CN103804670A - Polyester diol synthesis process - Google Patents
Polyester diol synthesis process Download PDFInfo
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Abstract
The present invention discloses a polyester diol synthesis process, which sequentially comprises: (1) a normal pressure reaction, wherein a diol and a diacid or a dicarboxylic anhydride are subjected to an esterification reaction under a normal pressure under protection of nitrogen gas or inert gas at a temperature of 150-200 DEG C, the water yield is recorded, heating is performed to achieve a temperature of 200-250 DEG C when the water yield achieves more than 50% of the theoretical water yield so as to continuously carry out the esterification reaction, the acid value is detected when the water yield achieves more than 90% of the theoretical water yield, the constant temperature is maintained when the acid value is 15-50 mg KOH/g, and the vacuum reaction is performed; and (2) a vacuum reaction, wherein the esterification reaction is continuously performed and the acid value is detected under the vacuum condition of pressure of less than 0.01 MPa, and the esterification reaction is stopped when the acid value is less than 0.50 mg KOH/g to prepare the polyester diol with the hydroxyl value of 25-130 mg KOH/g. According to the synthesis process, the quantification treatment is performed on the process, such that the synthesis stability of the polyester diol is substantially improved, and the acid value and the hydroxyl value can be concurrently controlled in the case of fixation of the feeding ratio.
Description
Invention field
The present invention relates to a kind of synthesis technique of polyester diol, the polyester diol that this synthesis technique makes can be for base polyurethane prepolymer for use as.
Background technology
Polyester polyol is the very important starting material of polyurethane chemistry, is widely used in polyurethane elastomer and foam.Polyester diol has two important characteristic parameters---acid value and hydroxyl value, wishes that acid value is as much as possible close to zero on polyurethane industrial, and hydroxyl value can be in span of control simultaneously.
Synthetic two kinds of reactions, i.e. esterification and the transesterification reaction of relating to of polyester polyol.Esterification is the reaction between carboxyl and hydroxyl, discharges water byproduct, makes the quantitative change of system molecule large, and viscosity raises; Transesterification reaction is the reaction between ester group and hydroxyl, does not change the molecular-weight average of system, but changes molecular weight distribution.
The esterification of polyester polyol is generally to react between organic acid and alcohol, and organic acid boiling point is higher, and esterification temperature is generally difficult for volatilization loss relatively, and some small molecules in polyvalent alcohol system are easily volatilization, causes final product hydroxyl value to be difficult to control.
The production technique of polyester polyol is divided into pre-polymerization section and polymeric segment at present, and in pre-polymerization section process, aquifer yield is larger, improper if reactor and condenser temperature are controlled, and tends to be entrained with much lower boiling alcohol in exiting water process; When polymeric segment, carboxyl and hydroxyl concentration in system are lower, shipwreck is to remove in time, esterification speed reduces greatly, and in order effectively to remove fast the water in system, industrial what generally adopt is two kinds of solvent bank water law and vacuum methodes, the normal solvent using of solvent method band water has toluene, dimethylbenzene etc., the product colourity obtaining is darker, compares the former, and the latter is adopted more widely on low acid value polyester polyol is produced.As do not reached suitable pre-polymerization degree in pre-polymerization section, polymeric segment, in vaccum dewatering process, can be taken away a large amount of alcohol.
Polyester building-up reactions is subject to progressively polymerization mechanism control, the feed ratio of raw material is very important, directly determine target molecular weight, if cause significant loss on synthesis technique, can cause material rate variation, the actual molecular weight of product and theoretical molecular deviation are very large like this, when technique is unstable, same initial feed ratio often can not get the product of acceptable quality, and the molecular weight fluctuation of different batches product is very large.
In order to reach the product with qualified hydroxyl value, the way of alcohol is added in industrial frequent employing, makes up the alcohol losing in pre-polymerization in early stage and polymerization process, and this method is got half the result with twice the effort.
Summary of the invention
For the above-mentioned deficiency of prior art, according to embodiments of the invention, wish to propose a kind of synthesis technique to be carried out to quantification processing, greatly improve synthesising stability, fixed feeding area than in the situation that can control the synthesis technique of the polyester diol of acid value and hydroxyl value simultaneously.
In order to solve the problems of the technologies described above, the synthesis technique of polyester diol provided by the invention is divided into two stages: the first stage is reacted by dibasic alcohol and diprotic acid/anhydride esterifying under normal pressure and nitrogen/protection of inert gas, by aquifer yield control level of response, in the time that level of response reaches stated limit, rising temperature is further reacted, acid value falls into after target interval, keeps constant temperature, enters subordinate phase; Subordinate phase is vacuum reaction, and equipment should seal, and prevents that air from entering, and continues vacuum reaction and constantly detects acid value, until the acid value of product approaches zero.
