CN103724598A - High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol - Google Patents
High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol Download PDFInfo
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- CN103724598A CN103724598A CN201310653203.6A CN201310653203A CN103724598A CN 103724598 A CN103724598 A CN 103724598A CN 201310653203 A CN201310653203 A CN 201310653203A CN 103724598 A CN103724598 A CN 103724598A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a high functional aromatic polyester polyol for rigid foam. The high functional aromatic polyester polyol comprises the following components in parts by weight: 5 to 25 parts of trimellitic anhydride, 5 to 20 parts of pyromellitic dianhydride, 65 to 70 parts of polyhydric alcohol for recycling micromolecules, 2 to 5 parts of glycerol and 0.01 to 0.025 part of a catalytic agent. A method for preparing the high functional aromatic polyester polyol comprises the following steps: putting a dihydric alcohol raw material recycling the micromolecules, the glycerol, the trimellitic anhydride, the pyromellitic dianhydride and the catalytic agent into a polyester reaction kettle; slowly rising the temperature to 230 DEG C under the protection of N2, vacuumizing when the acid value is less than or equal to 25 mg KOH/g, and stopping reacting when the acid value of the product is less than or equal to 2 mg KOH/g; cooling to below 90 DEG C, filter-pressing, and discharging so as to obtain the high functional aromatic polyester polyol. The product disclosed by the invention is used in a rigid foam composition, the mechanical strength, the temperature resistance performance and the inflaming retarding performance of the rigid foam can be improved.
Description
Technical field
The present invention relates to a kind of polyester polyol and preparation method thereof, especially one is hard bubbled with high official's energy aromatic polyester polyol and preparation method thereof.
Background technology
Aromatic polyester polyol is one of important source material of synthesis of polyurethane resin, owing to there being the existence of phenyl ring and ester bond, has given polyurethane foam many premium propertiess, as toughness, flame retardant resistance, cohesiveness, chemical resistant properties, oil-proofness, thermotolerance, wear resistance etc.Due to the high emulsibility energy of polyester, make the abscess exquisiteness of polyurethane foam, thermal conductivity is low, and makes the water-intake rate of foam be down to lower level, can improve the heat resistance of foam, save energy.Aromatic polyester polyol is with polyprotonic acid or acid anhydrides and polyol reaction containing phenyl ring, finally with the compound of hydroxy-end capped chain-like structure, is widely used in the fields such as refrigerator, sterilizing-cabinet, freezer, pipeline, building board, imitative wooden furniture and spray material.
Although mixing of common low sense aromatic polyester polyol can be improved the fine and smooth degree, insulation of hard polyurethane foam, fire-retardant, oil resistant and wear resisting property, functionality is relatively low, and when addition is large, goods easily shrink.Along with the development of petrochemical industry, can constantly produce small molecules dibasic alcohol waste liquid, but do careful rectification and purification work, not only energy consumption is large, and can increase considerably tooling cost.
The functionality of existing common aromatic polyester polyol is relatively low, and when in polyurethane hard bubble composite material, consumption is large, the physical strength of the rigid polyurethane brewage of preparation and heat resistance are good not, and glycol ether finished product raw materials cost is high.
Summary of the invention
In order to reduce energy consumption, fully represent and reclaim polyvalent alcohol added value, the present invention utilizes and reclaims small molecules dibasic alcohol, glycerine reacts with trimellitic acid 1,2-anhydride, Pyromellitic Acid, prepares and can meet the requirement of different businessmans to aromatic polyester polyol.
The technical scheme solving the problems of the technologies described above is:
One is hard bubbled with high official's energy aromatic polyester polyol, and according to mass fraction meter, component is as follows:
5～25 parts of trimellitic acid 1,2-anhydrides;
5～20 parts of pyromellitic dianhydrides;
Reclaim 65～70 parts of small molecules polyvalent alcohols;
2～5 parts of glycerine;
0.01～0.025 part of catalyzer.
Hard bubble by a preparation method for high official's energy aromatic polyester polyol, step is as follows:
To reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, pyromellitic dianhydride and catalyzer drops in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining high official can aromatic polyester polyol.
Further, the massfraction sum of described trimellitic acid 1,2-anhydride and Pyromellitic Acid is no more than 33 parts.
Further, the hydroxyl value scope of described recovery small molecules dibasic alcohol is 800～1000mg KOH/g, and moisture≤1%, colourity (platinum-cobalt number)≤250.
Further, the content of described glycerine is not less than 95%, and other impurity can be water and ester class any one or a few.
Further, the molecular weight of described ester class is in 240g/mol, and boiling point is less than 300 ℃.
Further, described catalyzer is Mono-n-butyltin, and accounts for 0.01～0.025% of all raw material total masses.
Adopted such scheme, obtained one and hard bubble with high official's energy aromatic polyester polyol.Use product of the present invention to hard bubble composite material, can improve physical strength, heat resistance and the flame retardant properties of hard bubbling.
