CN106866946B - A kind of preparation method of high-quality polyester polyol - Google Patents
A kind of preparation method of high-quality polyester polyol Download PDFInfo
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- CN106866946B CN106866946B CN201710113242.5A CN201710113242A CN106866946B CN 106866946 B CN106866946 B CN 106866946B CN 201710113242 A CN201710113242 A CN 201710113242A CN 106866946 B CN106866946 B CN 106866946B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of high-quality polyester polyol, it the following steps are included: (a) to dicarboxylic acids and dihydric alcohol are added in rectifying column, churned mechanically reaction kettle, the temperature for being gradually warming up to 180 ~ 200 DEG C under inert gas atmosphere and carrying out esterification dehydration, and control the top of the distillation column is 95 ~ 110 DEG C；(b) catalyst is added into reaction kettle, is warming up to 220 ~ 250 DEG C with the speed of 5 ~ 10 DEG C/30min, and be performed under reduced pressure polycondensation reaction；The reduced pressure is to be incremented to 0.1MPa from 0.01MPa with the speed of 0.005 ~ 0.015MPa and kept for 0.5 ~ 1 hour after being incremented by every time, and the quality of the catalyst is the 0.005 ~ 0.05% of the dicarboxylic acids and dihydric alcohol gross mass.To the molecular weight distribution of guarantee system technique and product, hydroxyl value, acid value, chromatic number stabilization.
Description
Technical field
The present invention relates to a kind of preparation methods of polyalcohol, and in particular to a kind of preparation side of high-quality polyester polyol
Method.
Background technique
The molecular backbone of polyester polyol is made of alkyd ester group, and end group is hydroxyl, can be used as surfactant or
The basic material of person's polyurethane material.It is the polyurethane material intensity with higher that is prepared using polyester polyol as raw material, excellent
Wear-resisting property, oil resistivity, weatherability and anti-hydrolytic performance, also have good biodegradability, can be used for producing poly-
Urethane elastomer, coating, adhesive, foamed material etc., therefore polyester polyol is former as a kind of novel high performance polyurethane
Material receives will be widely welcomed for manufacturer.The production method of polyester polyol classics is by binary acid (acid anhydrides) and two
First alcohol (polyalcohol) is condensed, and the control of production technology is most important, otherwise will lead to molecular weight distribution, hydroxyl value, acid value,
The variation of the performances such as coloration, moisture.The molecular weight distribution of product has large effect to downstream product physical property；And hydroxyl value
Range size then affect formulation stability of the Downstream Market in product use process so that influence product mechanics
Performance；The height of coloration has intuitive influence to the appearance of downstream product；For polyurethane reaction system, water can be with isocyanide
Acid esters reacts, so the height of moisture content can seriously affect the ratio of NCO/OH in the starting material of downstream formula, hair
Raw more side reaction and then generation gel etc. lead to scrap of the product.
Summary of the invention
A kind of preparation side of high-quality polyester polyol is provided the invention aims to overcome the deficiencies in the prior art
Method.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is: a kind of high-quality polyester polyol
Preparation method, it the following steps are included:
(a) dicarboxylic acids and dihydric alcohol are added into the reaction kettle with rectifying column, gradually rises under inert gas atmosphere
The temperature that temperature carries out esterification dehydration, and control the top of the distillation column to 180~200 DEG C is 90~110 DEG C；
(b) catalyst is added into reaction kettle, is warming up to 220~250 DEG C with the speed of 5~10 DEG C/30min, and subtracting
Polycondensation reaction is carried out under the conditions of pressure；The reduced pressure is to be incremented to the speed of 0.005~0.015MPa from 0.01MPa
0.1MPa is simultaneously kept for 0.5~1 hour after being incremented by every time, and the quality of the catalyst is the dicarboxylic acids and the total matter of dihydric alcohol
The 0.005~0.05% of amount.
