CN103087304A - Production method of polyester polyol - Google Patents
Production method of polyester polyol Download PDFInfo
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- CN103087304A CN103087304A CN2013100202085A CN201310020208A CN103087304A CN 103087304 A CN103087304 A CN 103087304A CN 2013100202085 A CN2013100202085 A CN 2013100202085A CN 201310020208 A CN201310020208 A CN 201310020208A CN 103087304 A CN103087304 A CN 103087304A
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Abstract
The invention discloses a production method of polyester polyol. According to the method, natural oil is modified by maleic anhydride and then reacts with small-molecule polyol, dicarboxylic acid or carboxylic ester to obtain a polyester polyol product with high cyclopentane solubility. According to the invention, the modified oil can be led into a polyester body relatively completely so as to improve the functionality of the whole product; the cost of the adopted raw materials is low, and the technology is easy to operate; and particularly in the process of producing low-density polyurethane foam, the solubility of the adopted cyclopentane in polyester polyol can be improved at least to 25%.
Description
Technical field
The present invention relates to the production method of the production field of polyurethane foam, particularly polyester polyol.
Background technology
Foam production business uses aromatic polyester polyol and other composition production polyurethane foams.Other compositions may comprise polyether glycol, organic silicon surfactant, various amine or metal catalyst and whipping agent.Such mixing, being called the combined polyether glycol formula is for the manufacture of important component part of polyurethane foam.Other important component parts are isocyanic ester.Also having another important composition is whipping agent.There is no whipping agent, it is the porous plastics that impossible make low density and have very high strength-weight ratio.On market, suitable whipping agent is fluorocarbon now, hydrocarbon polymer, and carbon dioxide.
Water and isocyanate reaction form a unsettled carboxylamine, are decomposed to form amine and carbonic acid gas.The amine immediate response forms an extra isocyanic ester and replaces urea.As adopting too much water as whipping agent, urea can cause polyurethane foam crisp and frangible, thereby worsens foam and substrate adherence energy.On the other hand, carbonic acid gas has higher infiltration than air in polyurethane foam, thereby may cause low-density polyurethane foam to shrink.Moreover the isocyanate reaction of the water reaction 2mol of 1mol discharges the 1mol carbonic acid gas, and the isocyanic ester price on market is higher now, thereby it neither a very economical whipping agent.Meanwhile, carbon dioxide has higher thermal conductivity than fluorocarbon and hydrocarbon polymer, and because it generally is insoluble to most ofs common polyethers or polyester, so little to the effect of viscosity of reduction combined polyether, thus the use of combined polyether glycol is affected to some extent.
Modal fluorocarbon master is on market: HCFC-141b(dichloro one fluoroethane), HFC-245fa(1,1,1,3,3 pentafluoropropanes) and HFC-134a(1,1,1,2-Tetrafluoroethane) etc., be all welcome pneumatogen.For HCFC-141b, according to the requirement of Montreal protocol, comprise that the developing country of China will maintain the achievements of one's predecessors superseded to the acceleration of its production and consumption before the year two thousand thirty.For HFC-245fa and HFC-134a, because their boiling point is lower than room temperature, so need a rated pressure container to store combined polyether glycol.What be worth paying special attention to is that under the weather of sweltering heat, when HFC-245fa was mixed with combined polyether glycol, boiling point was that the HFC-245fa of 15.3 degrees centigrade is not easy operation very much.Although, can replace part HFC-245fa for water, reduce the vapour pressure of combined polyether glycol with this, if but too many water is to be used in combined polyether glycol, the physicals of some foams will suffer damage, compare simultaneously water and hydrocarbon polymer, HFC-245fa is the whipping agent of a costliness.
As the hydrocarbon polymer of whipping agent, now the most frequently used is the pentane of isomer.On urethane foam market, the pentane of three kinds of isomer is arranged: pentamethylene, iso-pentane and Skellysolve A.Abroad, for the application of the pentane processing mode according to foam, substantially be divided into: heat preservation plate material has adopted a kind of ratio of mixture at the Skellysolve A of 0.2:0.8 to 0.8:0.2 and the miscellany of iso-pentane; The spraying bubble adopts 95% pentamethylene; Pentamethylene and the iso-pentane of blending ratio from 20:80 to 50:50 is used for the cast foam.Adopt the advantage of pentane as follows: pentane is cheap and relatively be easy to get, and the pentane gas thermal conductivity is lower than carbonic acid gas.Adopt the pentane shortcoming to comprise following: it is a kind of inflammable liquid, need to carry out special processing; The intermiscibility of it and present high hydroxyl value and high function aromatic polyester polyol is poor; It has reduced the usage quantity of water at combined polyether.
Comprehensive relatively above three class whipping agents, hydrocarbon class pentane series whipping agent is the strongest candidate products in the polyurethane rigid foam plastic system applies.
