CN103724602A - Method for preparing sebacic acids polyester polyol by using recovered alcohol - Google Patents
Method for preparing sebacic acids polyester polyol by using recovered alcohol Download PDFInfo
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- CN103724602A CN103724602A CN201310653717.1A CN201310653717A CN103724602A CN 103724602 A CN103724602 A CN 103724602A CN 201310653717 A CN201310653717 A CN 201310653717A CN 103724602 A CN103724602 A CN 103724602A
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- sebacic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for preparing a sebacic acids polyester polyol by using recovered alcohol. The method comprises the following steps: 1) putting recovered alcohol, sebacic acid, a catalyst and the like into a polyester reaction kettle in one time; 2) heating to 142-145 DEG C, and reacting for 1-2 h; 3) continuously heating to 180-185 DEG C, and reacting for 1-2 h; 4) heating to 225-228 DEG C, and keeping the temperature for 1-2 h; 5) vacuumizing, and stopping the reaction till an acid value of a product is smaller than or equal to 0.9 mg KOH/g; 6) reducing the temperature below to 75 DEG C and discharging to obtain the sebacic acids polyester polyol. By adopting the technical scheme, the heating efficiency is higher, more simplicity and convenience are provided, environmental protection and energy saving are realized, at the same time, the recovered alcohol (main components are ethylene glycol and diethylene glycol) is used as a raw material, so that the production cost is low, and environmental-friendly and low-energy reuse of the recovered alcohol is realized.
Description
Technical field
The present invention relates to the synthetic field of decanediol kind polyester polyvalent alcohol, be specifically related to a kind of method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol that reclaims of utilizing.
Background technology
Polyester polyol is the main raw material of synthesis of polyurethane (PU) resin, and its relative molecular mass is 1000～3000, is widely used in the fields such as tackiness agent, coating, footwear material and synthetic leather.Preparing at present the raw materials used hexanodioic acid that mostly is of urethane is polyester polyol, it is with polyprotonic acid and polyol reaction, finally with the compound of the chain-like structure of-OH end-blocking, polyester polyol has totally biodegradable ability, can, to environment, not or not studying relatively is deeply also to have most one of environment-friendly materials of industrial prospect.But this raw material cannot be for the preparation of the PU elastomerics that has particular requirement, as hydrolytic resistance.
Chinese patent CN201110400183.2 discloses a kind of method and device of producing polyester polyol, belong to polyvalent alcohol production technical field, according to mol ratio (1.1～2.0): 1.0: (0.0001～0.0005) configuration polyalcohols, polyprotonic acid (ester) class and zinc acetate, the mixture of one or more in antimony glycol or titanate ester, adopt three grades of microwaves or Electromagnetic Heating, one-level is progressively warming up to 110～150 ℃ by material by room temperature, secondary continues to be warming up to 180～200 ℃ by material, three grades are warming up to 200～250 ℃ again by material, vacuum hydro-extraction reactant to its acid number is less than or equal to 1mg KOH/g and obtains polyester polyol.
The energy consumption of existing type of heating is high, not energy-conservation, and low molecular polylol finished product raw materials cost is high.
Summary of the invention
In order to reduce costs, fully represent the added value that reclaims alcohol, it is raw material that the present invention utilizes itself and sebacic acid, adopts high temperature and high pressure steam heating and the disposable method feeding intake, the sebacic acid kind polyester polyvalent alcohol that can meet customer need of preparing different hydroxyl values, concrete steps are as follows:
1) will reclaim in the disposable input pet reaction stills such as alcohol, sebacic acid, catalyzer;
2) adopt the method for high temperature and high pressure steam heating, be warming up to 142～145 ℃, reaction 1～2h;
3) pass into N
2make protection gas and keep not interrupting, being warming up to 180～185 ℃, reaction 1～2h;
4) be warming up to 225～228 ℃, insulation 1～2h;
5) vacuumize, vacuum tightness and temperature are finally stabilized in 0.09～0.095MPa, 225～228 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately;
6) be cooled to 75 ℃ with bottom discharge, obtain sebacic acid kind polyester polyvalent alcohol.
Further, described recovery alcohol refers to the alcohol mixture containing ethylene glycol and Diethylene Glycol.
Further, described recovery alcohol colourity is not higher than the transparent liquid of 50Hazen.
Further, it is characterized in that, in described recovery alcohol, the mass ratio of ethylene glycol and Diethylene Glycol and sebacic acid is (5～60): (5～40): 100, and molar ratio of alcohol to acid is 1.2～2.2.
Further, the hydroxyl value scope of described recovery alcohol is 500～750mg KOH/g.
Further, content >=90% of ethylene glycol and Diethylene Glycol in described recovery alcohol, and other impurity can be water, or the mixture of water and small molecules polyvalent alcohol.
