CN1208734A - Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer - Google Patents
Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer Download PDFInfo
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- CN1208734A CN1208734A CN 97113380 CN97113380A CN1208734A CN 1208734 A CN1208734 A CN 1208734A CN 97113380 CN97113380 CN 97113380 CN 97113380 A CN97113380 A CN 97113380A CN 1208734 A CN1208734 A CN 1208734A
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- terminal hydroxy
- liquid polymer
- water
- hydrogen peroxide
- polybutadiene liquid
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- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 20
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 19
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000003750 conditioning effect Effects 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 238000007701 flash-distillation Methods 0.000 claims description 4
- MWCADZVQNIHFGT-UHFFFAOYSA-N 1-anilinopropan-2-ol Chemical compound CC(O)CNC1=CC=CC=C1 MWCADZVQNIHFGT-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GZYBSURBYCLNSM-UHFFFAOYSA-N 3-anilinopropan-1-ol Chemical compound OCCCNC1=CC=CC=C1 GZYBSURBYCLNSM-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the prepn. of multi dispersity terminal hydroxy poly butadiene liquid polymer. It uses butadiene as monomer, water as solvent, hydrogen peroxide as initiator, organic alcohol as regulator. Said method is low in specification requirement of raw material, both industrial and recovered alcohol can be used. The method is characterized by that the yield is high and can be more than 65%, it is simple in operation, low in cost, and wide in product adaptability.
Description
The present invention relates to a kind of preparation method of liquid polymers, specifically a kind of preparation method of hydroxy terminated polybutadiene polymkeric substance.
Terminal hydroxy polybutadiene liquid polymer belongs to the functional polymer compound, recent two decades obtains very fast development abroad, be used to high-tech areas such as space flight, weapons, because the characteristic of itself, the application aspect chemical industry, machinery, building is also extensive day by day more.
The technology of preparing of terminal hydroxy polybutadiene liquid polymer mainly contains ionic polymerization, polymer degradation, polymer terminal group conversion and radical polymerization etc.It is a lot of to adopt the free radical solution polymerization legal system to be equipped with the reported in literature of liquid polybutadiene of terminal hydroxy groupization, as US3673168, US3796762, US4518770 etc., be characterized in that adopt with organic reagents such as ether, alcohol, ketone is the method for solvent more, CN1092781 discloses a kind of with aqueous ethanolic solution, wherein alcoholic acid content is the free radical technology of preparing of 75%-95%, but molecular weight is little, and viscosity is bigger than normal, has limited its purposes.Make solvent with organic compound such as alcohol, ether, ketone or their high density (generally more than 85%) solution, its benefit is to make the narrower polymkeric substance of molecular weight distribution, but simultaneously in polymerization is produced this kind solvent also brought drawback, mainly show as:
1. solvent purity requires highly, and preparation difficulty and cause being worth high has improved the cost of polymer product, has influenced its application in fields such as oil, chemical industry, building materials, civilian tackiness agents;
2. solvent contamination environment, it is big to reclaim energy consumption;
3. solvent easy recurring structure distortion when high temperature polymerization, the separation and purification difficulty, cause the full-flow process cycle long, operation is numerous and diverse, the facility investment expense is big, energy consumption is high, product yield is low, generally below 60%;
4. the goods controllability is poor, product grade is single, is difficult to satisfy the requirement of different purposes.
The purpose of this invention is to provide a kind of to raw material specification require low, with low cost, separate easily, flow process is short, operating procedure is simple, product yield is high, the preparation method of a kind of polymolecularity terminal hydroxy polybutadiene liquid polymer that application range of products is wide.
For achieving the above object, the method applied in the present invention is to be monomer with the divinyl, and hydrogen peroxide is an initiator, and water is solvent, C
2-C
5Organic alcohol as the preparation method of the liquid polymers of the polyhutadiene of the polymolecularity terminal hydroxy groupization of conditioning agent.