Commercial polyester polyol has certain pentane solubility, but higher solubleness is necessary, although (solubility property of all kinds of pentanes is different to some extent, but relevant little, so following we adopt pentamethylene and polyester polyol to illustrate), the solubleness that 5～20% pentamethylene are arranged due to present commercial polyvalent alcohol, but along with the polyvalent alcohol that adds to of more and more measuring many pentamethylene, such solubleness easily makes pentamethylene separate.So when producing low-density polyurethane foam now, for preventing that pentamethylene from separating, employing increases the intermiscibility of pentamethylene by adding the emulsifying agent method, but can have influence on the intermiscibility (as water content, polyester consumption etc.) of pentamethylene due to other many factors, this class combined polyether glycol lacks permanent stability.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind ofly can prevent that pentamethylene from separating and can have with pentamethylene the production method of the polyester polyol of high intermiscibility.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of production method of polyester polyol, the method comprises the steps:
1) at first cis-butenedioic anhydride and natural fats and oils are placed in reactor, then are heated to 160～200 ℃, and in 160～200 ℃ of insulations cooling after 1～6 hour, obtain the yellow transparent thick liquid, be the modified natural grease, stay subsequent reactions to use; Wherein the mol ratio of cis-butenedioic anhydride and natural fats and oils is 1:1 to 1:3;
2) the modified natural grease that obtains in small molecules polyvalent alcohol, di-carboxylic acid and acid anhydrides and ester thereof, step 1) is added in reaction vessel, and then add the catalyzer heating reflux reaction, 220～230 ℃ are incubated and detect acid number, after acid number drops to below 5mgKOH/g, cool to 180～220 ℃, the beginning rectification under vacuum, vacuum degree control-0.065～-0.095mPa, until the acid number of the product after rectifying drops to below 1.0mgKOH/g, the moisture content mass fraction is lower than 0.1% rear cooling discharge, namely obtain described polyester polyol, wherein
Small molecules polyvalent alcohol: 45～65%
Di-carboxylic acid and dicarboxylic acid anhydride: 20～30%
Ester: 0～10%
Modified natural grease: 10～20%.
In step 1), be warming up to 180 ℃ after first cis-butenedioic anhydride and natural fats and oils progressively being warmed up to 160 ℃ in 2 hours, then be warming up to 200 ℃ from 180 ℃ in 1 hour, at last at 200 ℃ of insulations cooling discharge after 4 hours.
Natural fats and oils described above comprises Semen Maydis oil, soybean oil, Oleum Cocois, Oleum Gossypii semen, Toenol 1140, sweet oil, plam oil, palm-kernel oil, peanut oil, Oleum Helianthi, process leach any one or more in the natural fats and oils of purifying and the lipid acid of purifying out through acidifying again after saponification from natural fats and oils.
Step 2) in, small molecules polyvalent alcohol, di-carboxylic acid, ester, the modified natural grease that obtains in step 1) add and are heated to 170 ℃ in reaction vessel, then add after catalyzer temperature to be controlled at 200 ℃ and slowly are warming up to 230 ℃, and insulation detects acid number.
Described small molecules polyvalent alcohol is the mixture of glycol ether, triglycol, polyoxyethylene glycol, glycerine, sorbyl alcohol, tetramethylolmethane.
Described di-carboxylic acid and dicarboxylic acid anhydride and ester thereof can select to comprise terephthalic acid and by product; Tetra hydro Phthalic anhydride and by product thereof; Polyethylene terephthalate (PET polyester) and byproduct are with fragrant same clan carboxylic acid etc.
Described catalyzer is esterifying catalyst.
Described esterifying catalyst includes any in organic titanate class catalyzer, organic tin catalyzer, calcium oxide, zinc oxide.Described organic titanate class catalyzer is any in isopropyl titanate, butyl (tetra) titanate.
Described organic tin catalyzer is any in di-n-butyl stannic oxide (DBTO), Mono-n-butyltin (MBTO).
Compared with prior art, the present invention is by being incorporated into the grease after modification in the middle of the polyester body than more completely, thereby improved the functionality of whole product, compare and directly add the Aromatic Polyester Polyols of grease to compare, advantage on performance is so more arranged, especially aspect the intermiscibility of cyclopentanes.The invention has the beneficial effects as follows like this: the raw materials cost that uses is cheap, technological operation is easy, the present invention is after first utilizing cis-butenedioic anhydride to carry out modification to natural fats and oils, with the small molecules polyvalent alcohol, di-carboxylic acid and acid anhydrides and carboxylicesters reaction can obtain the polyester polyol product of high pentamethylene solubility again.Especially in producing the low-density polyurethane foam process, can improve pentamethylene used solubleness in polyester polyol, make solubleness be increased at least 25% (quality).
