CN101851328B - High-functionality polyester polyol and preparation method thereof - Google Patents
High-functionality polyester polyol and preparation method thereof Download PDFInfo
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- CN101851328B CN101851328B CN2010102054510A CN201010205451A CN101851328B CN 101851328 B CN101851328 B CN 101851328B CN 2010102054510 A CN2010102054510 A CN 2010102054510A CN 201010205451 A CN201010205451 A CN 201010205451A CN 101851328 B CN101851328 B CN 101851328B
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Abstract
The invention relates to high-functionality polyester polyol and a preparation method thereof. The polyol is prepared from 400-450 parts of PTA oxidation residue, 180-210 parts of glycerol, 80-140 parts of diglycol, 20-30 parts of pentaerythritol, 50-90 parts of oleic acid and 1-2 parts of catalyst. The preparation method comprises the following steps of: extracting various raw materials according to the proportion, sending the raw materials into a reaction kettle, heating, stirring and introducing nitrogen gas; evaporating all water of the raw materials in the kettle; cooling after evaporating all water, and stopping the introduction of nitrogen gas; heating and vacuumizing the kettle to form high temperature and high vacuum; polymerizing all raw materials at high temperature and in high vacuum, and greatly increasing the molecular weight of polyester; and discharging to obtain the finished product after various indexes of the molecular weight of polyester are measured to reach specified values. The high-functionality polyester polyol has the advantages of high wear resistance, strength, stability, heat resistance, aging resistance and the like.
Description
Technical field
The present invention relates to the polyester polyol technical field, specifically high-functionality polyester polyol and preparation method thereof.
Background technology
Urethane resin has expandable, elasticity, wear resistance, cementability, lower temperature resistance, characteristics such as solvent resistance and resistance to biodeterioration, therefore of many uses, it is to develop a kind of faster high molecular synthetic material, and polyurethane industrial has formed bigger industrial scale.
China's polyurethane industrial originates in late 1950s, and 50 years of development histories have been arranged so far.As the polyester polyol of one of urethane main raw material, its domestic needs is also in continuous expansion.Domestic in recent years is the raw material production polyester polyol with PTA residue and PTA oxidation residua, and it is subjected to affirming and favorable comment of users with its cheap price and superior performance, and has occupied certain market share rapidly.But because of residue is a kind of mixture of complexity, a lot of single acid are contained in the inside, have influenced the performance of product, make hard bubbling that it sends out shortcake occur sending out, and bad proterties such as contraction have had a strong impact on the quality of product.The crosslinked polyurethane material that makes of polyurethane material intramolecularly appropriateness is in hardness, softening temperature, and Young's modulus, elongation at break, tension set and the aspects such as swelling property in solvent all are improved.The functionality that improves polyurethane polyol just can improve the degree of crosslinking of polyurethane material.The polyester polyol of domestic production at present all is two functionality products.
Summary of the invention
The purpose of this invention is to provide high-functionality polyester polyol and preparation method thereof, the high-functionality polyester polyol for preparing with this preparation method has all good advantages such as wear resistance, intensity, stability, thermotolerance, ageing resistance.
Technical scheme of the present invention is: high-functionality polyester polyol, this polyvalent alcohol are to be made by the raw material of following weight part: PTA oxidation residua 400-450 part, glycerol 180-210 part, glycol ether 80-140 part, tetramethylolmethane 20-30 part, oleic acid 50-90 part, catalyzer 1-2 part.Its preparation method comprises following processing step: extract each raw material and each raw material is sent in the reactor by the above-mentioned raw materials proportioning, heat temperature raising is treated to begin to stir after each raw materials melt, and is fed nitrogen.Moisture content when reactor temperature reaches 145-165 ℃ in each raw material begins to be steamed, and continues to heat to make reactor temperature reach 175-215 ℃, keeps this temperature 9-11 hour, and the moisture content in each raw material is all steamed from reactor.Moisture content in each raw material is steamed the back to be continued to keep said temperature 1-2 hour.Stop then heating and lowering the temperature, when temperature is reduced to 90-100 ℃, stop to feed nitrogen and begin slowly to be evacuated to 0.08Mpa, kept 1 hour.Continue to be evacuated to 0.099-0.1Mpa, heating when vacuumizing makes temperature reach 220-230 ℃, and each raw material carries out polycondensation in reactor under above-mentioned high vacuum, high-temperature, and the polycondensation time is 4-9 hour.Its molecular weight of polyesters increase was very fast when raw material carried out polycondensation.In the polycondensation period, constantly measure every index of molecular weight of polyesters, when the hydroxyl value of molecular weight of polyesters reaches 400-430mgKOH/g, acid number reaches≤3.0mgKOH/g, viscosity is 4000-6000mPa.S/25 ℃, the quality percentage of moisture is below 0.025, functionality＞3 o'clock just from reactor discharging obtain finished product.