Although mixing of common low sense aromatic polyester polyol can be improved the fine and smooth degree, insulation of hard polyurethane foam, fire-retardant, oil resistant and wear resisting property, functionality is relatively low, and when addition is large, goods easily shrink.The pyromellitic acid anhydride of the trimellitic acid 1,2-anhydride of trifunctional and four senses is incorporated in polyester polyol, can improve the functionality of polyester polyol, can not only make like this hard polyurethane foam have advantages of that common low sense aromatic polyester polyol gives, and can improve physical strength, heat resistance and the flame retardant properties of goods.
Aromatic polyester polyol of the present invention has higher functionality, and it can not only increase oil-proofness, the wear resistance of rigid polyurethane brewage, reduces the thermal conductivity of goods, can also improve physical strength, heat resistance and the flame retardant resistance of goods.Adopt high temperature and high pressure steam heating method, to reclaim small molecules dibasic alcohol as raw material, heating efficiency improves, and production cost is low, can realize the environmental protection less energy-consumption recycling of useless alcohol simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1:
One is hard bubbled with high official's energy aromatic polyester polyol, and according to mass fraction meter, component is as follows: trimellitic acid 1,2-anhydride 50Kg; Pyromellitic Acid 15.95Kg; Reclaim small molecules polyvalent alcohol (hydroxyl value 1000mg KOH/) 130Kg; Glycerine 4Kg; Mono-n-butyltin 0.05Kg.
Hard bubble by a preparation method for high official's energy aromatic polyester polyol, will reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, Pyromellitic Acid and Mono-n-butyltin and drop in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining thick transparent Melon yellow look high official can aromatic polyester polyol (hydroxyl value 336mgKOH/g, acid number 1.5mg KOH/g, moisture 0.05%).
Embodiment 2:
One is hard bubbled with high official's energy aromatic polyester polyol, and according to mass fraction meter, component is as follows: trimellitic acid 1,2-anhydride 25.95Kg; Pyromellitic acid anhydride 40Kg; Reclaim small molecules polyvalent alcohol (hydroxyl value 1000mg KOH/) 130Kg; Glycerine 4Kg; Mono-n-butyltin 0.04Kg.
Hard bubble by a preparation method for high official's energy aromatic polyester polyol, will reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride and Mono-n-butyltin and drop in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining thick transparent Melon yellow look high official can aromatic polyester polyol (hydroxyl value 350mgKOH/g, acid number 1.6mg KOH/g, moisture 0.06%).
Embodiment 3:
One is hard bubbled with high official's energy aromatic polyester polyol, and according to mass fraction meter, component is as follows: trimellitic acid 1,2-anhydride 49.97Kg; Pyromellitic Acid 10Kg; Reclaim small molecules polyvalent alcohol (hydroxyl value 800mg KOH/) 130Kg; Glycerine 10Kg; Mono-n-butyltin 0.03Kg.
Hard bubble by a preparation method for high official's energy aromatic polyester polyol, will reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, Pyromellitic Acid and Mono-n-butyltin and drop in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining thick transparent Melon yellow look high official can aromatic polyester polyol (hydroxyl value 288mg KOH/g, acid number 1.7mg KOH/g, moisture 0.05%).
Embodiment 4:
One is hard bubbled with high official's energy aromatic polyester polyol, and according to mass fraction meter, component is as follows: trimellitic acid 1,2-anhydride 10Kg; Pyromellitic acid anhydride 40Kg; Reclaim small molecules polyvalent alcohol (hydroxyl value 800mg KOH/) 139.98Kg; Glycerine 10Kg; Mono-n-butyltin 0.02Kg.
Hard bubble by a preparation method for high official's energy aromatic polyester polyol, will reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, pyromellitic acid anhydride and Mono-n-butyltin and drop in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining thick transparent Melon yellow look high official can aromatic polyester polyol (hydroxyl value 256mg KOH/g, acid number 1.1mg KOH/g, moisture 0.05%).
Claims (7)
1. hard bubble with high official's energy aromatic polyester polyol, it is characterized in that, according to mass fraction meter, component is as follows:
5～25 parts of trimellitic acid 1,2-anhydrides;
5～20 parts of pyromellitic dianhydrides;
Reclaim 65～70 parts of small molecules polyvalent alcohols;
2～5 parts of glycerine;
0.01～0.025 part of catalyzer.
2. hard bubble by a preparation method for high official's energy aromatic polyester polyol, it is characterized in that, step is as follows:
To reclaim small molecules dibasic alcohol raw material, glycerine, trimellitic acid 1,2-anhydride, pyromellitic dianhydride and catalyzer drops in pet reaction still; Pass into N
2protection, the method that adopts high temperature and high pressure steam to heat, slowly rises to 230 ℃ by temperature, and gas phase temperature is controlled at below 102 ± 2 ℃; When acid number≤25mg KOH/g, start to vacuumize, vacuum tightness≤0.090MPa, temperature maintains 220～225 ℃, stopped reaction when product acid number≤2mg KOH/g; Be cooled to 90 ℃ of following press filtration dischargings, obtaining high official can aromatic polyester polyol.