According to embodiment, the synthesis technique of polyester diol provided by the invention, in turn includes the following steps:
(1) synthesis under normal pressure: at normal pressure, nitrogen or protection of inert gas, 150-200 ℃, dibasic alcohol and diprotic acid or dibasic acid anhydride generation esterification, record aquifer yield, when aquifer yield reaches 50% when above of theoretical aquifer yield, be warming up to 200-250 ℃ and continue esterification, when aquifer yield be greater than theoretical aquifer yield 90% time, detect acid value, in the time that acid value is 15-50mgKOH/g, keep constant temperature, carry out vacuum reaction;
(2) vacuum reaction: be less than at pressure under the vacuum condition of 0.01MPa, continue esterification and detect acid value, stop esterification in the time that acid value is less than 0.50mgKOH/g, make the polyester diol that hydroxyl value is 25-130mgKOH/g.
In the synthesis technique of the aforementioned polyester diol of the present invention, dibasic alcohol can be small molecules, can be also oligopolymer.Small molecules dibasic alcohol is aliphatic organic compound, there is 2-12 carbon atom, as ethylene glycol, Diethylene Glycol, 1, 2-propylene glycol, 1, ammediol, 1, 4-butyleneglycol, 1, 3-butyleneglycol, neopentyl glycol, cyclohexanedimethanol, 2-methyl isophthalic acid, ammediol, 2-methyl-2-butyl-1, ammediol, dihydroxymethyl heptane, 2, 2, 4-trimethylammonium-1, 3-pentanediol, tetramethyl ethylene ketone, 2, 4, 4-trimethylammonium-1, 6-hexylene glycol etc., oligopolymer dibasic alcohol comprises polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran and oxyethane, the copolymerization product of one or more monomers in propylene oxide and tetrahydrofuran (THF).
In the synthesis technique of the aforementioned polyester diol of the present invention, diprotic acid comprises aliphatics and aromatic series, preferably has the compound of 2-20 carbon atom.Aliphatic dibasic acid is as hexanodioic acid, succsinic acid, pentanedioic acid, sebacic acid, suberic acid, butyl malonic acid, diethyl malonic acid, dimethylated pentanedioic acid; Aromatic acid is as adjacent (or to) phthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acid; In addition diprotic acid also comprises such as above-mentioned aromatic dicarboxylic acid hydrogenated products.Above-mentioned diprotic acid also can be corresponding acid anhydrides and replaces, and replaces as succsinic acid can be succinyl oxide, and phthalic acid can be Tetra hydro Phthalic anhydride and replaces.
In the synthesis technique of the aforementioned polyester diol of the present invention, in the synthesis under normal pressure stage, need to add nitrogen/protection of inert gas; then be slowly warmed up to 150-200 ℃; treat that raw material fully melts evenly, start to stir, constantly record aquifer yield; when reaching theory, aquifer yield goes out 50% when above of water inventory; further be warming up to 200-250 ℃, continue to record aquifer yield, when aquifer yield reach theory go out water inventory 90% time; start vacuum reaction, until acid value is qualified.
In the synthesis technique of the aforementioned polyester diol of the present invention, in the vacuum reaction stage, should keep conversion unit sealing, prevent that air from entering, otherwise can cause product flavescence.
In the synthesis technique of the aforementioned polyester diol of the present invention, the catalyzer of esterification comprises organic zinc, organotin and organic titanium class.Conventional zinc acetate, zinc propionate, Dibutyltin oxide, stannous octoate, butyl (tetra) titanate and the iso-butyl titanate etc. of comprising.Catalyzer contributes to Reaction time shorten, and consumption, within the scope of 10-100ppm, is preferably less than 50ppm, and catalyst levels is excessive, can cause final product its colour changed into yellow.In synthesis technique of the present invention, can add catalyzer, also can not add catalyzer.
Traditional method relatively, technique of the present invention is taked quantization method, strictly controls the reaction of normal pressure section and vacuum zone reaction, can control well acid value and the hydroxyl value of polyester diol, without additionally adding raw material simultaneously again.The polyester diol number-average molecular weight that synthesis technique of the present invention makes, within the scope of 500-4000, is suitable for preparing base polyurethane prepolymer for use as.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as being only not used in and limiting the scope of the invention for the present invention is described.After having read the content of the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modification falls into the scope of the claims in the present invention equally.
