CN1092781A - The polymerization process for preparing of terminal hydroxy liquid polybutadiene - Google Patents
The polymerization process for preparing of terminal hydroxy liquid polybutadiene Download PDFInfo
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- CN1092781A CN1092781A CN 94110409 CN94110409A CN1092781A CN 1092781 A CN1092781 A CN 1092781A CN 94110409 CN94110409 CN 94110409 CN 94110409 A CN94110409 A CN 94110409A CN 1092781 A CN1092781 A CN 1092781A
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- polymerization process
- terminal hydroxy
- liquid polybutadiene
- polymerization
- hydroxy liquid
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Abstract
The present invention relates to a kind of is the aqueous ethanolic solution polymerization process of the terminal hydroxy liquid polybutadiene of raw material with divinylic monomer, ethanol and hydrogen peroxide, is that the certain ethanol of terminal hydroxy liquid polybutadiene polymerization technique employing is solvent, the H with 30%
2O
2Be initiator, carry out polyreaction, H in the polymerization process under given conditions
2O
2Divide 3-5 times and add, its polymerization cycle is 3 hours, H
2O
2Consumption reduced by 10-15%, monomer conversion has improved 50%, it is few compared with prior art to have a facility investment, technology is simple, solvent recovering rate height, advantage such as product price is low.
Description
The present invention relates to a kind of is the polymerization process of feedstock production liquid hydroxyl polyhutadiene with divinylic monomer, ethanol and hydrogen peroxide etc.
Terminal hydroxy liquid polybutadiene claims polybutadiene diol again, (being called for short HTPB) (hydroxyl-terminated polybutadiene), it is a kind of liquid polymers that the eighties just moves towards the industrialization afterwards in the world, HTPB is one of main raw material of polyurethane industrial, has a wide range of applications at aspects such as foam material, coating, tackiness agent, elastomerics, RIM goods, cast tires.The method of synthetic HTPB has several different methods such as anionoid polymerization, polymer degradation, polymer terminal group conversion, free radical solution polymerization, but really realizes the industrialized free radical solution polymerization method of having only.Used solvent has the mixture of Virahol, acetone, hexanaphthene, methyl alcohol and benzene.As described in United States Patent (USP) 3673168, its solvent is ether alcohol, keto-alcohol, ketone etc., and the solvent that Arco company is used to produce HTPB is a Virahol.The free radical solution polymerization that carries out HTPB with ether alcohol, Virahol and ketones solvent exists following shortcoming:
1. solvent is worth height, has caused the product cost height.
2. the very easily oxidation of above-mentioned solvent can be oxidized to more than 20 kind of organism such as aldehyde, acid, has brought a lot of troubles for product purification and solvent recuperation.
3. because multiple organic generation had both consumed solvent, can cause the pollution of environment and product again.
4. monomer conversion is low, and general transformation efficiency is 50%.
5. solvent recuperation and product purification complex process, facility investment is big.
The objective of the invention is to overcome the shortcoming that exists in the prior art, seeking a kind of is solvent with ethanol, adopts the polymerization process of conventional feedstock production terminal hydroxy liquid polybutadiene product, and make this processing method technology simple, facility investment is few, the solvent recovering rate height, and product cost is low.
In order to realize the foregoing invention purpose, the present invention is a main raw material with divinylic monomer, ethanol and hydrogen peroxide etc., by a certain percentage in stainless steel autoclave, according to adding hydrogen peroxide earlier, add ethanol again, add the order of addition(of ingredients) of divinyl then, under certain polymerization temperature, polymerization pressure and polymerization cycle condition, carry out polymerization, ethanol to aqueous phase after polymerization finishes reclaims, and oil phase is made product again after washing, filtration and evaporation.Polymerization process is to add H in aqueous ethanolic solution
2O
2Be initiator, make divinylic monomer carry out polymerization.The present invention is that solvent has starting material and is easy to get with the alcoholic acid aqueous solution compared with prior art, reclaims that technology is simple, the rate of recovery is high and can be recycled, and initiator amount is few, and product cost is low, and facility investment waits outstanding advantage less.