3. one according to claim 1 and 2 is hard bubbled with high official's energy aromatic polyester polyol and preparation method thereof, it is characterized in that, the massfraction sum of described trimellitic acid 1,2-anhydride and Pyromellitic Acid is no more than 33 parts.
4. a kind of hard bubbling by the preparation method of high official's energy aromatic polyester polyol according to claim 2, it is characterized in that, the hydroxyl value scope of described recovery small molecules dibasic alcohol is 800～1000mg KOH/g, and moisture≤1%, colourity (platinum-cobalt number)≤250.
5. a kind of hard bubbling by the preparation method of high official's energy aromatic polyester polyol according to claim 2, is characterized in that, the content of described glycerine is not less than 95%, and other impurity can be water and ester class any one or a few.
6. a kind of hard bubbling by the preparation method of high official's energy aromatic polyester polyol according to claim 5, is characterized in that, the molecular weight of described ester class is in 240g/mol, and boiling point is less than 300 ℃.
7. one according to claim 1 and 2 is hard bubbled with high official's energy aromatic polyester polyol and preparation method thereof, it is characterized in that, described catalyzer is Mono-n-butyltin, and accounts for 0.01～0.025% of all raw material total masses.
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| CN201310653203.6A CN103724598A (en) | 2013-12-06 | 2013-12-06 | High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol |
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| CN201310653203.6A CN103724598A (en) | 2013-12-06 | 2013-12-06 | High functional aromatic polyester polyol for rigid foam and preparation method of high functional aromatic polyester polyol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910356A (en) * | 2015-07-07 | 2015-09-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of pyromellitic acid polyester polyol |
| CN104945614A (en) * | 2015-07-07 | 2015-09-30 | 北京市建筑工程研究院有限责任公司 | Method for preparing polyester ether polyol |
| CN105153410A (en) * | 2015-07-07 | 2015-12-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of flame retardant polyester ether polyol |
| CN105237728A (en) * | 2015-09-23 | 2016-01-13 | 四川东材科技集团股份有限公司 | Material used for preparing rigid foamed plastic, and preparation method of rigid foamed plastic |
| CN116515092A (en) * | 2023-05-11 | 2023-08-01 | 旭川化学（苏州）有限公司 | Polyester polyol and preparation method and application thereof |
| WO2024012849A1 (en) | 2022-07-11 | 2024-01-18 | Basf Se | Polyester polyol and polyurethane foam system containing the same |
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| US20040176494A1 (en) * | 2003-03-05 | 2004-09-09 | Feske Elbert F. | Preparation of flame retarded polyisocyanurate foams |
| CN102942685A (en) * | 2012-10-13 | 2013-02-27 | 江苏盈天化学有限公司 | Modified polyester polyol for rigid polyurethane foam |
| CN103360588A (en) * | 2013-07-26 | 2013-10-23 | 万华化学集团股份有限公司 | Fire-retardant and high-functionality aromatic polyester polyol and preparation method and applications thereof |
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2013
- 2013-12-06 CN CN201310653203.6A patent/CN103724598A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040176494A1 (en) * | 2003-03-05 | 2004-09-09 | Feske Elbert F. | Preparation of flame retarded polyisocyanurate foams |
| CN102942685A (en) * | 2012-10-13 | 2013-02-27 | 江苏盈天化学有限公司 | Modified polyester polyol for rigid polyurethane foam |
| CN103360588A (en) * | 2013-07-26 | 2013-10-23 | 万华化学集团股份有限公司 | Fire-retardant and high-functionality aromatic polyester polyol and preparation method and applications thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910356A (en) * | 2015-07-07 | 2015-09-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of pyromellitic acid polyester polyol |
| CN104945614A (en) * | 2015-07-07 | 2015-09-30 | 北京市建筑工程研究院有限责任公司 | Method for preparing polyester ether polyol |
| CN105153410A (en) * | 2015-07-07 | 2015-12-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of flame retardant polyester ether polyol |
| CN105153410B (en) * | 2015-07-07 | 2019-03-19 | 北京市建筑工程研究院有限责任公司 | A kind of preparation method of flame retardant polyester ethoxylated polyhydric alcohol |
| CN105237728A (en) * | 2015-09-23 | 2016-01-13 | 四川东材科技集团股份有限公司 | Material used for preparing rigid foamed plastic, and preparation method of rigid foamed plastic |
| CN105237728B (en) * | 2015-09-23 | 2017-12-26 | 四川东材科技集团股份有限公司 | A kind of material and its rigid foam preparation method for manufacturing rigid foam |
| WO2024012849A1 (en) | 2022-07-11 | 2024-01-18 | Basf Se | Polyester polyol and polyurethane foam system containing the same |
| CN116515092A (en) * | 2023-05-11 | 2023-08-01 | 旭川化学（苏州）有限公司 | Polyester polyol and preparation method and application thereof |
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Application publication date: 20140416 |