operational path, optimized the last handling process after reaction conditions and the polyreaction, can produce qualified stable terminal hydroxy liquid polybutadiene.Solved the difficult problem of kiss-coating, polymkeric substance influence stirring and polyreaction.Shorten operational path, reduced the mechanical separation mode that prior art adopts, increased sedimentation, changed secondary water washing and be once washing, solved the emulsion of product.Thin film evaporation has replaced traditional tower still distillatory method, and product drying is effective, and the yield height has improved quality product greatly.On reaction unit, can increase divinyl and alcoholic acid retrieving arrangement, reduce production costs greatly.The terminal hydroxy liquid polybutadiene outward appearance that the present invention obtains is colourless or light yellow thick liquid, hydroxyl value (mmol/g) is 0.55～1.05, and number-average molecular weight (Mn) is 2300～4500, moisture≤0.10 (m/m), superoxide is in hydrogen peroxide≤0.05% (m/m).
The terminal hydroxy liquid polybutadiene that the present invention produces has characteristics such as viscosity is low, transparency good, color is pure, taste is little, and quality product has obtained the favorable comment in market.
Embodiment
The present invention is not limited by following examples.
Embodiment one
Divinyl is fed in the caustic treater of 10% sodium hydroxide with pump, the stopper in the divinyl is deviate to 30ppm, feed water washing tank then micro-alkali remaining in the divinyl is removed, the back is standby in the divinyl test tank.
Divinyl mass concentration through above-mentioned processing is 99.5%, wherein alkynes content is less than 50ppm, with mass concentration be that 27.5% hydrogen peroxide, mass concentration are that 95% ethanol joins in 1000 liters of reactors of mechanical seal according to weight ratio 1: 0.047: 0.8 (amounting to scale), in half an hour, be warming up to 117 ℃ and reacted 2.5 hours rapidly.Product after the polyreaction is cooled to 75 ℃, after outgasing material from still after filtration to slurry tank sedimentation layering, oil phase (glue) moves to water washing tank with 90 ℃ of hot washes, sedimentation layering again, glue is gone in the glue jar with air pressure, dewater in thin-film evaporator under 150 ℃, the back obtains finished product with air pressure with the glue in the middle finished product jar after filtration in middle finished product jar.
The hydroxyl value of product terminal hydroxy liquid polybutadiene is 0.83 mmol/g, and number-average molecular weight is 2900, and viscosity is 3.6 (Pa.S, 40 ℃), moisture 0.05, superoxide＜0.05.
Embodiment two:
According to the technology of embodiment one, divinyl and 27.5% hydrogen peroxide, 95% ethanol react according to weight ratio 1: 0.030: 0.65 (amounting to scale).119 ℃ of temperature of reaction, 2 hours reaction times.
The hydroxyl value of product terminal hydroxy liquid polybutadiene is 0.60 mmol/g, and number-average molecular weight is 3800, and viscosity is 8.4 (Pa.S, 40 ℃), moisture 0.05 (m/m), superoxide＜0.05% (m/m).
Embodiment three:
According to the technology of embodiment one, divinyl and 27.5% hydrogen peroxide, 95% ethanol react according to weight ratio 1: 0.041: 0.95 (amounting to scale).115 ℃ of temperature of reaction, 3 hours reaction times.
The hydroxyl value of product terminal hydroxy liquid polybutadiene is 0.76mmol/g, and number-average molecular weight is 3000, and viscosity is 3.1 (Pa.S, 40 ℃), moisture 0.05 (m/m), superoxide＜0.05% (m/m).
Embodiment four:
According to the technology of embodiment one, divinyl and 30% hydrogen peroxide, 95% Virahol react according to weight ratio 1: 0.072: 1.2 (amounting to scale).116 ℃ of temperature of reaction, 2.5 hours reaction times.
The hydroxyl value of product terminal hydroxy liquid polybutadiene is 1.02mmol/g, and number-average molecular weight is 2200, and viscosity is 1.95 (Pa.S, 40 ℃), moisture 0.05 (m/m), superoxide＜0.05% (m/m).
Claims (10)
1, the optimization production technology of terminal hydroxy liquid polybutadiene, be to be initiator with the hydrogen peroxide, divinyl is the polyreaction that monomer carries out under organic solvent, it is characterized in that product after the polyreaction is through being cooled to 60～85 ℃, the degassing, filtering, sedimentation layering then, the water washing of oil phase reusable heat, last dewatering and filtering obtains product.
2, technology according to claim 1 is characterized in that described hot water wash is meant the hot water more than 60 ℃.
3, technology according to claim 1 is characterized in that described dehydration employing thin film evaporation, and temperature is 120～200 ℃.
4, technology according to claim 1, divinyl alkali cleaning before it is characterized in that reacting removes stopper, to level of inhibitor less than 30ppm, wash then.
5, technology according to claim 1 is characterized in that disposable join in the reaction system of described initiator hydrogen peroxide cause divinyl and carry out polyreaction.
6, technology according to claim 1 is characterized in that temperature of reaction is 90～120 ℃.
7, technology according to claim 6 is characterized in that the reaction times is 1.0～3.0 hours.
8, technology according to claim 1, the weight ratio that it is characterized in that divinyl, hydrogen peroxide, organic solvent is 1: (0.021～0.16): 0.5～1.5.
9,, it is characterized in that described organic solvent is methyl alcohol, ethanol, Virahol or acetone according to claim 1 or 8 described technologies.
10,, it is characterized in that organic solvent is an ethanol, ethanol mass concentration 〉=95%, hydrogen peroxide mass concentration 〉=27.5%, divinyl mass concentration 〉=99.5%, alkynes content＜50ppm in the divinyl according to claim 1 or 8 described technologies.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021100950A CN1179988C (en) | 2002-03-02 | 2002-03-02 | Optimized production process of terminal hydroxy liquid polybutadiene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021100950A CN1179988C (en) | 2002-03-02 | 2002-03-02 | Optimized production process of terminal hydroxy liquid polybutadiene |
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| CN1442436A CN1442436A (en) | 2003-09-17 |
| CN1179988C true CN1179988C (en) | 2004-12-15 |
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| CNB021100950A Expired - Fee Related CN1179988C (en) | 2002-03-02 | 2002-03-02 | Optimized production process of terminal hydroxy liquid polybutadiene |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565863A (en) * | 2016-10-14 | 2017-04-19 | 北京理工大学 | Refined HTPB used for pouring PBX explosives and propellants and preparation method |
| CN114276479A (en) * | 2021-12-22 | 2022-04-05 | 天元(杭州)新材料科技有限公司 | Preparation method of carboxyl-terminated liquid rubber |
| CN115197644A (en) * | 2022-08-16 | 2022-10-18 | 福建中意铁科新型材料有限公司 | Cold-coating non-curing rubber asphalt waterproof coating, preparation and construction |
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Granted publication date: 20041215 |