In the present invention, in order to reduce the consumption of initiator, the present invention has improved the method for three kinds of whole disposable addings of raw material in the HTPB Jian Xiefa production technique, in reaction time, with required H
2O
2Divide 3-5 time and add, make H
2O
2Consumption reduced 10-20%.
Example 1.
320 kilograms of divinylic monomers, 320 kilograms of 95% industrial alcohols, 90 kilograms of 30% hydrogen peroxide carry out polymerization in 1000 liters stainless steel autoclave, order of addition(of ingredients) is to add 40 kilograms of hydrogen peroxide earlier, add ethanol, add divinyl again, polymerization temperature is 110-125 ℃, and polymerization pressure is 15-25MPa, polymerization cycle is three hours, adds 25 kilograms of hydrogen peroxide after polymerization when one hour and two hours respectively.After reaction finished, unreacted monomer reclaimed through evaporator overhead condenser.Reaction product is after washing in 1: 1, and water removes the ethanol recovery tower, reclaims 295 kilograms of 95% ethanol.Oil phase washes twice again, and the film under vacuum vaporizer is sent in centrifuging, steams micro-moisture, makes water-content 1 * 10
-4-1 * 10
-3Final 270 kilograms of products, the product water-content 1.6 * 10 of getting
-4, number-average molecular weight is 2100, and hydroxy functionality is 2.04, and viscosity (25 ℃) is 4500cp.
Example 2.
300 kilograms of divinylic monomers, 330 kilograms of 75% ethanol, 30%H
2O
2100 kilograms, its operation steps such as example 1 get 260 kilograms of products, water-content 1.35 * 10
-4, number-average molecular weight 1850, hydroxyl functionality 2.03, viscosity (25 ℃) 4000cp.
Claims (3)
1, the present invention relates to a kind of is the method for feedstock production terminal hydroxy liquid polybutadiene with divinylic monomer, ethanol hydrogen peroxide etc., and it is characterized in that: polymerization process is in aqueous ethanolic solution, adds H
2O
2Be initiator, make divinylic monomer carry out polymeric.
2, the polymerization process for preparing of terminal hydroxy liquid polybutadiene according to claim 1 is characterized in that its alcoholic acid content is 75-95% in the aqueous ethanolic solution.
3, the polymerization process for preparing of terminal hydroxy liquid divinyl according to claim 1 is characterized in that being H
2O
2Adding be to take gradation adding method, generally be that branch 3-5 time adds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110409 CN1092781A (en) | 1994-01-11 | 1994-01-11 | The polymerization process for preparing of terminal hydroxy liquid polybutadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110409 CN1092781A (en) | 1994-01-11 | 1994-01-11 | The polymerization process for preparing of terminal hydroxy liquid polybutadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1092781A true CN1092781A (en) | 1994-09-28 |
Family
ID=5034380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94110409 Pending CN1092781A (en) | 1994-01-11 | 1994-01-11 | The polymerization process for preparing of terminal hydroxy liquid polybutadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1092781A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075821C (en) * | 1997-08-14 | 2001-12-05 | 中国石油化工集团公司 | Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer |
| CN100453587C (en) * | 2007-04-13 | 2009-01-21 | 青岛伊科思新材料股份有限公司 | Recovery and using method of solution and unreaction monomer in process of producting polymer by solution polymerization process |
-
1994
- 1994-01-11 CN CN 94110409 patent/CN1092781A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075821C (en) * | 1997-08-14 | 2001-12-05 | 中国石油化工集团公司 | Method for prepn. of polydispersity terminal hydroxy polybutadiene liquid polymer |
| CN100453587C (en) * | 2007-04-13 | 2009-01-21 | 青岛伊科思新材料股份有限公司 | Recovery and using method of solution and unreaction monomer in process of producting polymer by solution polymerization process |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |