CN107602831B - Production method of polyester polyol for hard foam - Google Patents
Production method of polyester polyol for hard foam Download PDFInfo
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- CN107602831B CN107602831B CN201711049574.8A CN201711049574A CN107602831B CN 107602831 B CN107602831 B CN 107602831B CN 201711049574 A CN201711049574 A CN 201711049574A CN 107602831 B CN107602831 B CN 107602831B
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Abstract
The invention relates to a production method of polyester polyol for hard foam, which is prepared by reacting and modifying melamine with dicarboxylic acid or anhydride, and then carrying out polycondensation reaction with micromolecular polyol and dicarboxylic acid or anhydride under the action of a catalyst. Wherein: the mass portions of the melamine and the dicarboxylic acid or the anhydride are as follows: 15-30 parts of melamine and 70-85 parts of dicarboxylic acid or anhydride. In order to overcome the defects of the prior art, the invention provides a production method of polyester polyol for hard foam, which has the characteristics of environmental protection, high efficiency, low toxicity and long time; the produced structural flame-retardant polyester polyol does not reduce the flame-retardant property after long-term use, and has the advantages of low raw material price, relatively dominant cost and higher cost performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane products, and particularly relates to a production method of polyester polyol for hard foam.
Background
The rigid polyurethane foam plastic, polyurethane rigid foam for short, is used in the polyurethane product in an amount which is second to that of the polyurethane flexible foam. The polyurethane hard foam is mostly of a closed-cell structure, has the excellent characteristics of good heat insulation effect, light weight, high specific strength, convenient construction and the like, has the characteristics of sound insulation, shock resistance, electric insulation, heat resistance, cold resistance, solvent resistance and the like, is widely used for heat insulation materials of refrigerator bodies of refrigerators and freezer cases, cold storages, refrigerated trucks and the like, and heat insulation materials of buildings, storage tanks and pipelines, and is used for non-heat insulation occasions in a small amount, such as imitation wood, packaging materials and the like. In general, the lower density rigid polyurethane foam is mainly used as a thermal insulation material, and the higher density rigid polyurethane foam is used as a structural material (imitation wood).
The oxygen index of the common rigid polyurethane foam is generally about 16-18, and the requirement of building flame retardance cannot be met, so that the increase of the flame retardance of the foam is extremely important. The flame retardant property is excellent, and simultaneously, various physical and mechanical properties of the foam meet the use requirements of the original foam, and the flame retardant has important significance for large-scale application of polyurethane foam in the building industry. Experimental research shows that the temperature resistance and the flame retardant property of polyester polyol, especially foam synthesized by the polyester polyol containing an aromatic structure are obviously superior to those of polyether polyol. The polyol raw material of the hard polyurethane foam which is used in the construction field abroad is mainly polyester polyol, wherein products represented by phthalic anhydride polyester polyol form a large series. The research on the phthalic anhydride polyester polyol is relatively late in China, and the comprehensive performance and the flame retardance of the product are less researched.
The flame-retardant polyol is a polyol containing a flame-retardant element or a flame-retardant group in a molecular main chain or a side chain, and can be classified into phosphorus flame-retardant polyols, halogen flame-retardant polyols, composite flame-retardant polyols, aromatic heterocyclic flame-retardant polyols and the like. With more and more attention paid to the flame retardant property of polyurethane thermal insulation materials, the research of flame retardant polyol becomes a trend. The organic micromolecule additive flame retardant has the defects of easy migration, non-lasting flame retardant property, damage to the mechanical property of foam and the like, so that the requirements are difficult to meet in use. The flame-retardant polyol can achieve a lasting flame-retardant effect when applied to polyurethane foam, and comprises phosphate ester, phosphite ester, phosphoramidate, halogen, melamine, polyimide, oxazolidone, polyurea polyol, and polyol containing heterocyclic structures such as benzene ring, isocyanurate ring and the like.
