CN104910356A - Preparation method of pyromellitic acid polyester polyol - Google Patents
Preparation method of pyromellitic acid polyester polyol Download PDFInfo
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- CN104910356A CN104910356A CN201510389883.4A CN201510389883A CN104910356A CN 104910356 A CN104910356 A CN 104910356A CN 201510389883 A CN201510389883 A CN 201510389883A CN 104910356 A CN104910356 A CN 104910356A
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- pyromellitic acid
- pyromellitic
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- polyvalent alcohol
- polyester polyol
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Abstract
The invention belongs to the technical field of chemical synthesis, and specifically relates to a preparation method of pyromellitic acid polyester polyol. The method is that pyromellitic dianhydride and micromolecule dihydric alcohol are used as reacting substances and subjected to ring-opening polymerization to prepare pyromellitic acid polyester polyol. The method comprises the steps of feeding pyromellitic dianhydride, micromolecule dihydric alcohol and a catalyst into a polyesterification reaction bottle; charging N2 for protecting; slowly heating to be 230 to 240 DEG C; pumping vacuum when the acid value is not greater than 20mgKOH/g; stopping reacting after the acid value of a product is not greater than 1.5mgKOH/g; cooling to be less than 90 DEG C; pressing and filtering; discharging to obtain pyromellitic acid polyester polyol. The hydroxyl value of the prepared pyromellitic acid polyester polyol is 200 to 450mgKOH/g, and the acid value is 0.9 to 1.5mgKOH/g; benzene ring is introduced, so that the flame retarding performance of pyromellitic acid polyester polyol to a polyurethane foam material is improved; the polyfunctionality structure is beneficial for the generation of the foam material with high degree of crosslinking; the strength and ageing resistance of the foam material can be improved.
Description
Technical field
The invention belongs to technical field of chemical synthesis, specifically, relate to a kind of preparation method of Pyromellitic Acid kind polyester polyvalent alcohol.
Background technology
Polyester polyol is one of main raw material(s) of polyurethane foamed material, the performance quality of polyurethane foamed material has inseparable relation with the quality of polyester polyol, the performance of undressed hard polyurethane foams also exists some defects, such as: flame retardant properties is poor, intensity is not high, and ageing-resistant performance is more weak.The performance being improved polyurethane foamed material by the quality promoting polyester polyol is investigator's institute's work taken up always, and the present invention is by synthesis pyromellitic dianhydride kind polyester polyvalent alcohol.Pyromellitic Acid kind polyester polyvalent alcohol is a kind of polyester polyol of high functionality, and the obtained hard polyurethane foam of itself and isocyanate reaction has good stability of the dimension, excellent fireproof performance and the advantage such as ageing-resistant performance is good.
Summary of the invention
The object of the invention is to prepare a kind of Pyromellitic Acid kind polyester polyvalent alcohol, to improve polyurethane foam performance.
Pyromellitic Acid kind polyester polyvalent alcohol of the present invention is made by ring-opening reaction, its concrete building-up process is as follows: pyromellitic dianhydride, dibasic alcohol and catalyzer are added successively in four-hole boiling flask, logical nitrogen protection, heat temperature raising, heating rate is regulated when temperature rises to 130 ~ 155 DEG C, control backflow tower top temperature at 100 ~ 102 DEG C, control leaving condenser water speed, prevent a large amount of water vapour from taking a small amount of Diethylene Glycol out of a point flow condenser; Temperature is slowly risen to 175 ~ 180 DEG C of insulation 2 ~ 4h, then temperature is risen to 210 ~ 220 DEG C, after moisture stops completely, esterification completes substantially, stops logical water coolant, vacuumizes, cooling, obtained Pyromellitic Acid kind polyester polyvalent alcohol;
Described Pyromellitic Acid kind polyester polyvalent alcohol, hydroxyl value is 200 ~ 450mgKOH/g, acid number≤1.5mgKOH/g, water ratio≤0.03%.
