CN86101033A - A kind of synthetic method of polyester polyol - Google Patents
A kind of synthetic method of polyester polyol Download PDFInfo
- Publication number
- CN86101033A CN86101033A CN 86101033 CN86101033A CN86101033A CN 86101033 A CN86101033 A CN 86101033A CN 86101033 CN86101033 CN 86101033 CN 86101033 A CN86101033 A CN 86101033A CN 86101033 A CN86101033 A CN 86101033A
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- CN
- China
- Prior art keywords
- ester
- acid
- polyester polyol
- reaction
- production process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is a kind of synthetic method of polyester polyol.The waste residue (G ester) or the p-methylbenzoic acid of discharging in mixed dicarboxylic acid that reclaims in the waste liquid with the discharge of hexanodioic acid production process and the poly terephthalic acid Diethylene Glycol ester production process, the waste residue of discharging in the dimethyl terephthalate (DMT) production process (C ester), dibasic alcohol and trivalent alcohol, preparation is produced polyester polyol through over-churning and transesterification reaction by a certain percentage.Raw materials used needn't separation and make with extra care, thereby production cost that can general production method descends 54%, and polyester form has the good advantage of Fire retardance temperature tolerance, do not produce secondary environmental pollution.
Description
The invention belongs to the synthetic method of resin.Products obtained therefrom can be used for polyurethane industrial etc.
Urethane foam is to develop one of synthetic materials faster at present both at home and abroad, and it has the branch of polyester type and polyether-type.The development of polyester type material and suitability for industrialized production, prior to polyether-type, and at aspects such as physical strength, oil resistant, fire-retardant, resistance toheats, all than polyether-type for good.But in the long term, because the raw materials cost height of synthesizing polyester section bar material, and make it in development and application, be subjected to certain restriction.
Polyester polyol is a main raw material of producing urethane, and in prior art, the many alcohol of synthesizing polyester generally adopt organic multicomponent acid as hexanodioic acid, pimelic acid etc. or acid anhydrides such as phthalic anhydride and polyvalent alcohol such as ethylene glycol, propylene glycol, butyleneglycol, a condensed ethandiol, tirethylene glycol etc.; Trivalent alcohol compound such as TriMethylolPropane(TMP), glycerol etc. are produced through polycondensation.(see China Chemical Industry Press at " urethane foam ", volumes such as Zhu Fang Yusheng Lv Min) in (the 215th page to 220 pages) book, introduced the main raw material of producing rigid urethane foam, the production of polyester polyol is with hexanodioic acid, phthalate anhydride and TriMethylolPropane(TMP) (or glycerine), with mol ratio preparation in 2.5: 0.25: 4, about 200 ℃, decompression down, through the condensation reaction more than 20 hours, just can finish.Polyprotonic acid and the polyvalent alcohol of also having introduced other in the book are raw material, produce the method for polyester polyol.But described the whole bag of tricks all is that employing is single, and purified polyprotonic acid and polyvalent alcohol are raw material, produce polyester polyol.This also is the high one of the main reasons of polyester polyol production cost.
Purpose of the present invention is to seek a kind of new many pure raw materials of synthesizing polyester and preparation method thereof.Make its refuse obtain comprehensive utilization, eliminate environmental pollution, reduce the production cost of polyester polyol simultaneously.
Main points of the present invention, be the main raw material of the many alcohol of synthesizing polyester, be to utilize the mixed dicarboxylic acid that from the waste liquid that the hexanodioic acid production process is discharged, reclaims, waste residue of discharging in poly terephthalic acid binaryglycol ester (PET) production process (being called for short the G ester) or p-methylbenzoic acid (PTA), the waste residue of discharging in dimethyl terephthalate (DMT) (DMT) production process (being called for short the C ester).
Mixed dicarboxylic acid is formed: Succinic Acid 18 to 30%
Pentanedioic acid 55 to 70%
Hexanodioic acid 15 to 25%
The G ester is formed:
Ethylene glycol 20 to 30%
Diethylene Glycol 8 to 12%
Terephthaldehyde's acid diethylene glycol and derivative 40 to 58% thereof.
The C ester is formed:
1）H
3CooC-
-CooCH
314%
2）H
3CooC-
9%
3）H
3Coo-
8%
4）H
3CooC-
-o-CH
2-
-CooCH
348%
5) other
-CH
2-
-CooCH
3Deng 21%
These raw materials all needn't separate and make with extra care, and are directly used in the synthetic of polyester.Technological process is as follows:
The heating and melting mixed dicarboxylic acid, then with the fused mixed dicarboxylic acid, dibasic alcohol, trivalent alcohol, prepare in reactor to 1/2nd with 1/5th of mixed dicarboxylic acid weight to 1.0 and G ester or C ester by mole ratio 1: 1.2 to 2.1: 0.2.Reaction needs through esterification and transesterification reaction.Esterification in advance, heat up in the limit, and stir on the limit, and esterification reaction temperature is controlled at 130 ℃ to 220 ℃, and when temperature reached 140 ℃, constant temperature 2 hours reacted under normal pressure and nitrogen protection.The water that is generated is reclaimed through condensation by the discharge of reactor top.Transesterification reaction, after same reactor relaying esterification, carry out, when temperature of reaction reaches 220 ℃, constant temperature is 3 to 6 hours again, begin to vacuumize, make the still internal pressure reduce to 600 mmhg by normal pressure, the low-boiling-point substances such as by product alcohols that reaction is generated still reclaim by condenser, when acid number≤when the 2mgKOH/g hydroxyl value reaches 450 to 550mgKOH/g, finish total overall reaction.Entire reaction course needs 20 to 21 hours.
