CN104987497A - Method for removing acid value in polyester polyol by column chromatography separation - Google Patents
Method for removing acid value in polyester polyol by column chromatography separation Download PDFInfo
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- CN104987497A CN104987497A CN201510425929.3A CN201510425929A CN104987497A CN 104987497 A CN104987497 A CN 104987497A CN 201510425929 A CN201510425929 A CN 201510425929A CN 104987497 A CN104987497 A CN 104987497A
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Abstract
The invention relates to a method for removing an acid value in polyester polyol by column chromatography separation. The method comprises the following steps: adding organic dicarboxylic acid (anhydride or ester) and polyol (including glycol) into a reactor, and carrying out melting; then introducing nitrogen, and carrying out reaction at about 150 DEG C so as to generate water; gradually evaporating the reaction-generated water, allowing the temperature in the reactor to gradually rise with the evaporation of water, and determining the acid value in the evaporating process; adding 15 to 100 ppm of organic catalyst at 170 to 230 DEG C when the acid value is not greater than 30mgKOH/g; and then starting vacuum pumping so as to remove the reaction-generated water and low-molecular-weight polyester polyol, and allowing the acid value to be not greater than 2mgKOH/g; and carrying out cooling to 80 to 100 DEG C and passing through an alkali column with a certain flow velocity so as to obtain the polyester polyol with the acid value of not greater than 0.5mgKOH/g. The method for removing the acid value in polyester polyol provided by the invention has the advantages of simple process, low cost and good market prospect.
Description
Technical field
The invention belongs to synthetic resins field, be specifically related to a kind of method crossing acid number in post removal polyester polyol.
Background technology
Polyester polyol is normally by Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) condensation (or transesterify) or formed by lactone and polymerization, is mainly used in the synthesis material of urethane resin.Its preparation process generally all adopts interrupter method to produce: first Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) are added melting in reactor when namely producing, pass into nitrogen, in about 150 DEG C water generation reactions, progressively steam, in still, generate low polyester mixture (low-molecular-weight polyester polyvalent alcohol).Steaming with moisture, temperature in the kettle raises gradually, and at 170 ~ 230 DEG C, vacuum tightness progressively drops to 500Pa, steamed together with the residuary water excessive dibasic alcohol and a small amount of side reaction product (low molecule polyester, aldehyde and ketone) and reaction are generated.The several indexs important for polyester polyol are hydroxyl values, acid number, moisture, viscosity, molecular weight, density and colourity etc., wherein the synthesis of acid number to next step urethane has a great impact, so usually require that the acid number of polyester polyol is less than 0.5mgKOH/g, reach this acid number requirement, the method of general employing is that the phase adds excessive low-molecular-weight diol or finally adds KOH after the reaction, the NaOH aqueous solution neutralizes, but the phase adds excessive low-molecular-weight diol and makes remaining acid material complete reaction after the reaction, a large amount of low-molecular-weight diols need be used, the excessive low-molecular-weight diol energy consumption of recovery increased and loss, and finally add the neutralization of KOH, NaOH aqueous solution except acid number, then easily make polyester polyol produce saponification phenomenon.
Summary of the invention
For overcoming up to standard the taked technique way Problems existing of existing polyester polyol acid number, the present invention adopts parlkaline post to remove the acid number of polyester polyol.
technical scheme of the present invention is:
1, the preparation of alkaline post:
Diameter be 30-50cm, highly for the stainless steel column of 1.0m in load alkaline matter, dress post height is 0.5-0.8m, for subsequent use.
2, the synthesis of polyester polyol:
Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) are added melting in reactor, passes into nitrogen, in about 150 DEG C water generation reactions, progressively steam water generation reaction.Steaming with moisture, temperature in the kettle raises gradually, and measures acid number during the course.At 170 ~ 230 DEG C, when acid number is less than 30mgKOH/g, add 15 ~ 100ppm organic catalyst, and start to vacuumize removing water generation reaction and low-molecular-weight polyester polyvalent alcohol, acid number is made to be less than 2mgKOH/g, then be cooled to 80-100 DEG C, with certain flow velocity by alkaline post, obtain the polyester polyol that acid number is less than 0.5mgKOH/g.
Alkaline matter of the present invention is one or more in KOH, NaOH, sodium methylate, sodium ethylate, sodium propylate, sodium butylate.
Polyester polyol of the present invention is 5g-10kg/min by the flow velocity of alkaline post.
Beneficial outcomes of the present invention is that the acid number removal technique of polyester polyol is simple, with low cost.
Embodiment
Be down several specific embodiment of the present invention below, further illustrate the present invention, but the present invention be not limited only to this.
embodiment 1
Terephthalic acid and ethylene glycol are added melting in reactor, passes into nitrogen, in 150 DEG C of water generation reactions, progressively steam water generation reaction.Steaming with moisture, temperature in the kettle is increased to 190 DEG C gradually, when mensuration acid number is 25mgKOH/g, add 80ppm titanium isopropylate catalyzer, and start to vacuumize removing water generation reaction and low-molecular-weight polyester polyvalent alcohol, mensuration acid number is 1.5mgKOH/g, is then cooled to 90 DEG C, with 10g/min flow velocity by diameter be 50cm, height be the height that is equipped with of 1.0m is the KOH of 0.8m stainless steel column alkalescence post, obtains the polyester polyol that acid number is 0.45mgKOH/g.
embodiment 2
Hexanodioic acid and butyleneglycol are added melting in reactor, passes into nitrogen, in 155-158 DEG C of water generation reaction, progressively steam water generation reaction.Steaming with moisture, temperature in the kettle is increased to 200 DEG C gradually, when mensuration acid number is 27mgKOH/g, add 70ppm tetrabutyl titanate catalyst, and start to vacuumize removing water generation reaction and low-molecular-weight polyester polyvalent alcohol, mensuration acid number is 1.9mgKOH/g, is then cooled to 100 DEG C, with 8kg/min flow velocity by diameter be 40cm, height be the height that is equipped with of 1.0m is the sodium ethylate of 0.9m stainless steel column alkalescence post, obtains the polyester polyol that acid number is 0.41mgKOH/g.