Embodiment
The invention will be further described below in conjunction with embodiment.Should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the principle of the invention, can also make some modification and improvement, these also should be considered within the scope of protection of the present invention.
Complete the production method of the polyester polyol of embodiment 1 to embodiment 6 according to the formula of table 1, the method comprises the steps:
The first step, be warming up to 180 ℃ after adding natural fats and oils and cis-butenedioic anhydride progressively to be warmed up to 160 ℃ in the glass reaction still of 2 liters in 2 hours, be warming up to 200 ℃ from 180 ℃ in 1 hour again, 200 ℃ the insulation 4 hours after cooling discharge, obtain the yellow transparent thick liquid stand-by, the yellow transparent thick liquid is the modified natural grease.Wherein in embodiment 1 and 2, natural fats and oils is soybean oil, and the mol ratio of soybean oil and cis-butenedioic anhydride is 1:2; In embodiment 3 and 4, natural fats and oils is vegetable oil acid, and the mol ratio of vegetable oil acid and cis-butenedioic anhydride is 1:1; In embodiment 5 and 6, natural fats and oils is Semen Maydis oil, and the mol ratio of Semen Maydis oil and cis-butenedioic anhydride is 1:3.
second step, the vacuum pump that is equipped with to 1 liter, reflux exchanger, separator column, in the glass reaction still of susceptor and electric mantle, add respectively the interpolation glycol ether by table 1 formula, triglycol, glycerine, polyoxyethylene glycol, tetramethylolmethane, sorbyl alcohol, Tetra hydro Phthalic anhydride, terephthalic acid, the modified natural grease that PET polyester and the first step obtain is heated to 170 ℃, add that the leaving water temperature(LWT) according to reflux exchanger is controlled at below 100 ℃ after 0.5～1%DBTO catalyzer of total charging capacity, carry out slowly reactant being warming up to 230 ℃, insulation detects after acid number is down to below 5mgKOH/g, stopped heating, open vacuum pump after cooling to 200 ℃ and carry out rectifying, slowly gas clean-up until-below 0.09mPa, reactive distillation processes last till reaction mixture to water content lower than 0.1% (weight), survey acid number reach acid number drop to 1.0mgKOH/g following after cooling discharge get polyester polyol, detect respectively the performance of polyester polyol.
The characteristics of consequent polyester polyol are determined hydroxyl value, acid number, viscosity and pentane solubility.Polyvalent alcohol production has following characteristic as stated above.
Table 1:
These results show, embodiment 1 to embodiment 6 has low oil content and has the characteristics of high pentamethylene solubleness, and the solubleness of comparing polyester polyol 5～20% pentamethylene of existing commercialization can be greatly improved, and structure does not have great variation simultaneously.These characteristics, make final froth product, can improve the consumption of polyester under the prerequisite of not sacrificing the foam physics performance, and the content of aromatic acid does not have great variation, the basic physical and chemical performance of polyester polyol all relatively is suitable for existing foam system simultaneously.
Embodiment 7: substantially the same manner as Example 1, difference is: described natural fats and oils is Oleum Cocois, Oleum Gossypii semen, and Toenol 1140, sweet oil, plam oil, palm-kernel oil, peanut oil, Oleum Helianthi, process leach any in the natural fats and oils of purifying.
Embodiment 8: substantially the same manner as Example 1, difference is: described esterifying catalyst comprises any in isopropyl titanate, butyl (tetra) titanate, Mono-n-butyltin (MBTO), calcium oxide, zinc oxide.
Claims (10)
1. the production method of a polyester polyol, is characterized in that, the method comprises the steps:
1) at first cis-butenedioic anhydride and natural fats and oils are placed in reactor, then are heated to 160～200 ℃, and in 160～200 ℃ of insulations cooling after 1～6 hour, obtain the yellow transparent thick liquid, be the modified natural grease, stay subsequent reactions to use; Wherein the mol ratio of cis-butenedioic anhydride and natural fats and oils is 1:1 to 1:3;
2) with the small molecules polyvalent alcohol, di-carboxylic acid and dicarboxylic acid anhydride and ester thereof, the modified natural grease that obtains in step 1) adds in reaction vessel, and then add the catalyzer heating reflux reaction, be warmed up to 220～230 ℃ of insulations and detect acid number, after acid number drops to below 5mgKOH/g, cool to 180～220 ℃, the beginning rectification under vacuum, vacuum degree control-0.065～-0.095mPa, until the acid number of the product after rectifying drops to below 1.0mgKOH/g, the moisture content massfraction is lower than 0.1% rear cooling discharge, namely obtain described polyester polyol, wherein the mass fraction of each component is:
Small molecules polyvalent alcohol: 45～65%
Di-carboxylic acid and dicarboxylic acid anhydride: 20～30%
Ester: 0～10%
Modified natural grease: 10～20%.
