CN103087304B - Production method of polyester polyol - Google Patents
Production method of polyester polyol Download PDFInfo
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- CN103087304B CN103087304B CN201310020208.5A CN201310020208A CN103087304B CN 103087304 B CN103087304 B CN 103087304B CN 201310020208 A CN201310020208 A CN 201310020208A CN 103087304 B CN103087304 B CN 103087304B
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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, is called that combined polyether glycol formula is for the manufacture of polyurethane foam important component part.Other important component parts are isocyanic ester.Another important composition is also had to be whipping agent.Do not have whipping agent, it is the porous plastics that impossible make low density and have very high strength-weight ratio.Now commercially suitable whipping agent is fluorocarbon, hydrocarbon polymer, and carbon dioxide.
Water and isocyanate reaction form a unstable carboxylamine, are decomposed to form amine and carbonic acid gas.Amine immediate response forms an extra isocyanic ester substituted urea.As adopted too much water as whipping agent, urea can cause polyurethane foam crisp and frangible, thus worsens foam and substrate adherence energy.On the other hand, carbonic acid gas, in polyurethane foam, has higher infiltration than air, thus low-density polyurethane foam may be caused to shrink.Moreover the isocyanate reaction release 1mol carbonic acid gas of the water reaction 2mol of 1mol, existing isocyanic ester price is commercially higher, and thus it neither a very economical whipping agent.Meanwhile, carbon dioxide has higher thermal conductivity than fluorocarbon and hydrocarbon polymer, and because it is generally insoluble to most of common polyethers or polyester, so little to the effect of the viscosity reducing combined polyether, thus the use of combined polyether glycol is affected to some extent.
Commercially modal fluorocarbon master is: 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, the developing country comprising 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.Be worth it is specifically intended that in hot weather, when being mixed with combined polyether glycol by HFC-245fa, boiling point is that the HFC-245fa of 15.3 degrees Celsius is not easy operation very much.Although, energy water replaces part HFC-245fa, the vapour pressure of combined polyether glycol is reduced with this, if but too many water is used in combined polyether glycol, the physicals of some foams will suffer damage, compare water and hydrocarbon polymer, HFC-245fa is an expensive whipping agent simultaneously.
As the hydrocarbon polymer of whipping agent, now the most frequently used is the pentane of isomer.On urethane foam market, there is the pentane of three kinds of isomer: pentamethylene, iso-pentane and Skellysolve A.Abroad, for the application of pentane according to the processing mode of foam, be substantially divided into: heat preservation plate material have employed the Skellysolve A of a kind of ratio of mixture at 0.2:0.8 to 0.8:0.2 and the miscellany of iso-pentane; Spraying bubble then adopts 95% pentamethylene; The pentamethylene of blending ratio from 20:80 to 50:50 and iso-pentane are then for pouring into a mould in foam.Adopt the advantage of pentane as follows: pentane is cheap and compare and be easy to get, and pentane gas thermal conductivity is lower than carbonic acid gas.Pentane shortcoming is adopted to comprise following: it is a kind of inflammable liquid, needs to carry out special processing; The intermiscibility of it and current high hydroxyl value and high function aromatic polyester polyol is poor; Which reduce the usage quantity of water at combined polyether.
More than Integrated comparative three class whipping agents, hydrocarbon class pentane series whipping agent is candidate products the strongest in the application of polyurethane rigid foam plastic system.
Commercial polyester polyvalent alcohol has certain pentane solubility, but higher solubleness is necessary, although (solubility property of all kinds of pentane is different to some extent, but it is relevant little, so we adopt pentamethylene and polyester polyol to illustrate below), because present commercial polyvalent alcohol has the solubleness of 5 ~ 20% pentamethylene, but add polyvalent alcohol to along with what more and more measure many pentamethylene, such solubleness easily makes pentamethylene be separated.So when producing now low-density polyurethane foam, be separated for preventing pentamethylene, adopt the intermiscibility increasing pentamethylene by adding emulsifying agent method, but the many factors due to other can have influence on the intermiscibility (as water content, polyester consumption etc.) of pentamethylene, this kind of combined polyether glycol lacks permanent stability.