Optimally, in step (a), the gradually heating is first to rise temperature of reaction kettle with the speed of 5~10 DEG C/30min
To 120~130 DEG C, heat preservation 1~3 hour, 150~160 DEG C, heat preservation 1~2 hour are continuously heating to, then are warming up to 180~200
DEG C, heat preservation 0.5~1 hour.
Optimally, the dicarboxylic acids is selected from succinic acid, glutaric acid, adipic acid, decanedioic acid, dimeric dibasic acid, terephthaldehyde
One of acid, dimethyl terephthalate (DMT), M-phthalic acid and phthalic anhydride are a variety of.
Optimally, the dihydric alcohol is selected from ethylene glycol, diethylene glycol, 1,2-PD, 1,3-PD, 1,3- fourth two
Alcohol, 1,4- butanediol, 1,5- pentanediol, 3- methyl-1, one of 5- methyl pentanediol and hexylene glycol or a variety of.
Due to the above technical solutions, the present invention has the following advantages over the prior art: high-quality of the present invention is poly-
On the one hand the preparation method of ester polyol accurately controls the top of the distillation column temperature, can prevent the loss of small molecular alcohol in turn
Product yield is influenced, so as to improve the yield of product；It, can will be small by carrying out polycondensation reaction in specific reduced pressure
The by-products such as molecule alcohols material and oligomer alcohols take reaction system out of, thus the molecular weight of guarantee system technique and product
The stabilization of the indexs such as distribution, hydroxyl value, acid value, chromatic number, moisture content.
Specific embodiment
The preparation method of high-quality polyester polyol of the present invention, it the following steps are included: (a) to the reaction with rectifying column
Dicarboxylic acids and dihydric alcohol are added in kettle, is gradually warming up to 180~200 DEG C under inert gas atmosphere and carries out esterification dehydration instead
The temperature answered, and control the top of the distillation column is 90~110 DEG C；(b) catalyst is added, into reaction kettle with 5~10 DEG C/30min
Speed be warming up to 220~250 DEG C, and be performed under reduced pressure polycondensation reaction；The reduced pressure be with 0.005~
The gradient speed of 0.015MPa is incremented to 0.1MPa from 0.01MPa and is kept for 0.5~1 hour after being incremented by every time, the catalysis
The quality of agent is the 0.005~0.05% of the dicarboxylic acids and dihydric alcohol gross mass.On the one hand it is precisely controlled the top of the distillation column
Temperature, can prevent small molecular alcohol loss so that influence product yield, so as to improve the yield of product；By in spy
Fixed reduced pressure carries out polycondensation reaction, this is because after catalyst is added, it can be using negative pressure or carrier gas condition by small point
The by-products such as sub- alcohols material and oligomer alcohols take reaction system out of, thus the molecular weight of guarantee system technique and product point
Cloth, hydroxyl value, acid value, chromatic number and moisture content stabilization.
In step (a), the gradually heating for temperature of reaction kettle is risen to 120 first with the speed of 5~10 DEG C/30min~
130 DEG C, heat preservation 1~3 hour are continuously heating to 150~160 DEG C, heat preservation 0.5~1 hour, then are warming up to 180~200 DEG C, protect
Temperature 0.5~1 hour, can be avoided in this way reaction kettle wall temperature it is excessively high cause material be carbonized and influence product color.Dicarboxylic acids
Using those of conventional, such as selected from succinic acid, glutaric acid, adipic acid, decanedioic acid, dimeric dibasic acid, terephthalic acid (TPA), to benzene two
One of formic acid dimethyl ester, M-phthalic acid and phthalic anhydride are a variety of.Dihydric alcohol is such as selected from second two using those of routine
Alcohol, diethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methyl-1,
One of 5- methyl pentanediol and hexylene glycol are a variety of.Catalyst is using existing, such as butyl titanate titanate esters
The catalyst perhaps combination of bronsted acid, tertiary amine and organic base or quaternary ammonium compound.
Below in conjunction with embodiment, invention is further explained.