With the divinyl is monomer, is initiator with the hydrogen peroxide, it is characterized in that it is solvent that its free radical solution polymerization adopts with water, with C
2-C
5Organic alcohol is conditioning agent, and promptly the add-on in divinyl, hydrogen peroxide, water is 100 mass parts, and each forms add-on: divinyl is 20～85 mass parts, and water is 10～75 mass parts, and hydrogen peroxide is 2～25 mass parts; Method is: the hydrogen peroxide behind divinyl, water and the dilute with water is joined respectively in the polymeric kettle that has whipping appts, hydrogen peroxide can once add or add continuously, intermittent type adds, polyreaction is carried out under 80～150 ℃, the polymerization temperature control mode is preferably ladder cooling or cooling continuously, with C
2-C
5Organic alcohol as conditioning agent, being preferably in polyreaction carries out the process discontinuous or joins in the reactor continuously, can add with hydrogen peroxide, also can add separately, the consumption of alcohol is 0～80m% of the add-on of water, after polyreaction finishes, unreacted divinyl is through flash distillation and compression Separation and Recovery, after alcohol is extracted, the polymkeric substance glue is through leaving standstill, washing, promptly get goods after the drying, concrete grammar as: alcohol extract by distillation tower, the glue that contains polymkeric substance leaves standstill 24～36 hours after scouring under 20～105 ℃, can wash for several times with aqueous sodium hydroxide washes earlier, wash with water, last polymer mother liquor promptly got goods through roll bed or thermopnore moisture eliminator down in dry 0.1～26 hour at 105～185 ℃.
Contained vinylacetylene in the polymerization single polymerization monomer divinyl of the present invention, propine, butene-1, the concentration of impurity such as dimer is not more than 1060ppm and gets final product, the optimal addn of divinyl is 40～75 mass parts, water can be deionized water, distilled water or contain 0.1～15%N, the ortho-water of two (2-hydroxypropyl) aniline of N-, N, being added in the polymerization process of two (2-hydroxypropyl) aniline of N-is favourable to improving dispersion effect, the optimal addn of water is 35～70 mass parts, the most handy good mixing effect of type of agitator, good dispersity, the agitator that shearing force is little, as cloth Shandong Martin's type, frame-type etc., the polymerization temperature control mode is preferably ladder cooling or cooling continuously, the reaction initial temperature generally is controlled at more than 100 ℃, rising with polymerisation conversion reduces polymerization temperature gradually, cooling is per hour to fall 2.5-18 ℃ of the best, optimal reaction temperature is 100～135 ℃, the optimal addn of alcohol is 12～60m% of the add-on of water, organic alcohol as conditioning agent comprises ethanol, Virahol, the trimethyl carbinol, season amylalcohol, specification requirement to alcohol is wide, industry, recovery and reagent alcohol all do not influence the quality of the polymkeric substance of the preparation method's gained that adopts polymolecularity hydroxy-terminated polybutadienes polymkeric substance of the present invention.
Characteristics of the present invention are:
1. adopt preparation method of the present invention, low to the specifications of raw materials requirement, be solvent owing to adopt, and organic alcohol just add as conditioning agent with water, add-on reduces greatly, therefore reduced the cost of polymer product, widened Application Areas, avoided the disadvantage that adopts organic compound to bring as solvent, a whole set of techniqueflow is short, operating procedure is simple, three-waste free pollution, the product yield height can reach more than 65%.
2. adopt preparation method of the present invention, alcohol mainly is to use as conditioning agent, suppressing the ultra-high molecular weight polyhutadiene forms, avoid reaction between the macromole and gelation, promote the polymer phase capacitive of different molecular weight simultaneously, thereby improve the molecular parameter and the quality product of hydroxy-terminated polybutadienes, its consumption can be regulated according to the field difference of polymer product application, alcohol adds in polymerization process in addition, avoided alcohol that distortion at high temperature takes place, alcohol is fully utilized, can meets the demands with few add-on.
3. adopt preparation method of the present invention, the control mode of polymerization temperature is preferably ladder cooling or cooling continuously.Ladder cooling or continuous cooling can be satisfied the reaction requirement of the polymerization system of different polymer contents, under polymerization initial stage high temperature, to improve low viscosity system productive rate, reduce temperature of reaction gradually with reaction, with the purpose of avoiding cross-linking reaction between the macromole preferably, reaching to improve the polymeric articles quality and improve product yield.
The preparation method of polymolecularity terminal hydroxy polybutadiene liquid polymer of the present invention, have that technical process is short, simple to operate, separation and dehumidification system be reasonable, three-waste free pollution, low to the specifications of raw materials requirement, the product yield height can reach the characteristics more than 65%, the polymeric articles rerum natura wide ranges that obtains, be suitable for different application field such as urethane, coating, tackiness agent, modifying plastics, RIM goods, cast tire etc., can reduce product cost 1/2～2/3, remarkable in economical benefits.