The present invention compares with the method for producing polyester polyol is arranged earlier, and its production technique is simple, and raw materials used is waste liquid, waste residue, do not need again through separation and refining, thereby generally production method method production cost descends 54%, and Fire retardance is good.Because waste liquid, waste residue has obtained whole comprehensive utilizations, can not produce secondary environmental pollution.The polyester polyol that while present method is produced is used to produce rigid urethane foam and present general urethane foam is compared, and especially has the good characteristics of heat resistance.
Example one:
In one 3000 milliliters there-necked flask, add mixed dicarboxylic acid 500 grams, ethylene glycol 448 grams, glycerine 180 grams, G ester 250 grams place there-necked flask in the electric food warmer, heating while stirring, when treating that temperature of charge rises to 140 ℃, constant temperature 2 hours.Under nitrogen protection, continue to be warming up to 220 ℃, constant temperature was driven vacuum pump after 3 to 4 hours again, made its pressure reduce to 600 mmhg gradually by normal pressure.As acid number≤2mgKOH/g, when hydroxyl value is 450 to 550mgKOH/g, get final product discharging.The total overall reaction process needs 20 hours.Pair product water that generates in the reaction process after condenser condenses, separates.The gross weight that feeds intake 1378 grams, product 1074.8 grams, yield 78%.
Quality product: hydroxyl value 490mgKOH/g
Acid number 1.26mgKOH/g
Viscosity (25 ℃) 2500 centipoises
Frothing test: good
Example two:
With example one method, drop into mixed dicarboxylic acid 533 grams, ethylene glycol 508 grams, glycerine 325 grams, C ester 150 grams.
The total amount that feeds intake 1516 grams, output 1167 grams, yield 77%.
Quality product: hydroxyl value 504.9mgKOH/g
Acid number 2mgKOH/g
Viscosity (25 ℃) 3200 centipoises
Frothing test: good
Claims (3)
1; a kind of synthetic method of polyester polyol; with polyprotonic acid and polyvalent alcohol; normal pressure to the decompression and nitrogen protection under; through esterification and transesterification reaction; the present invention is characterised in that: the waste residue (being called for short the G ester) of discharging in mixed dicarboxylic acid that reclaims in the effluent discharge of employing adipic acid production process and poly terephthalic acid binaryglycol ester (PET) production process; or p-methylbenzoic acid (PTA); the main raw material of the waste residue of discharging in dimethyl terephthalate (DMT) (DMT) production process (being called for short the C ester); elder generation's heating and melting mixed dicarboxylic acid; then with mixed dicarboxylic acid; dibasic alcohol; trivalent alcohol by mole ratio 1: 1.2 to 2.1: 0.2 to 1 and G ester or C ester; with 1/5th to 1/2nd of mixed dicarboxylic acid weight; in reactor, prepare; esterification reaction temperature is controlled at 130 ℃ to 200 ℃; when temperature rises to 220 ℃; the beginning transesterification reaction; constant temperature three to six hours; begin decompression; make the still internal pressure reduce to 600 mmhg, as reaction mass acid number≤2mgKOH/g, when the carboxylic value reaches 450 to 550mgKOH/g by normal pressure; reaction finishes, and reaction needs 20 to 24 hours altogether.
2, by the synthetic method of the described polyester polyol of claim 1, it is characterized in that raw materials used mixed dicarboxylic acid, G ester or C ester do not need to be directly used in the reaction through separating and refinement treatment.
3,, when it is characterized in that esterification reaction temperature rises to 140 ℃, needed constant temperature two hours by the synthetic method of the described polyester polyol of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86101033A CN86101033B (en) | 1986-01-31 | 1986-01-31 | Synthesis of polyester of polyhydric alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86101033A CN86101033B (en) | 1986-01-31 | 1986-01-31 | Synthesis of polyester of polyhydric alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101033A true CN86101033A (en) | 1987-09-09 |
| CN86101033B CN86101033B (en) | 1988-01-20 |
Family
ID=4801268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101033A Expired CN86101033B (en) | 1986-01-31 | 1986-01-31 | Synthesis of polyester of polyhydric alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86101033B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979423A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Water-based polymer-polyurethane prepolymer preparation method and application |
| CN110105522A (en) * | 2019-05-31 | 2019-08-09 | 山东理工大学 | The preparation method of waste paint slag polyurethane foamed material |
| CN113234413A (en) * | 2021-05-12 | 2021-08-10 | 新疆天利高新石化股份有限公司 | Efficient recycling method for BI waste liquid |
-
1986
- 1986-01-31 CN CN86101033A patent/CN86101033B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979423A (en) * | 2010-10-15 | 2011-02-23 | 济南大学 | Water-based polymer-polyurethane prepolymer preparation method and application |
| CN110105522A (en) * | 2019-05-31 | 2019-08-09 | 山东理工大学 | The preparation method of waste paint slag polyurethane foamed material |
| CN113234413A (en) * | 2021-05-12 | 2021-08-10 | 新疆天利高新石化股份有限公司 | Efficient recycling method for BI waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN86101033B (en) | 1988-01-20 |
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