Claims (4)
1. cross the method that acid number in polyester polyol removed by post, its preparation process is:
Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) are added melting in reactor, pass into nitrogen, in about 150 DEG C water generation reactions, progressively steam water generation reaction, steaming with moisture, temperature in the kettle raises gradually, and measure acid number during the course, at 170 ~ 230 DEG C, when acid number is less than 30mgKOH/g, add 15 ~ 100ppm organic catalyst, and start to vacuumize removing water generation reaction and low-molecular-weight polyester polyvalent alcohol, acid number is made to be less than 2mgKOH/g, then 80-100 DEG C is cooled to, with certain flow velocity by alkaline post, obtain the polyester polyol that acid number is less than 0.5mgKOH/g.
2. a kind of method crossing acid number in post removal polyester polyol according to claims 1, is characterized in that the preparation method of described alkaline post is:
Diameter be 30-50cm, highly for the stainless steel column of 1.0m in load alkaline matter, dress post height is 0.5-0.8m.
3. a kind of according to claims 1 crosses the method that acid number in polyester polyol removed by post, it is characterized in that described alkaline matter is one or more in KOH, NaOH, sodium methylate, sodium ethylate, sodium propylate, sodium butylate.
4. a kind of method crossing acid number in post removal polyester polyol according to claims 2, it is characterized in that, polyester polyol of the present invention is 5g-10kg/min by the flow velocity of alkaline post.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510425929.3A CN104987497A (en) | 2015-07-20 | 2015-07-20 | Method for removing acid value in polyester polyol by column chromatography separation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510425929.3A CN104987497A (en) | 2015-07-20 | 2015-07-20 | Method for removing acid value in polyester polyol by column chromatography separation |
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| CN104987497A true CN104987497A (en) | 2015-10-21 |
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| CN201510425929.3A Pending CN104987497A (en) | 2015-07-20 | 2015-07-20 | Method for removing acid value in polyester polyol by column chromatography separation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978254A (en) * | 2016-12-20 | 2017-07-25 | 烟台固特丽生物科技股份有限公司 | A kind of high efficiency DHA grease discoloration method |
| CN108129642A (en) * | 2017-12-20 | 2018-06-08 | 福建师范大学泉港石化研究院 | A kind of method for preventing polyester polyol sour regurgitation |
| CN109988067A (en) * | 2018-12-21 | 2019-07-09 | 江门谦信化工发展有限公司 | A kind of novel purifying niacin dibutyl ester industrialization process |
| CN111458453A (en) * | 2020-05-12 | 2020-07-28 | 万华化学集团股份有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
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| CN1747982A (en) * | 2001-12-15 | 2006-03-15 | 三星电子株式会社 | The recovery method and the salvage material thereof of useless polyester |
| CN103214663A (en) * | 2013-03-28 | 2013-07-24 | 帝斯曼先达合成树脂(佛山)有限公司 | Polyester, aqueous composition including polyester and preparation method of aqueous composition, double-component paint including aqueous composition and preparation method of double-component paint |
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2015
- 2015-07-20 CN CN201510425929.3A patent/CN104987497A/en active Pending
Patent Citations (3)
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| CN1178539A (en) * | 1995-02-27 | 1998-04-08 | 国际壳牌研究有限公司 | Byproduct stream purification in the preparation of 1 ,3 -propanediol-based polyesters |
| CN1747982A (en) * | 2001-12-15 | 2006-03-15 | 三星电子株式会社 | The recovery method and the salvage material thereof of useless polyester |
| CN103214663A (en) * | 2013-03-28 | 2013-07-24 | 帝斯曼先达合成树脂(佛山)有限公司 | Polyester, aqueous composition including polyester and preparation method of aqueous composition, double-component paint including aqueous composition and preparation method of double-component paint |
Non-Patent Citations (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978254A (en) * | 2016-12-20 | 2017-07-25 | 烟台固特丽生物科技股份有限公司 | A kind of high efficiency DHA grease discoloration method |
| CN108129642A (en) * | 2017-12-20 | 2018-06-08 | 福建师范大学泉港石化研究院 | A kind of method for preventing polyester polyol sour regurgitation |
| CN108129642B (en) * | 2017-12-20 | 2020-01-21 | 福建师范大学泉港石化研究院 | Method for preventing polyester polyol from acid reversion |
| CN109988067A (en) * | 2018-12-21 | 2019-07-09 | 江门谦信化工发展有限公司 | A kind of novel purifying niacin dibutyl ester industrialization process |
| CN111458453A (en) * | 2020-05-12 | 2020-07-28 | 万华化学集团股份有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
| CN111458453B (en) * | 2020-05-12 | 2022-07-12 | 万华化学(四川)有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
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