2. the production method of polyester polyol according to claim 1, it is characterized in that, in step 1), be warming up to 180 ℃ after first cis-butenedioic anhydride and natural fats and oils progressively being warmed up to 160 ℃ in 2 hours, then be warming up to 200 ℃ from 180 ℃ in 1 hour, at last at 200 ℃ of insulations cooling discharge after 4 hours.
3. the production method of polyester polyol according to claim 1 and 2, it is characterized in that, described natural fats and oils comprises Semen Maydis oil, soybean oil, Oleum Cocois, Oleum Gossypii semen, Toenol 1140, sweet oil, plam oil, palm-kernel oil, peanut oil, Oleum Helianthi, process leach any one or more in the natural fats and oils of purifying and the lipid acid of purifying out through acidifying again after saponification from natural fats and oils.
4. the production method of polyester polyol according to claim 1, it is characterized in that, step 2) in, the modified natural grease that obtains in small molecules polyvalent alcohol, di-carboxylic acid and dicarboxylic acid anhydride and ester thereof, step 1) is added be heated to 170 ℃ in reaction vessel, then add after catalyzer temperature to be controlled at 200 ℃ and slowly be warming up to 230 ℃, insulation detects acid number.
5. the production method of according to claim 1 or 4 described polyester polyols, is characterized in that, described small molecules polyvalent alcohol is the mixture of glycol ether, triglycol, polyoxyethylene glycol, glycerine, sorbyl alcohol, tetramethylolmethane.
6. the production method of according to claim 1 or 4 described polyester polyols, is characterized in that, described diprotic acid and dicarboxylic acid anhydride and ester thereof can select to comprise terephthalic acid and by product; Tetra hydro Phthalic anhydride and by product thereof; Polyethylene terephthalate and byproduct are with fragrant same clan carboxylic acid etc.
7. the production method of according to claim 1 or 4 described polyester polyols, is characterized in that, described catalyzer is esterifying catalyst.
8. the production method of polyester polyol according to claim 7, is characterized in that, described esterifying catalyst includes any in organic titanate class catalyzer, organic tin catalyzer, calcium oxide, zinc oxide.
9. the production method of polyester polyol according to claim 8, is characterized in that, described organic titanate class catalyzer is any in isopropyl titanate, butyl (tetra) titanate.
10. the production method of polyester polyol according to claim 8, is characterized in that, described organic tin catalyzer is any in di-n-butyl stannic oxide, Mono-n-butyltin.
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| CN104262596A (en) * | 2014-09-23 | 2015-01-07 | 四川东材科技集团股份有限公司 | High-functionality degree polyester polyol and preparation method thereof |
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN111978524A (en) * | 2020-09-08 | 2020-11-24 | 江苏德励达新材料有限公司 | Method for preparing nitrogenous heterocyclic polyester polyol with good pentane compatibility |
| CN113512172A (en) * | 2021-06-02 | 2021-10-19 | 茂施农业科技有限公司 | Polyester polyol polyurethane controlled-release fertilizer film material synthesized by sebacic acid byproduct fatty acid |
| CN114249883A (en) * | 2022-01-06 | 2022-03-29 | 衡水新光新材料科技有限公司 | Water-soluble oil dispersant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262596A (en) * | 2014-09-23 | 2015-01-07 | 四川东材科技集团股份有限公司 | High-functionality degree polyester polyol and preparation method thereof |
| CN104262596B (en) * | 2014-09-23 | 2016-08-31 | 四川东材科技集团股份有限公司 | A kind of high-functionality polyester polyol and preparation method thereof |
| CN106750211A (en) * | 2016-12-16 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN106750211B (en) * | 2016-12-16 | 2019-06-28 | 上海华峰材料科技研究院（有限合伙） | The good aromatic polyester polyol and preparation method thereof with pentamethylene compatibility |
| CN111978524A (en) * | 2020-09-08 | 2020-11-24 | 江苏德励达新材料有限公司 | Method for preparing nitrogenous heterocyclic polyester polyol with good pentane compatibility |
| CN113512172A (en) * | 2021-06-02 | 2021-10-19 | 茂施农业科技有限公司 | Polyester polyol polyurethane controlled-release fertilizer film material synthesized by sebacic acid byproduct fatty acid |
| CN113512172B (en) * | 2021-06-02 | 2022-02-22 | 茂施农业科技有限公司 | Sebacic acid byproduct fatty acid polyester polyol for polyurethane controlled release fertilizer coating |
| CN114249883A (en) * | 2022-01-06 | 2022-03-29 | 衡水新光新材料科技有限公司 | Water-soluble oil dispersant and preparation method thereof |
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