Embodiment 1
In 50 liters of stainless steel autoclaves, add divinylic monomer 10kg, be added with N, the pure water 5kg of N-(hydroxypropyl) aniline 0.5kg, 26.7% hydrogen peroxide 4kg, polymerization time are 4.5 hours, after polymerization, added 26.7% the hydrogen peroxide of 2kg and 1kg in the 3rd hour and the 4th hour respectively, polymerization temperature was controlled at 126 ℃ at the 1st hour, was controlled at 121 ℃ on the 2nd hour, was controlled at 116 ℃ on the 3rd hour, be controlled at 110 ℃ on the 4th hour, and be maintained to the reaction end.After polyreaction finished, unreacted divinyl was through flash distillation and compression Separation and Recovery, and the glue that contains polymkeric substance is washed 3 times with aqueous sodium hydroxide washes after leaving standstill 34 hours under 68 ℃ again, uses deionized water wash at last.The glue drying is finished in the thermopnore moisture eliminator, its bed temperature is 120 ℃, time of drying is at 12min, promptly get terminal hydroxy polybutadiene liquid polymer 8.5kg, yield reaches 85%, and its main physical index is Mn (GPC method, as follows) 3271, the molecular weight peak shape is the both shoulders peak, viscosity 14.77Pa.s.
Embodiment 2
In 50 liters of stainless steel autoclaves, add the 5kg deionized water, divinylic monomer 12kg, the hydrogen peroxide 6kg of disposable adding 25.7%, polymerization time is 4 hours, the polymerization initial temperature is controlled to be 129.8 ℃, adopt continuous cooling method, per hour lower the temperature 4.8 ℃, final temp is controlled at 104 ℃ of reactions to be finished, polymerization the 2.5th hour, 3.5 hour add 85% industrial alcohol 0.65kg and 1.2kg respectively, after reaction finished, unreacted divinyl was through flash distillation and compression Separation and Recovery, alcohol extracts through distillation tower, the glue that contains polymkeric substance is washed 3 times with aqueous sodium hydroxide washes after leaving standstill 28 hours under 95 ℃ again, uses deionized water wash at last.The glue drying is finished in the thermopnore moisture eliminator, and its bed temperature is 150 ℃, 5 hours time of drying.Obtain hydroxy terminated polybutadiene liquid polymeric 8.2kg, yield 68.3%, its main physical index is: Mn2926, the molecular weight peak shape is bimodal, viscosity 14.15Pa.s.
Embodiment 3
In 50 liters of stainless steel autoclaves, add deionized water 2kg, divinylic monomer 9kg, 24.8m% hydrogen peroxide 3.4kg, 24.8% hydrogen peroxide and the season amylalcohol 1.3kg of all the other 2.7kg, mend continuously from the 2nd hour per hour to increase progressively 20% speed, finish until reaction, polymerization time is 4.5 hours, and polymerization temperature is controlled to be the ladder cooling, wherein first hour 132 ℃, second hour 126 ℃, the 3rd hour 120 ℃, the 4th hour 114 ℃.Other aftertreatment can obtain terminal hydroxy polybutadiene liquid polymer 6.2kg with embodiment 2, and yield is 68.89%, and its main physical index is: Mn3006, molecular weight bimodal distribution, viscosity 5.3Pa.s.
Embodiment 4
In 50 liters of stainless steel autoclaves, add deionized water 6.8kg, divinylic monomer 10kg, 21.5% hydrogen peroxide 4kg, polymerization time are 3.5 hours, mended Virahol 4.6kg at the 2.5th hour, polymerization temperature control is with embodiment 3, and reaction finishes other aftertreatment of back with embodiment 2, can obtain hydroxy terminated polybutadiene liquid polymers 8.45kg, yield is 84.5%, its main physical index is: Mn2415, molecular weight is bimodal distribution, viscosity 5.36Pa.s.
Comparative example 1
In 50 liters of stainless steel autoclaves, add divinylic monomer 10kg, 24.5% hydrogen peroxide 7kg, dehydrated alcohol 5kg, polymerization temperature are 118 ℃, polymerization time is 4.5 hours, after reaction finishes, add the dehydrated alcohol of polymer mother liquor amount 40m%, sedimentation is after 24 hours, wash with water three times, polymkeric substance after the separation is sent into still formula moisture eliminator, obtains goods in dry 12 hours down at 105 ℃, and containing aqueous ethanolic solution in a large number must reclaim ethanol with the ethanol recovery tower.Obtain terminal hydroxy polybutadiene liquid polymer 3.2kg, yield is 45.7%, and its main physical index is: Mn2418, molecular weight is normal distribution, viscosity 11.85Pa.s.