Further, described small molecules polyvalent alcohol is a kind of dibasic alcohol or multiple dibasic alcohol, and molecular weight is in 200g/mol, and boiling point is less than 300 ℃.
Further, the content of described small molecules polyvalent alcohol is no more than 5%.
Further, high temperature and high pressure steam refers to water vapor, and vapor pressure is 1.0～5.5MPa.
Further, catalyzer is stannous octoate, and accounts for 0.01～0.03% of all raw material total masses.
Adopt such scheme, obtained a kind of sebacic acid kind polyester polyvalent alcohol.Overcome in prior art the energy consumption of type of heating high, not energy-conservation, the shortcomings such as low molecular polylol finished product raw materials cost height; Utilize the low molecular polylol reclaiming, can accomplish to make the best use of everything, adopt the method for high temperature and high pressure steam heating simultaneously, environmental protection and energy saving more, production cost is relatively low, and product has more market competition advantage.
The present invention adopts high temperature and high pressure steam heating method, compares traditional heating method, and heating efficiency is higher, easier and environmental protection and energy saving, the recovery alcohol (main component is ethylene glycol and Diethylene Glycol) of take is raw material simultaneously, and production cost is low, can realize the environmental protection less energy-consumption recycling of useless alcohol.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is operation step map of the present invention.
Embodiment
Embodiment 1:
1): 50Kg is reclaimed in the disposable input pet reaction stills such as alcohol (hydroxyl value 600mg KOH/g), 60Kg sebacic acid and 10g catalyzer;
2): adopt the method for high temperature and high pressure steam heating, be warming up to 142 ℃, reaction 2h;
3): pass into N
2make protection gas and keep not interrupting, continuing to be warming up to 180 ℃, reaction 2h;
4): be warming up to 225 ℃, insulation 2h;
5): start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 225 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately.
6): be cooled to 75 ℃ with bottom discharge, obtain solid-state sebacic acid kind polyester polyvalent alcohol (hydroxyl value 75mg KOH/g, acid number 0.4mg KOH/g).
Embodiment 2:
1): 50Kg is reclaimed in the disposable input pet reaction stills such as photovoltaic cutting fluid (hydroxyl value 598mg KOH/g), 50Kg sebacic acid and 10g catalyzer;
2): adopt the method for high temperature and high pressure steam heating, be warming up to 145 ℃, reaction 1h;
3): pass into N
2make protection gas and keep not interrupting, continuing to be warming up to 185 ℃, reaction 1h;
4): be warming up to 228 ℃, insulation 2h;
5): start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.095MPa, 225 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately.
6): be cooled to 75 ℃ with bottom discharge, obtain solid-state sebacic acid kind polyester polyvalent alcohol (hydroxyl value 80mg KOH/g, acid number 0.7mg KOH/g).
Embodiment 3:
1): 80Kg is reclaimed in the disposable input pet reaction stills such as alcohol (hydroxyl value 750mg KOH/g), 50Kg sebacic acid and 15g catalyzer;
2): adopt the method for high temperature and high pressure steam heating, be warming up to 142 ℃, reaction 1h;
3): pass into N
2make protection gas and keep not interrupting, continuing to be warming up to 180 ℃, reaction 1h;
4): be warming up to 225 ℃, insulation 2h;
5): start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.095MPa, 225 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately.
6): be cooled to 75 ℃ with bottom discharge, obtain thick transparent hexanodioic acid kind polyester polyvalent alcohol (hydroxyl value 126mg KOH/g, acid number 0.8mg KOH/g).
Embodiment 4:
1): 20Kg is reclaimed in the disposable input pet reaction stills such as alcohol (hydroxyl value 500mg KOH/g), 60Kg sebacic acid and 10g catalyzer;
2): adopt the method for high temperature and high pressure steam heating, be warming up to 145 ℃, reaction 1h;
3): pass into N
2make protection gas and keep not interrupting, continuing to be warming up to 180 ℃, reaction 2h;
4): be warming up to 228 ℃, insulation 2h;
5): start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 228 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately.
6): be cooled to 75 ℃ with bottom discharge, obtain solid-state sebacic acid kind polyester polyvalent alcohol (hydroxyl value 59mg KOH/g, acid number 0.6mg OH/g).
Claims (10)
1. utilize and reclaim the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, comprise the following steps:
1) will reclaim in the disposable input pet reaction stills such as alcohol, sebacic acid, catalyzer;
2) adopt the method for high temperature and high pressure steam heating, be warming up to 142～145 ℃, reaction 1～2h;
3) pass into N
2make protection gas and keep not interrupting, being warming up to 180～185 ℃, reaction 1～2h;
4) be warming up to 225～228 ℃, insulation 1～2h;
5) vacuumize, vacuum tightness and temperature are finally stabilized in 0.09～0.095MPa, 225～228 ℃, stopped reaction when product acid number≤0.9mg KOH/g separately;
6) be cooled to 75 ℃ with bottom discharge, obtain sebacic acid kind polyester polyvalent alcohol.