Embodiment 1
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 469.44g(ADA, 3.21mol), Diethylene Glycol 267.68g(DEG, 2.52mol), ethylene glycol 72.48g(EG, 1.17mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 58.07g(52% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 101.63g(91% theoretical value) time, start to measure acid value, now acid value is 45mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.22mgKOH/g, finish reaction, product hydroxyl value is 54mgKOH/g, and product number-average molecular weight is 2100.
Embodiment 2
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 596.16g(ADA, 4.08mol), ethylene glycol 319.05g(EG, 5.14mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 80.78g(55% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 135.13g(92% theoretical value) time, start to measure acid value, now acid value is 43mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.12mgKOH/g, finish reaction, product hydroxyl value is 126KOH/g, and product number-average molecular weight is 900.
Embodiment 3
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 480.96g(ADA, 3.29mol), Diethylene Glycol 440.01g(DEG, 4.15mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 66.32g(56% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 106.60g(90% theoretical value) time, start to measure acid value, now acid value is 48mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.20mgKOH/g, finish reaction, product hydroxyl value is 112mgKOH/g, and product number-average molecular weight is 1000.
Embodiment 4
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 476.64g(ADA, 3.26mol), 1, 4-butyleneglycol 291.04g(BDO, 3.23mol), 2-methyl isophthalic acid, 3-butyleneglycol 72.40g(MPG, 0.80mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 63.45g(52% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 107.11g(91% theoretical value) time, start to measure acid value, now acid value is 45mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.21mgKOH/g, finish reaction, product hydroxyl value is 69mgKOH/g, and product number-average molecular weight is 1620.
Embodiment 5
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 496.72g(ADA, 3.21mol), polyoxyethylene glycol 79.44g(PEG-600, MW=600, 0.13mol), ethylene glycol 252.64g(EG, 4.07mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 61.17g(50% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 111.38g(91% theoretical value) time, start to measure acid value, now acid value is 46mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.16mgKOH/g, finish reaction, product hydroxyl value is 67mgKOH/g, and product number-average molecular weight is 1670.
Comparative example 1
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 469.44g(ADA, 3.21mol), Diethylene Glycol 267.68g(DEG, 2.52mol), ethylene glycol 72.48g(EG, 1.17mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 44.67g(40% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 101.63g(91% theoretical value) time, start to measure acid value, now acid value is 45mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.22mgKOH/g, finish reaction, product hydroxyl value is 42mgKOH/g, and product number-average molecular weight is 2670.
Pre-polymerization section is 160 ℃ of stages, and pre-polymerization is insufficient, and alcohol loss is more, and compared with embodiment 1, the hydroxyl value of final product is on the low side.
Comparative example 2
Under normal pressure to agitator is housed, in the 1L four-hole boiling flask of temperature thermopair and reflux condensing tube, add hexanodioic acid 469.44g(ADA, 3.21mol), Diethylene Glycol 267.68g(DEG, 2.52mol), ethylene glycol 72.48g(EG, 1.17mol), catalyst Ti acid butyl ester 10ppm, pass into nitrogen and in 2h, be slowly warming up to 160 ℃, after system raw material melts evenly, open and stir, record aquifer yield, when aquifer yield reaches the 58.07g(52% theoretical value of theoretical water) time, in 30min, be warming up to 200 ℃, continue to record aquifer yield, accumulative total aquifer yield reaches 89.35g(80% theoretical value) time, start to measure acid value, now acid value is 45mgKOH/g.Start vacuum reaction, constantly measure acid value, when last acid value reaches 0.22mgKOH/g, finish reaction, product hydroxyl value is 40mgKOH/g, and product number-average molecular weight is 2800.
Before vaccum dewatering starts, pre-polymerization degree is on the low side, causes alcohol loss larger, and compared with embodiment 1, the hydroxyl value of final product is on the low side.
Claims (9)
1. a synthesis technique for polyester diol, is characterized in that, in turn includes the following steps:
(1) synthesis under normal pressure: at normal pressure, nitrogen or protection of inert gas, 150-200 ℃, dibasic alcohol and diprotic acid or dibasic acid anhydride generation esterification, record aquifer yield, when aquifer yield reaches 50% when above of theoretical aquifer yield, be warming up to 200-250 ℃ and continue esterification, when aquifer yield be greater than theoretical aquifer yield 90% time, detect acid value, in the time that acid value is 15-50mgKOH/g, keep constant temperature, carry out vacuum reaction;
(2) vacuum reaction: be less than at pressure under the vacuum condition of 0.01MPa, continue esterification and detect acid value, stop esterification in the time that acid value is less than 0.50mgKOH/g, make the polyester diol that hydroxyl value is 25-130mgKOH/g.