The mol ratio of described pyromellitic dianhydride and dibasic alcohol is 1: 4 ~ 1: 6.
The weight ratio of described pyromellitic dianhydride and catalyzer is 100: 0.03 ~ 0.1.
Described catalyzer potassium fluotitanate or Dibutyltin oxide.
Beneficial effect of the present invention is: the present invention adopts pyromellitic dianhydride and dibasic alcohol ester to obtain Pyromellitic Acid kind polyester polyvalent alcohol, introduces benzene radicals in the polyester, is conducive to the flame retardant properties improving polyurethane foamed material; Introduce the polyester of high functionality, the crosslinking degree of material can be improved, the overall performance of material is improved.
Embodiment
The present invention is illustrated below in conjunction with embodiment.
Embodiment 1:
By pyromellitic dianhydride 43.6g (0.2mol), Diethylene Glycol 42.4g (0.4mol) and potassium fluotitanate (0.022g) add in four-hole boiling flask successively, logical nitrogen protection, heating, heating rate is regulated when temperature rises to 130 ~ 155 DEG C, control backflow tower top temperature at 100 ~ 102 DEG C, control leaving condenser water speed, temperature is slowly risen to 175 ~ 180 DEG C of insulation 2.5h, then temperature is risen to 210 ~ 220 DEG C, when stopping logical water coolant after water outlet completely, start vacuum pump evacuation, survey hydroxyl value at regular intervals, acid number and moisture, blowing of lowering the temperature is started after indices is qualified, obtain pyromellitic dianhydride kind polyester polyvalent alcohol.Its hydroxyl value is 310mgKOH/g, and acid number is 0.5mgKOH/g, and water ratio is 0.01%.
Embodiment 2:
By pyromellitic dianhydride 43.6g (0.2mol), Diethylene Glycol 84.8g (0.8mol) and potassium fluotitanate (0.044g) add in four-hole boiling flask successively, logical nitrogen-sealed, heating, heating rate is regulated when temperature rises to 130 ~ 155 DEG C, control backflow tower top temperature at 100 ~ 102 DEG C, control leaving condenser water speed, temperature is slowly risen to 175 ~ 180 DEG C of insulation 4h, then temperature is risen to 210 ~ 220 DEG C, when stopping logical water coolant after water outlet completely, start vacuum pump evacuation, survey hydroxyl value at regular intervals, acid number and moisture, blowing of lowering the temperature is started after indices is qualified, obtain pyromellitic dianhydride kind polyester polyvalent alcohol.Its hydroxyl value is 375mgKOH/g, acid number 0.3mgKOH/g, and water ratio is 0.02%.
Claims (5)
1. the preparation method of a Pyromellitic Acid kind polyester polyvalent alcohol, it is characterized in that, comprise the following steps: pyromellitic dianhydride, dibasic alcohol and catalyzer are added in four-hole boiling flask successively, logical nitrogen-sealed, heating, heating rate is regulated when temperature rises to 130 ~ 155 DEG C, control backflow tower top temperature at 100 ~ 102 DEG C, control leaving condenser water speed, prevent a large amount of water vapour from taking a small amount of dibasic alcohol out of a point flow condenser; Temperature is slowly risen to 175 ~ 180 DEG C of insulation 2 ~ 4h, then temperature is risen to 210 ~ 220 DEG C, after moisture stops completely, esterification completes substantially, stops logical water coolant, vacuumizes, cooling, obtained Pyromellitic Acid kind polyester polyvalent alcohol;
Described Pyromellitic Acid kind polyester polyvalent alcohol, hydroxyl value is 200 ~ 450mgKOH/g, acid number≤1.5mgKOH/g, water ratio≤0.03%.
2. the preparation method of Pyromellitic Acid kind polyester polyvalent alcohol according to claim 1, is characterized in that, the mol ratio of described pyromellitic dianhydride and dibasic alcohol is 1: 4 ~ 1: 6.