Summary of the invention
In order to overcome the deficiencies in the prior art, a kind of pentamethylene that can prevent is the object of the present invention is to provide to be separated the production method also can with 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) first cis-butenedioic anhydride and natural fats and oils are placed in reactor, are then heated to 160 ~ 200 DEG C, and in 160 ~ 200 DEG C of insulations cooling after 1 ~ 6 hour, obtain yellow transparent thick liquid, be 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 obtained in small molecule polyol, di-carboxylic acid and acid anhydrides and ester thereof, step 1) is added in reaction vessel, and then add catalyzer heating reflux reaction, 220 ~ 230 DEG C are incubated and detect acid number, after acid number drops to below 5mgKOH/g, cool to 180 ~ 220 DEG C, start rectification under vacuum, vacuum degree control is at-0.065 ~-0.095mPa, until the acid number of product after rectifying drops to below 1.0mgKOH/g, moisture content mass fraction is lower than 0.1% rear cooling discharge, namely described polyester polyol is obtained, wherein
Small molecule polyol: 45 ~ 65%
Di-carboxylic acid and dicarboxylic acid anhydride: 20 ~ 30%
Ester: 0 ~ 10%
Modified natural grease: 10 ~ 20%.
In step 1), in 2 hours, be warming up to 180 DEG C after first cis-butenedioic anhydride and natural fats and oils being progressively warmed up to 160 DEG C, then in 1 hour, be warming up to 200 DEG C from 180 DEG C, cooling discharge after being finally incubated 4 hours at 200 DEG C.
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, through leaching any one or more in the natural fats and oils and the lipid acid of purifying out through acidifying again after saponification from natural fats and oils of purifying.
Step 2) in, small molecule polyol, di-carboxylic acid, ester, the modified natural grease obtained in step 1) adds in reaction vessel and is heated to 170 DEG C, and after then adding catalyzer, temperature controls slowly to be warming up to 230 DEG C at 200 DEG C, and insulation detects acid number.
Described small molecule polyol 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, be with fragrant same clan carboxylic acid etc.
Described catalyzer is esterifying catalyst.
Described esterifying catalyst includes any one in organic titanate class catalyzer, organic tin catalyzer, calcium oxide, zinc oxide.Described organic titanate class catalyzer is any one in isopropyl titanate, butyl (tetra) titanate.
Described organic tin catalyzer is any one in di-nbutyltin oxide (DBTO), Mono-n-butyltin (MBTO).
Compared with prior art, the present invention is by being incorporated into modified grease than more completely in the middle of polyester body, thus improve the functionality of whole product, compare the Aromatic Polyester Polyols directly adding grease to compare, so more there is the advantage in performance, especially in the intermiscibility of cyclopentanes.The invention has the beneficial effects as follows like this: the low raw-material cost used, technological operation are easy, the present invention first utilizes cis-butenedioic anhydride to carry out modified to natural fats and oils, again with small molecule polyol, di-carboxylic acid and acid anhydrides and carboxylicesters reaction can obtain the polyester polyol product of high pentamethylene solubility.Especially, in production low-density polyurethane foam process, pentamethylene used solubleness in polyester polyol can be improved, make solubleness at least be increased to 25% (quality).
Embodiment
Below in conjunction with embodiment, the invention will be further described.It should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles 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, add in the glass reaction still of 2 liters after natural fats and oils and cis-butenedioic anhydride are progressively warmed up to 160 DEG C and be warming up to 180 DEG C in 2 hours, within 1 hour, be warming up to 200 DEG C from 180 DEG C again, cooling discharge after being incubated 4 hours at 200 DEG C, obtain yellow transparent thick liquid stand-by, yellow transparent thick liquid is 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, to 1 liter vacuum pump is housed, reflux exchanger, separator column, in the glass reaction still of susceptor and electric mantle, fill a prescription by table 1 and add interpolation glycol ether respectively, 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 DEG C, control below 100 DEG C according to the leaving water temperature(LWT) of reflux exchanger after adding 0.5 ~ 1%DBTO catalyzer of total charging capacity, carry out slowly reactant being warming up to 230 DEG C, insulation detects after acid number is down to below 5mgKOH/g, stop heating, open vacuum pump after cooling to 200 DEG C and carry out rectifying, slow gas clean-up is until below-0.09mPa, reactive distillation processes lasts till reaction mixture to water content lower than 0.1% (weight), survey acid number to reach acid number and drop to cooling discharge after below 1.0mgKOH/g and obtain polyester polyol, detect the performance of polyester polyol respectively.
Feature determination hydroxyl value, acid number, viscosity and the pentane solubility of consequent polyester polyol.Polyvalent alcohol is produced following characteristic as stated above.