Most of polyester polyols in the market are mostly additive type polyester polyols, on the basis of the original common polyester polyols, a large amount of phosphorus-containing, nitrogen-containing or halogen-containing flame retardant is added to improve the flame retardance of the polyester, but most of the additive type flame retardant polyester polyols are unstable in flame retardance and cannot sustain the flame retardance, and sometimes a heart-burning phenomenon occurs due to large addition amount.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a production method of polyester polyol for hard foam, which has the characteristics of environmental protection, high efficiency, low toxicity and long time; the produced structural flame-retardant polyester polyol does not reduce the flame-retardant property after long-term use, and has the advantages of low raw material price, relatively dominant cost and higher cost performance.
The polyester polyol for the hard foam is prepared by reacting and modifying melamine with dicarboxylic acid or anhydride, and then carrying out polycondensation reaction with micromolecular polyol and dicarboxylic acid or anhydride under the action of a catalyst.
Wherein:
the mass portions of the melamine and the dicarboxylic acid or the anhydride are as follows: 15-30 parts of melamine and 70-85 parts of dicarboxylic acid or anhydride.
The dicarboxylic acid or anhydride is one or two of phthalic anhydride, terephthalic acid or isophthalic acid.
The small molecular polyol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, glycerol or pentaerythritol.
The mass parts of an intermediate, micromolecular polyhydric alcohol, dicarboxylic acid or anhydride and a catalyst generated by the reaction modification of melamine and dicarboxylic acid or anhydride are as follows: 10-20 parts of intermediate, 40-60 parts of micromolecular polyhydric alcohol, 20-50 parts of dicarboxylic acid or anhydride and 0.01-0.02 part of catalyst.
The catalyst is one of organic titanium or organic tin.
The organotin is preferably T-9 and T-12, and the organotitanium catalyst is preferably n-butyl titanate and isopropyl titanate.
The manufacturers of T-9 and T-12 are air chemical Co.
The production method of the polyester polyol for the hard foam comprises the following steps:
(1) adding melamine and dicarboxylic acid or anhydride into a reaction kettle, heating to 260-class temperature 270 ℃, dehydrating, carrying out melt reaction for 2-3 hours, and cooling to 100-class temperature 120 ℃ to obtain an intermediate;
(2) adding micromolecular polyalcohol and dicarboxylic acid or anhydride, raising the material temperature to 160-170 ℃, preserving the temperature for two hours, and then carrying out post-treatment.
As a preferred technical solution, the method for producing polyester polyol for hard foam according to the present invention comprises the following steps:
(1) firstly, adding melamine and dibasic acid or anhydride into a reaction kettle, heating to 260-class temperature 270 ℃, removing water generated in the reaction under reduced pressure, carrying out a melting reaction for 2-3 hours, and then cooling to 100-class temperature 120 ℃ to obtain an intermediate;
(2) adding a set amount of micromolecule polyol and dicarboxylic acid or anhydride, raising the material temperature to 160-170 ℃, starting to discharge water, preserving the heat for two hours, slowly raising the material temperature to 225-230 ℃, controlling the temperature of a reflux tower to 97-103 ℃, preserving the heat for two hours, gradually vacuumizing, sampling and testing the acid value until the acid value is reduced to 2.0mgKOH/g, stopping vacuumizing, reducing the temperature, and reducing the temperature to below 90 ℃ to obtain the polyester polyol.
The polyester polyol for hard foam produced by the method is used in polyurethane hard foam, the hydroxyl value is between 200 and 500mg KOH/g, and the acid value is less than 2.0mg KOH/g.
The polyester polyol disclosed by the invention is a reactive flame-retardant mechanism, no flame retardant is physically added, a polyamide structure with better flame retardance is introduced in the reaction, and the polyester polyol is a structural flame-retardant polyester polyol with excellent performance. The polyurethane rigid foam prepared from the polyester polyol has good foam strength, fine foam pores and high oxygen index.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the reactive flame-retardant polyester polyol overcomes the defects of the additive flame-retardant polyester, has the characteristics of environmental protection, high efficiency, low toxicity and long time, and plays an increasingly important role in the flame-retardant research of polyurethane.