2. a kind of utilization according to claim 1 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, described recovery alcohol refers to the alcohol mixture containing ethylene glycol and Diethylene Glycol.
3. a kind of utilization according to claim 1 and 2 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, described recovery alcohol colourity is not higher than the transparent liquid of 50Hazen.
4. according to a kind of method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol that reclaims of utilizing described in claim 1 or 2 any one, it is characterized in that, in described recovery alcohol, the mass ratio of ethylene glycol and Diethylene Glycol and sebacic acid is (5～60): (5～40): 100, and molar ratio of alcohol to acid is 1.2～2.2.
5. a kind of utilization according to claim 2 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, the hydroxyl value scope of described recovery alcohol is 500～750mg KOH/g.
6. a kind of method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol that reclaims of utilizing according to claim 2, it is characterized in that, content >=90% of ethylene glycol and Diethylene Glycol in described recovery alcohol, and other impurity can be water, or the mixture of water and small molecules polyvalent alcohol.
7. a kind of utilization according to claim 6 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, described small molecules polyvalent alcohol is a kind of dibasic alcohol or multiple dibasic alcohol, and molecular weight is in 200g/mol, and boiling point is less than 300 ℃.
8. a kind of utilization according to claim 6 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, the content of described small molecules polyvalent alcohol is no more than 5%.
9. a kind of utilization according to claim 1 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, high temperature and high pressure steam refers to water vapor, and vapor pressure is 1.0～5.5MPa.
10. a kind of utilization according to claim 1 reclaimed the method that alcohol is prepared sebacic acid kind polyester polyvalent alcohol, it is characterized in that, catalyzer is stannous octoate, and accounts for 0.01～0.03% of all raw material total masses.
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| CN201310653717.1A CN103724602A (en) | 2013-12-06 | 2013-12-06 | Method for preparing sebacic acids polyester polyol by using recovered alcohol |
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| CN201310653717.1A CN103724602A (en) | 2013-12-06 | 2013-12-06 | Method for preparing sebacic acids polyester polyol by using recovered alcohol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945605A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Acrylic-acid-modified water-based alkyd resin and preparation method thereof |
| CN104945567A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Modified waterborne alkyd resin and preparation method thereof |
| CN106279653A (en) * | 2016-08-15 | 2017-01-04 | 上海回天新材料有限公司 | A kind of purposes of the method preparing aromatic polyester polyol and products thereof |
| CN116515092A (en) * | 2023-05-11 | 2023-08-01 | 旭川化学（苏州）有限公司 | Polyester polyol and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482153A (en) * | 2003-08-11 | 2004-03-17 | 北京理工大学 | Process for preparing high-molecular aliphatic polyester |
| CN101245133A (en) * | 2007-02-16 | 2008-08-20 | 天津佳用水漆有限公司 | Polyester dihydric alcohol |
-
2013
- 2013-12-06 CN CN201310653717.1A patent/CN103724602A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482153A (en) * | 2003-08-11 | 2004-03-17 | 北京理工大学 | Process for preparing high-molecular aliphatic polyester |
| CN101245133A (en) * | 2007-02-16 | 2008-08-20 | 天津佳用水漆有限公司 | Polyester dihydric alcohol |
Non-Patent Citations (1)
| Title |
|---|
| 杨建军等: "癸二酸系聚酯多元醇的合成", 《合成橡胶工业》, vol. 22, no. 4, 15 July 1999 (1999-07-15), pages 230 - 232 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945605A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Acrylic-acid-modified water-based alkyd resin and preparation method thereof |
| CN104945567A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Modified waterborne alkyd resin and preparation method thereof |
| CN104945567B (en) * | 2015-05-20 | 2019-02-15 | 安徽省金盾涂料有限责任公司 | A kind of modified water-based alkyd resin and preparation method thereof |
| CN106279653A (en) * | 2016-08-15 | 2017-01-04 | 上海回天新材料有限公司 | A kind of purposes of the method preparing aromatic polyester polyol and products thereof |
| CN106279653B (en) * | 2016-08-15 | 2018-03-27 | 上海回天新材料有限公司 | A kind of purposes of the method for preparing aromatic polyester polyol and products thereof |
| CN116515092A (en) * | 2023-05-11 | 2023-08-01 | 旭川化学（苏州）有限公司 | Polyester polyol and preparation method and application thereof |
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Application publication date: 20140416 |