3. the preparation method of Pyromellitic Acid kind polyester polyvalent alcohol according to claim 1, is characterized in that, described dibasic alcohol is one or more of ethylene glycol, 1.4-butyleneglycol or glycol ether.
4. the preparation method of Pyromellitic Acid kind polyester polyvalent alcohol according to claim 1, is characterized in that, described is 100: 0.03 ~ 0.1 with the weight ratio of catalyzer.
5. the preparation method of Pyromellitic Acid kind polyester polyvalent alcohol according to claim 1, is characterized in that, described catalyzer potassium fluotitanate or Dibutyltin oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510389883.4A CN104910356A (en) | 2015-07-07 | 2015-07-07 | Preparation method of pyromellitic acid polyester polyol |
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| CN201510389883.4A CN104910356A (en) | 2015-07-07 | 2015-07-07 | Preparation method of pyromellitic acid polyester polyol |
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| CN104910356A true CN104910356A (en) | 2015-09-16 |
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| CN201510389883.4A Pending CN104910356A (en) | 2015-07-07 | 2015-07-07 | Preparation method of pyromellitic acid polyester polyol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801834A (en) * | 2016-05-11 | 2016-07-27 | 周家仁 | Preparation method of polyester-ether polyol |
| CN105968333A (en) * | 2016-05-12 | 2016-09-28 | 周家仁 | Preparation method of pyromellitic acid polyester polyol |
| CN111423557A (en) * | 2020-05-28 | 2020-07-17 | 浙江华峰合成树脂有限公司 | Two-liquid type bonding layer polyurethane resin for gold stamping and preparation method thereof |
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| US20080119609A1 (en) * | 2006-11-20 | 2008-05-22 | Kiarash Alavi Shooshtari | Binder comprising a crosslinked polyanhydride grafted with a lower molecular weight anhydride |
| CN101693797A (en) * | 2009-10-19 | 2010-04-14 | 湖南工业大学 | Environment-friendly water-based polyurethane ink and preparation method thereof |
| US20120004334A1 (en) * | 2009-03-24 | 2012-01-05 | Dow Global Technologies Llc | Production of rigid polyurethane foams and the use thereof |
| CN103396536A (en) * | 2013-08-05 | 2013-11-20 | 桂林理工大学 | Polyester polyol epoxy resin flexibilizer |
| CN103724598A (en) * | 2013-12-06 | 2014-04-16 | 江苏盈天化学有限公司 | High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol |
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2015
- 2015-07-07 CN CN201510389883.4A patent/CN104910356A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080119609A1 (en) * | 2006-11-20 | 2008-05-22 | Kiarash Alavi Shooshtari | Binder comprising a crosslinked polyanhydride grafted with a lower molecular weight anhydride |
| US20120004334A1 (en) * | 2009-03-24 | 2012-01-05 | Dow Global Technologies Llc | Production of rigid polyurethane foams and the use thereof |
| CN101693797A (en) * | 2009-10-19 | 2010-04-14 | 湖南工业大学 | Environment-friendly water-based polyurethane ink and preparation method thereof |
| CN103396536A (en) * | 2013-08-05 | 2013-11-20 | 桂林理工大学 | Polyester polyol epoxy resin flexibilizer |
| CN103724598A (en) * | 2013-12-06 | 2014-04-16 | 江苏盈天化学有限公司 | High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801834A (en) * | 2016-05-11 | 2016-07-27 | 周家仁 | Preparation method of polyester-ether polyol |
| CN105968333A (en) * | 2016-05-12 | 2016-09-28 | 周家仁 | Preparation method of pyromellitic acid polyester polyol |
| CN111423557A (en) * | 2020-05-28 | 2020-07-17 | 浙江华峰合成树脂有限公司 | Two-liquid type bonding layer polyurethane resin for gold stamping and preparation method thereof |
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Application publication date: 20150916 |
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