Claims (6)
1. the preparation method of a polymolecularity terminal hydroxy polybutadiene liquid polymer is a monomer with the divinyl, is initiator with the hydrogen peroxide, it is characterized in that it is solvent that its free radical solution polymerization adopts with water, with C
2-C
5Organic alcohol is conditioning agent, and promptly the add-on in divinyl, hydrogen peroxide, water is 100 mass parts, and each forms add-on: divinyl is 20～85 mass parts, and water is 10～75 mass parts, and hydrogen peroxide is 2～25 mass parts; Method is: the hydrogen peroxide behind divinyl, water and the dilute with water is joined respectively in the polymeric kettle that has whipping appts, hydrogen peroxide once adding or continous way, intermittent type adds, and polyreaction is carried out under 80～150 ℃, with C
2～C
5Organic alcohol as conditioning agent, can add with hydrogen peroxide, also can add separately, the consumption of alcohol is 0～80m% of the add-on of water, after polyreaction finishes, promptly gets terminal hydroxy polybutadiene liquid polymer through aftertreatment.
2. the preparation method of terminal hydroxy polybutadiene liquid polymer according to claim 1 is characterized in that the polymerization temperature control mode is ladder cooling or cooling continuously.
3. the preparation method of terminal hydroxy polybutadiene liquid polymer according to claim 1 and 2, it is characterized in that aftertreatment is meant that unreacted divinyl is through flash distillation and compression Separation and Recovery, alcohol extracts through distillation tower, the glue that contains polymkeric substance left standstill under 20～105 ℃ 24～36 hours, and the polymer mother liquor after the washing promptly got terminal hydroxy polybutadiene liquid polymer in 0.1～26 hour through 105～185 ℃ of dryings.
4. the preparation method of terminal hydroxy polybutadiene liquid polymer according to claim 1 and 2 is characterized in that organic alcohol carries out the process discontinuous or joins in the reactor continuously in polyreaction.
5. the preparation method of terminal hydroxy polybutadiene liquid polymer according to claim 1 and 2 is characterized in that adding in the water N of 0.1～15m%, two (2-hydroxypropyl) aniline of N-.
6. the preparation method of terminal hydroxy polybutadiene liquid polymer according to claim 1 and 2 is characterized in that C
2-C
5Organic alcohol be ethanol, Virahol, the trimethyl carbinol, season amylalcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113380A CN1075821C (en) | 1997-08-14 | 1997-08-14 | Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97113380A CN1075821C (en) | 1997-08-14 | 1997-08-14 | Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1208734A true CN1208734A (en) | 1999-02-24 |
| CN1075821C CN1075821C (en) | 2001-12-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97113380A Expired - Fee Related CN1075821C (en) | 1997-08-14 | 1997-08-14 | Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer |
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| Country | Link |
|---|---|
| CN (1) | CN1075821C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443514C (en) * | 2006-08-17 | 2008-12-17 | 山东大学 | Polymer of terminal dihydroxy, and prepartion method |
| CN103467975A (en) * | 2013-09-12 | 2013-12-25 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| WO2015027367A1 (en) * | 2013-08-30 | 2015-03-05 | 中国石油天然气股份有限公司 | Macromolecule friction modifier with two polar ends |
| CN114031482A (en) * | 2021-05-19 | 2022-02-11 | 黎明化工研究设计院有限责任公司 | Method for reducing acetaldehyde content in alcohol recovered by hydroxyl-terminated polybutadiene production process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092781A (en) * | 1994-01-11 | 1994-09-28 | 青岛化工学院 | The polymerization process for preparing of terminal hydroxy liquid polybutadiene |
-
1997
- 1997-08-14 CN CN97113380A patent/CN1075821C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443514C (en) * | 2006-08-17 | 2008-12-17 | 山东大学 | Polymer of terminal dihydroxy, and prepartion method |
| WO2015027367A1 (en) * | 2013-08-30 | 2015-03-05 | 中国石油天然气股份有限公司 | Macromolecule friction modifier with two polar ends |
| CN104419498A (en) * | 2013-08-30 | 2015-03-18 | 中国石油天然气股份有限公司 | Macromolecule friction modifier with two polar ends |
| CN103467975A (en) * | 2013-09-12 | 2013-12-25 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| CN103467975B (en) * | 2013-09-12 | 2015-04-01 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| CN114031482A (en) * | 2021-05-19 | 2022-02-11 | 黎明化工研究设计院有限责任公司 | Method for reducing acetaldehyde content in alcohol recovered by hydroxyl-terminated polybutadiene production process |
| CN114031482B (en) * | 2021-05-19 | 2023-05-05 | 黎明化工研究设计院有限责任公司 | Method for reducing acetaldehyde content in alcohol recovered by hydroxyl-terminated polybutadiene production process |
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| Publication number | Publication date |
|---|---|
| CN1075821C (en) | 2001-12-05 |
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