Described catalyzer is a tetrabutyl titanate, stannous octoate, Dibutyltin oxide, dibutyltin diacetate, the mixture of one or more in the dibutyl tin dilaurate.
The preparation method of high-functionality polyester polyol comprises following processing step: with PTA oxidation residua 400-450 part, glycerol 180-210 part, glycol ether 80-140 part, tetramethylolmethane 20-30 part, oleic acid 50-90 part, catalyzer 1-2 part is sent in the reactor heat temperature raising, treat to begin to stir after each raw materials melt, and feed nitrogen.Water when reactor temperature reaches 145-165 ℃ in each raw material begins to be steamed, and continues to heat to make reactor temperature reach 175-215 ℃, keeps this temperature 9-11 hour, and the water in each raw material is all steamed from reactor.Water in each raw material is steamed the back to be continued to keep said temperature 1-2 hour.Stop then heating and lowering the temperature, when temperature is reduced to 90-100 ℃, stop to feed nitrogen and begin slowly to be evacuated to 0.08Mpa, kept 1 hour.Continue to be evacuated to 0.099-0.1Mpa, heating when vacuumizing makes temperature reach 220-230 ℃, and each raw material carries out polycondensation in reactor under above-mentioned high vacuum, high-temperature, and the polycondensation time is 4-9 hour.Its molecular weight of polyesters increase was very fast when raw material carried out polycondensation.In the polycondensation period, constantly measure every index of molecular weight of polyesters, when the hydroxyl value of molecular weight of polyesters reaches 400-430mgKOH/g, acid number reaches≤3.0mgKOH/g, viscosity is 4000-6000mPa.S/25 ℃, the quality percentage of moisture is below 0.025, functionality＞3 o'clock just from reactor discharging obtain finished product.
Described catalyzer is a tetrabutyl titanate, stannous octoate, Dibutyltin oxide, dibutyltin diacetate, the mixture of one or more in the dibutyl tin dilaurate.
Be adjacent more than 85% in the described PTA oxidation residua,, terephthalic acid, all the other are p-methylbenzoic acid, to carboxyl benzaldehyde, a small amount of phenylformic acid acetic acid etc.
According to the functionality calculation formula as can be known: y=(2Xg+3Xt-2)/(Xg+Xt-1).
Y is the functionality degree of branching.
Xg is the mol ratio of dibasic alcohol/diprotic acid.
Xt is the mol ratio of trivalent alcohol/diprotic acid.
When Xg=1, functionality degree of branching y=(2 * 1+3Xt-2) ÷ (1+Xt-1)=3, i.e. Zhi polyester trivalent alcohol.When Xg＞1,2＜y＜3, this is the most applications of synthesizing branched polyester, promptly adds the trivalent alcohol of minute quantity in raw material.When Xg＜1, y＞3.Because this moment, Xt just must be big in order to obtain hydroxyl telechelic polyester, and a large amount of trivalent alcohols, can make again easily produce in the building-up process crosslinked.At present the functionality degree of branching of the polyester polyol of producing with prior art is y＜3.The functionality degree of branching of the polyester polyol of producing with this preparation method is y＞3.