Embodiment 1
The present embodiment provides a kind of preparation method of high-quality polyester polyol, it the following steps are included:
(a) 146.0kg adipic acid (10.0mol) and 713.0kg ethylene glycol are added into the reaction kettle with rectifying column
(11.0mol) heats reaction mixture under nitrogen protection, and the temperature for controlling the top of the distillation column is 95 DEG C~100 DEG C, specifically
Heating process are as follows: 130-135 DEG C, heat preservation 1.5 hours are risen to the speed of 5 DEG C/30min, 150-160 DEG C is continuously heating to, protects
Temperature 0.5 hour, then it is warming up to 180 DEG C, heat preservation 0.5 hour；It is continuously heating to 220-230 DEG C of constant temperature 2-3 hours.
(b) 0.027kg catalyst (butyl titanate) is added into reaction kettle with carrier gas, then in 220 DEG C of insulation reactions 4
Hour；It is performed under reduced pressure polycondensation reaction, specifically: keep 0.4h, 0.02Mpa to keep 0.4h in 0.01Mpa,
0.03Mpa keeps 0.4h, 0.04Mpa that 0.4h, 0.05Mpa is kept to keep 0.4h, 0.06Mpa that 0.4h, 0.07Mpa is kept to keep
0.4h, 0.08Mpa keep 0.4h, 0.09Mpa that 1h, 0.099Mpa is kept to keep to reaction terminating, test product indices.
Embodiment 2
Base the present embodiment provides a kind of preparation method of high-quality polyester polyol, in preparation process and embodiment 1
This is consistent, unlike: the temperature control of the top of the distillation column is 90~95 DEG C.
Embodiment 3
Base the present embodiment provides a kind of preparation method of high-quality polyester polyol, in preparation process and embodiment 1
This is consistent, unlike: in step (a), specific heating process are as follows: first rise to temperature of reaction kettle with the speed of 10 DEG C/30min
135~145 DEG C, heat preservation 3 hours are continuously heating to 160-170 DEG C, heat preservation 2 hours, then are warming up to 220 DEG C, heat preservation to reaction knot
Beam.
Embodiment 4
Base the present embodiment provides a kind of preparation method of high-quality polyester polyol, in preparation process and embodiment 1
This is consistent, unlike: in step (b), specific decompression process are as follows: keep 0.4h, 0.015Mpa to keep 0.4h in 0.01Mpa,
0.02Mpa keeps 0.4h, 0.025Mpa that 0.4h, 0.03Mpa is kept to keep 0.4h, 0.035Mpa that 0.4h, 0.04Mpa is kept to keep
0.4h, 0.045Mpa keep 0.4h, 0.05Mpa to keep 0.4h, 0.055Mpa that 0.4h, 0.06Mpa is kept to keep 0.4h,
0.065Mpa keeps 0.4h, 0.07Mpa that 0.4h, 0.075Mpa is kept to keep 0.4h, 0.08Mpa that 0.4h, 0.085Mpa is kept to protect
0.4h is held, 0.09Mpa keeps 0.4h, 0.095Mpa that 0.4h, 0.099Mpa is kept to keep to reaction terminating.
Embodiment 5
Base the present embodiment provides a kind of preparation method of high-quality polyester polyol, in preparation process and embodiment 1
This is consistent, unlike: in step (a), the temperature control of the top of the distillation column is 100~110 DEG C；It is specific to depressurize in step (b)
Process are as follows: keep 1h, 0.02Mpa that 1h, 0.03Mpa is kept to keep 1h, 0.04Mpa that 1h, 0.05Mpa is kept to keep in 0.01Mpa
1h, 0.06Mpa keep 1h, 0.07Mpa that 1h, 0.08Mpa is kept to keep 2h, 0.09Mpa that 3h, 0.099Mpa is kept to keep to reacting
Terminate.