Table 1:
These results show, embodiment 1 to embodiment 6 has low oil content and has the feature of high pentamethylene solubleness, and the solubleness comparing polyester polyol 5 ~ 20% pentamethylene of existing commercialization can be greatly improved, and structure does not have great change simultaneously.This feature, make final froth product, can improve the consumption of polyester under the prerequisite of not sacrificing foam physics performance, and the content of aromatic acid does not have great change, the basic physical and chemical performance of polyester polyol all compares and 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, Toenol 1140, sweet oil, plam oil, palm-kernel oil, peanut oil, and Oleum Helianthi, process leach any one in the natural fats and oils of purifying.
Embodiment 8: substantially the same manner as Example 1, difference is: described esterifying catalyst comprises any one in isopropyl titanate, butyl (tetra) titanate, Mono-n-butyltin (MBTO), calcium oxide, zinc oxide.
Claims (10)
1. a production method for polyester polyol, is characterized in that, the method comprises the steps:
1) first cis-butenedioic anhydride and natural fats and oils are placed in reactor, are then heated to 160 ~ 200 DEG C, and in 160 ~ 200 DEG C of insulations cooling after 1 ~ 6 hour, obtain yellow transparent thick liquid, be 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) by small molecule polyol, di-carboxylic acid and dicarboxylic acid anhydride and ester thereof, the modified natural grease obtained in step 1) adds in reaction vessel, and then add catalyzer heating reflux reaction, be warmed up to 220 ~ 230 DEG C of insulations and detect acid number, after acid number drops to below 5mgKOH/g, cool to 180 ~ 220 DEG C, start rectification under vacuum, vacuum degree control is at-0.065 ~-0.095mPa, until the acid number of product after rectifying drops to below 1.0mgKOH/g, moisture content massfraction is lower than 0.1% rear cooling discharge, namely described polyester polyol is obtained, wherein the mass fraction of each component is:
Small molecule polyol: 45 ~ 65%
Di-carboxylic acid and dicarboxylic acid anhydride: 20 ~ 30%
Ester: 0 ~ 10%
Modified natural grease: 10 ~ 20%.
2. according to the production method of the polyester polyol described in claim 1, it is characterized in that, in step 1), in 2 hours, 180 DEG C are warming up to after first cis-butenedioic anhydride and natural fats and oils being progressively warmed up to 160 DEG C, then in 1 hour, 200 DEG C are warming up to from 180 DEG C, cooling discharge after being finally incubated 4 hours at 200 DEG C.
3. the production method of the polyester polyol according to claim 1 or 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, through leaching any one or more in the natural fats and oils and the lipid acid of purifying out through acidifying again after saponification from natural fats and oils of purifying.
4. according to the production method of the polyester polyol described in claim 1, it is characterized in that, step 2) in, the modified natural grease obtained in small molecule polyol, di-carboxylic acid and dicarboxylic acid anhydride and ester thereof, step 1) is added in reaction vessel and is heated to 170 DEG C, then after adding catalyzer, temperature controls slowly to be warming up to 230 DEG C at 200 DEG C, and insulation detects acid number.
5. the production method of the polyester polyol according to claim 1 or 4, is characterized in that, described small molecule polyol is the mixture of glycol ether, triglycol, polyoxyethylene glycol, glycerine, sorbyl alcohol, tetramethylolmethane.
6. the production method of the polyester polyol according to claim 1 or 4, is characterized in that, described diprotic acid and dicarboxylic acid anhydride and ester thereof, comprise terephthalic acid and by product; Tetra hydro Phthalic anhydride and by product thereof; Polyethylene terephthalate and byproduct.
7. the production method of the polyester polyol according to claim 1 or 4, is characterized in that, described catalyzer is esterifying catalyst.
8. according to the production method of the polyester polyol described in claim 7, it is characterized in that, described esterifying catalyst includes any one in organic titanate class catalyzer, organic tin catalyzer, calcium oxide, zinc oxide.
9. the production method of polyester polyol described according to Claim 8, it is characterized in that, described organic titanate class catalyzer is any one in isopropyl titanate, butyl (tetra) titanate.
10. the production method of polyester polyol described according to Claim 8, it is characterized in that, described organic tin catalyzer is any one in di-nbutyltin oxide, Mono-n-butyltin.
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| 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 |
| 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 |
| 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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| CN100528819C (en) * | 2007-02-07 | 2009-08-19 | 上海中科合臣股份有限公司 | Preparing method for high hydroxyl value plant oil polyhydric alcohol |
| CN101805258B (en) * | 2010-03-18 | 2013-03-27 | 宁波万华容威聚氨酯有限公司 | Preparation method of novel vegetable oil polyol for polyurethane rigid foam |
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