With the PTA oxidation residua is raw material, improve functionality with glycerol and tetramethylolmethane, and add the high-functionality polyester polyol that the oleic acid modification makes, greatly improved the intensity of polyester polyol, dimensional stability, also alleviated its swelling phenomenon in organic solvent of hard bubbling, made its ageing resistance further raising arranged.The increase of functionality further strengthens the molecular weight of polyester polyol, has improved the thermal stability of product, makes the use of product that more wide space arranged.
Advantage of the present invention has provided high-functionality polyester polyol and preparation method thereof, and the high-functionality polyester polyol for preparing with this preparation method has all good advantages such as wear resistance, intensity, stability, thermotolerance, ageing resistance.
Embodiment
Embodiment 1:
High-functionality polyester polyol is to be made by the raw material of following weight part, 400 parts of PTA oxidation residuas, 200 parts of glycerol, 100 parts of glycol ethers, 20 parts of tetramethylolmethanes, 80 parts of oleic acid, 1.5 parts of tetrabutyl titanates.Its preparation method comprises following processing step: extract each raw material and each raw material is sent in the reactor by the above-mentioned raw materials proportioning, heat temperature raising is treated to begin to stir after each raw materials melt, and is fed nitrogen.When reactor temperature reached 145-165 ℃, the moisture content in each raw material began to be steamed, and continuing to heat makes reactor temperature reach 175-215 ℃, keeps this temperature 9-11 hour, and the moisture content in each raw material is all steamed from reactor.Moisture content in each raw material is steamed the back to be continued to keep said temperature 1-2 hour.Stop then heating and lowering the temperature, when temperature is reduced to 90-100 ℃, stop to feed nitrogen and begin slowly to be evacuated to 0.08Mpa, kept 1 hour.Continue to be evacuated to 0.099-0.1Mpa, heating when vacuumizing makes temperature reach 220-230 ℃, and each raw material carries out polycondensation in reactor under above-mentioned high vacuum, high-temperature, and the polycondensation time is 4-9 hour.Its molecular weight of polyesters increase was very fast when raw material carried out polycondensation.In the polycondensation period, constantly measure every index of molecular weight of polyesters, when the hydroxyl value of molecular weight of polyesters reaches 400-430mgKOH/g, acid number reaches≤3.0mgKOH/g, viscosity is 4000-6000mPa.S/25 ℃, the quality percentage of moisture is below 0.025, functionality＞3 o'clock just from reactor discharging obtain finished product.
Embodiment 2:
High-functionality polyester polyol is to be made by the raw material of following weight part, 450 parts of PTA oxidation residuas, 210 parts of glycerol, 120 parts of glycol ethers, 25 parts of tetramethylolmethanes, 70 parts of oleic acid, 2 parts of stannous octoates.Its preparation method is identical with embodiment 1.
Embodiment 3:
High-functionality polyester polyol is to be made by the raw material of following weight part, 420 parts of PTA oxidation residuas, 190 parts of glycerol, 95 parts of glycol ethers, 22 parts of tetramethylolmethanes, 65 parts of oleic acid, 1.2 parts of dibutyl tin dilaurate.Its preparation method is identical with embodiment 1.
Claims (4)
1. high-functionality polyester polyol, it is characterized in that: this polyvalent alcohol is to be made by the raw material of following weight part: PTA oxidation residua 400-450 part, glycerol 180-210 part, glycol ether 80-140 part, tetramethylolmethane 20-30 part, oleic acid 50-90 part, catalyzer 1-2 part; Its preparation method comprises following processing step: extract each raw material and each raw material is sent in the reactor by the above-mentioned raw materials proportioning, heat temperature raising is treated to begin to stir after each raw materials melt, and is fed nitrogen; Moisture content when reactor temperature reaches 145-165 ℃ in each raw material begins to be steamed, and continues to heat to make reactor temperature reach 175-215 ℃, keeps this temperature 9-11 hour, and the moisture content in each raw material is all steamed from reactor; Moisture content in each raw material is steamed the back to be continued to keep said temperature 1-2 hour; Stop then heating and lowering the temperature, when temperature is reduced to 90-100 ℃, stop to feed nitrogen and begin slowly to be evacuated to 0.08Mpa, kept 1 hour; Continue to be evacuated to 0.099-0.1Mpa, when vacuumizing, heat and make temperature reach 220-230 ℃, each raw material carries out polycondensation in reactor under above-mentioned high vacuum, high-temperature, and the polycondensation time is 4-9 hour, and its molecular weight of polyesters increase was very fast when raw material carried out polycondensation; In the polycondensation period, constantly measure every index of molecular weight of polyesters, when the hydroxyl value of molecular weight of polyesters reaches 400-430mgKOH/g, acid number reaches≤3.0mgKOH/g, viscosity is 4000-6000mPa.S/25 ℃, the quality percentage of moisture is below 0.025, functionality＞3 o'clock just from reactor discharging obtain finished product.