Comparative example 1
Base the present embodiment provides a kind of preparation method of high-quality polyester polyol, in preparation process and embodiment 1
This is consistent, unlike: in step (b), 220 DEG C are warming up to the speed of 5 DEG C/min, then at constant-pressure conditions (0.1Mpa)
Carry out polycondensation reaction.From table 1 it follows that carrying out lockset reaction using constant pressure will cause polyester polyol molecule amount point
The increase of cloth, chromatic number is unfavorable for the stabilization of product quality.
The performance table of polyester polyol is made in 1 embodiment 1-5 of table, comparative example 1
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (1)
1. a kind of preparation method of high-quality polyester polyol, which is characterized in that it the following steps are included:
(a) dicarboxylic acids and dihydric alcohol are added into the reaction kettle with rectifying column, is gradually warming up under inert gas atmosphere
180 ~ 200 DEG C carry out esterification dehydration, and the temperature for controlling the top of the distillation column is 90 ~ 110 DEG C；
The dicarboxylic acids is selected from succinic acid, glutaric acid, adipic acid, decanedioic acid, dimeric dibasic acid, terephthalic acid (TPA), terephthaldehyde
One of dimethyl phthalate, M-phthalic acid and phthalic anhydride are a variety of；The dihydric alcohol is selected from ethylene glycol, diethylene glycol, 1,2-
Propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 3- methyl-1,5- methyl pentanediol and oneself
One of glycol is a variety of；
(b) catalyst is added into reaction kettle, is warming up to 220 ~ 250 DEG C with the speed of 5 ~ 10 DEG C/30min, and in reduced pressure
Lower carry out polycondensation reaction；The reduced pressure is to be incremented to 0.1MPa from 0.01MPa with the speed of 0.005 ~ 0.015MPa
And kept for 0.5 ~ 1 hour after being incremented by every time, the quality of the catalyst is the dicarboxylic acids and dihydric alcohol gross mass
0.005~0.05%；
In step (a), it is described gradually heating for by temperature of reaction kettle with the speed of 5 ~ 10 DEG C/30min first rise to 120 ~ 130 DEG C,
Heat preservation 1 ~ 3 hour is continuously heating to 150 ~ 160 DEG C, heat preservation 1 ~ 2 hour, then is warming up to 180 ~ 200 DEG C, heat preservation 0.5 ~ 1 hour.
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| CN108424510A (en) * | 2018-03-22 | 2018-08-21 | 上海联景高分子材料有限公司 | The preparation method of polyester polyol for adhesive for laminated film |
| CN108774313B (en) * | 2018-06-27 | 2019-10-11 | 吉林博尔士兰新材料科技有限公司 | A kind of synthesis technology of low coloration polyester polyol |
| CN109439382A (en) * | 2018-11-09 | 2019-03-08 | 深圳春雨润滑科技有限公司 | A kind of polymerization ester oil and preparation method thereof |
| CN114316225B (en) * | 2022-01-11 | 2024-02-02 | 万华化学集团股份有限公司 | Polyester polyol and preparation method and application thereof |
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| CN103804670B (en) * | 2012-11-08 | 2016-03-02 | 上海凯众材料科技股份有限公司 | The synthesis technique of polyester diol |
| CN102964581B (en) * | 2012-11-26 | 2015-02-11 | 山东一诺威聚氨酯股份有限公司 | Preparation method of butanedioic anhydride polyester polyols |
| CN104449531B (en) * | 2013-09-22 | 2017-12-22 | 湖北航天化学技术研究所 | A kind of metal packaging tank dual-component polyurethane resin and preparation method thereof |
| CN103694458B (en) * | 2013-12-11 | 2016-06-01 | 高鼎精细化工(昆山)有限公司 | A kind of biological poly ester polyol and its preparation method and application |
| CN105622905A (en) * | 2016-03-07 | 2016-06-01 | 美瑞新材料股份有限公司 | Technique for preparing polyester polyol |
| CN106220832B (en) * | 2016-08-15 | 2018-07-20 | 上海回天新材料有限公司 | A kind of method and apparatus producing polyester polyol |
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