2. the synthesis technique of polyester diol according to claim 1, is characterized in that, stops esterification when acid value is less than 0.20mgKOH/g.
3. the synthesis technique of polyester diol according to claim 1, is characterized in that, dibasic alcohol is small molecules dibasic alcohol or oligopolymer dibasic alcohol, and small molecules dibasic alcohol is aliphatic organic compound, has 2-12 carbon atom; Diprotic acid is the aliphatic dibasic acid with 2-20 carbon atom, the aromatic acid with 2-20 carbon atom, or aforementioned aromatic dicarboxylic acid hydrogenated products.
4. the synthesis technique of polyester diol according to claim 3, is characterized in that, small molecules dibasic alcohol is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,3-PD, BDO, 1,3-butyleneglycol, neopentyl glycol, cyclohexanedimethanol, 2-methyl isophthalic acid, ammediol, 2-methyl-2-butyl-1,3-PD, dihydroxymethyl heptane, 2,2,4-trimethylammonium-1,3-pentanediol, tetramethyl ethylene ketone or 2,4,4-trimethylammonium-1,6-hexylene glycol.
5. the synthesis technique of polyester diol according to claim 3, is characterized in that, oligopolymer dibasic alcohol is polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran, or the copolymerization product of one or more monomers in oxyethane, propylene oxide and tetrahydrofuran (THF).
6. the synthesis technique of polyester diol according to claim 3, is characterized in that, aliphatic dibasic acid is hexanodioic acid, succsinic acid, pentanedioic acid, sebacic acid, suberic acid, butyl malonic acid, diethyl malonic acid or dimethylated pentanedioic acid.
7. the synthesis technique of polyester diol according to claim 3, is characterized in that, aromatic acid is phthalic acid, m-phthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid or 4,4 '-diphenyl ether dicarboxylic acid.
8. the synthesis technique of the polyester diol described in any one according to claim 1-7, it is characterized in that, the catalyzer of esterification is zinc acetate, zinc propionate, Dibutyltin oxide, stannous octoate, butyl (tetra) titanate or iso-butyl titanate, and catalyst levels is 10-100ppm.
9. the synthesis technique of polyester diol according to claim 8, is characterized in that, catalyst levels is 10-50ppm.
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| CN104861139A (en) * | 2015-06-10 | 2015-08-26 | 北京高盟新材料股份有限公司 | Preparation method of high-temperature steam endurance polyurethane resin for ink |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| CN106866946A (en) * | 2017-02-28 | 2017-06-20 | 江苏华大新材料有限公司 | A kind of preparation method of high-quality PEPA |
| CN106883398A (en) * | 2017-02-25 | 2017-06-23 | 张家港南光化工有限公司 | A kind of synthetic method of polyester diol |
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| CN106883398A (en) * | 2017-02-25 | 2017-06-23 | 张家港南光化工有限公司 | A kind of synthetic method of polyester diol |
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| CN107779162A (en) * | 2017-11-17 | 2018-03-09 | 北京高盟新材料股份有限公司 | A kind of trans double component solvent-free polyurethane composite membrane adhesive and preparation method thereof |
| 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 |
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| CN109485815A (en) * | 2018-10-15 | 2019-03-19 | 中山大学 | A kind of preparation method of aqueous polyurethane emulsion and its aqueous polyurethane emulsion obtained and its application |
| CN109485815B (en) * | 2018-10-15 | 2021-01-01 | 中山大学 | Preparation method of waterborne polyurethane emulsion, waterborne polyurethane emulsion prepared by preparation method and application of waterborne polyurethane emulsion |
| CN111154083A (en) * | 2018-11-07 | 2020-05-15 | 万华化学集团股份有限公司 | Phthalic anhydride polyester polyol with narrow molecular weight distribution and preparation method thereof |
| CN111777509A (en) * | 2020-06-10 | 2020-10-16 | 上海康达化工新材料集团股份有限公司 | Dihydric alcohol modified anhydride toughening agent |
| CN114075324A (en) * | 2020-08-20 | 2022-02-22 | 南亚塑胶工业股份有限公司 | Method for producing polyester polyol |
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| CN112159728A (en) * | 2020-09-09 | 2021-01-01 | 湖北天基生物能源科技发展有限公司 | Method for reducing acid value of waste oil by esterification |
| CN112159728B (en) * | 2020-09-09 | 2023-01-06 | 湖北天基生物能源科技发展有限公司 | Method for reducing acid value of waste oil by esterification |
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