2. high-functionality polyester polyol according to claim 1 is characterized in that: described catalyzer is a tetrabutyl titanate, stannous octoate, Dibutyltin oxide, dibutyltin diacetate, the mixture of one or more in the dibutyl tin dilaurate.
3. the preparation method of high-functionality polyester polyol, it is characterized in that: with PTA oxidation residua 400-450 part, glycerol 180-210 part, glycol ether 80-140 part, tetramethylolmethane 20-30 part, oleic acid 50-90 part, catalyzer 1-2 part is sent in the reactor, heat temperature raising is treated to begin to stir after each raw materials melt, and is fed nitrogen; Moisture content when reactor temperature reaches 145-165 ℃ in each raw material begins to be steamed, and continues to heat to make reactor temperature reach 175-215 ℃, keeps this temperature 9-11 hour, and the moisture content in each raw material is all steamed from reactor; Moisture content in each raw material is steamed the back to be continued to keep said temperature 1-2 hour; Stop then heating and lowering the temperature, when temperature is reduced to 90-100 ℃, stop to feed nitrogen and begin slowly to be evacuated to 0.08Mpa, kept 1 hour; Continue to be evacuated to 0.099-0.1Mpa, when vacuumizing, heat and make temperature reach 220-230 ℃, each raw material carries out polycondensation in reactor under above-mentioned high vacuum, high-temperature, and the polycondensation time is 4-9 hour, and its molecular weight of polyesters increase was very fast when raw material carried out polycondensation; In the polycondensation period, constantly measure every index of molecular weight of polyesters, when the hydroxyl value of molecular weight of polyesters reaches 400-430mgKOH/g, acid number reaches≤3.0mgKOH/g, viscosity is 4000-6000mPa.S/25 ℃, the quality percentage of moisture is below 0.025, functionality＞3 o'clock just from reactor discharging obtain finished product.
4. the preparation method of high-functionality polyester polyol according to claim 3, it is characterized in that: described catalyzer is a tetrabutyl titanate, stannous octoate, Dibutyltin oxide, dibutyltin diacetate, the mixture of one or more in the dibutyl tin dilaurate.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2836534A1 (en) * | 2012-04-10 | 2015-02-18 | Huntsman International LLC | High functional polyester polyols |
| CN104072741B (en) * | 2014-07-09 | 2016-01-27 | 湖南工学院 | A kind of polyester polyol and polyurethane foams and preparation method |
| CN105461915B (en) * | 2015-12-24 | 2018-02-23 | 山东一诺威新材料有限公司 | Micropore PU soles polyesterether polyols, its preparation method and its PU soles systems of preparation and the preparation method of PU soles systems |
| CN107857896B (en) * | 2017-11-16 | 2019-07-09 | 上海炼升化工股份有限公司 | A kind of ester composition and preparation method thereof from PTA substandard goods |
| CN109824873A (en) * | 2019-01-25 | 2019-05-31 | 江苏康宏新材料有限公司 | It is a kind of for full water foamed polyester polyol and preparation method thereof |
| CN109847808B (en) * | 2019-01-28 | 2022-02-08 | 上海炼升化工股份有限公司 | Method for recovering heavy metal catalyst in PTA residues |
| CN110643011B (en) * | 2019-08-02 | 2022-02-08 | 上海炼升化工股份有限公司 | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof |
| CN110563935B (en) * | 2019-08-02 | 2021-08-24 | 上海炼升化工股份有限公司 | High-functionality polyester polyol and preparation method thereof |
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2010
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