(2) The flame-retardant element nitrogen is introduced into the polyol simultaneously or respectively through chemical reaction and participates in the reaction as a reaction component, the influence on the material performance is small, and the flame-retardant element nitrogen is stably combined into a polyurethane matrix, so that the polyurethane contains the flame-retardant component, and the flame-retardant performance cannot be reduced due to precipitation in the long-term use process.
(3) The used raw materials are low in price, relatively dominant in cost and high in cost performance, and are very popular with customers in the market.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Firstly, adding 15 parts of melamine and 85 parts of terephthalic acid into a reaction kettle, heating to 260 ℃, removing water generated in the reaction under reduced pressure, carrying out a melting reaction for 2.5 hours, and then cooling to 110 ℃ to obtain an intermediate 1.
(2) Sequentially adding 10 parts of the intermediate 1, 35 parts of diethylene glycol, 15 parts of glycerol, 40 parts of phthalic anhydride and 0.01 part of T-9 into a reaction kettle, raising the temperature of the material to 170 ℃, starting water discharge, preserving heat for two hours, slowly raising the temperature of the material to 230, controlling the temperature of a reflux tower to be 100 +/-3 ℃, preserving heat for two hours, gradually vacuumizing, sampling an acid value, testing the acid value, stopping vacuumizing and cooling until the acid value is reduced to 2.0mg KOH/g, and barreling at 90 ℃.
Example 2
(1) Firstly, adding 20 parts of melamine and 80 parts of phthalic anhydride into a reaction kettle, heating to 265 ℃, removing water generated in the reaction under reduced pressure, carrying out a melting reaction for 3 hours, and then cooling to 105 ℃ to obtain an intermediate 2.
(2) Sequentially adding 15 parts of intermediate 2, 35 parts of diethylene glycol, 10 parts of glycerol, 5 parts of triethylene glycol, 40 parts of terephthalic acid and 0.015 part of isopropyl titanate into a reaction kettle, raising the temperature of the material to 165 ℃, starting to discharge water, keeping the temperature for two hours, slowly raising the temperature of the material to 230 ℃, controlling the temperature of a reflux tower to be 100 +/-3 ℃, keeping the temperature for two hours, gradually vacuumizing, sampling and testing the acid value until the acid value is reduced to 2.0mg KOH/g, stopping vacuumizing, reducing the temperature, and barreling at 90 ℃.
Example 3
(1) Firstly, adding 20 parts of melamine and 80 parts of phthalic anhydride into a reaction kettle, heating to 270 ℃, removing water generated in the reaction under reduced pressure, carrying out melting reaction for 3 hours, and then cooling to 110 ℃ to obtain an intermediate 3.
(2) Sequentially adding 20 parts of the intermediate 3, 30 parts of diethylene glycol, 10 parts of ethylene glycol, 5 parts of pentaerythritol, 35 parts of terephthalic acid and 0.02 part of T-12 into a reaction kettle, raising the temperature of the material to 160 ℃, starting water discharge, keeping the temperature for two hours, slowly raising the temperature of the material to 230 ℃, controlling the temperature of a reflux tower to be 100 +/-3 ℃, keeping the temperature for two hours, gradually vacuumizing, sampling and testing the acid value until the acid value is reduced to 2.0mg KOH/g, stopping vacuumizing, reducing the temperature, and barreling when the acid value is reduced to 90 ℃.
Example 4
(1) Firstly, adding 15 parts of melamine and 85 parts of isophthalic acid into a reaction kettle, heating to 270 ℃, decompressing to remove water generated in the reaction, carrying out a melting reaction for 2 hours, and then cooling to 120 ℃ to obtain an intermediate 4.
(2) Sequentially adding 10 parts of a midbody 4, 30 parts of diethylene glycol, 20 parts of ethylene glycol, 5 parts of glycerol, 10 parts of phthalic anhydride, 25 parts of terephthalic acid and 0.02 part of n-butyl titanate into a reaction kettle, then raising the temperature of the material to 170 ℃, starting water discharge, preserving heat for two hours, then slowly raising the temperature of the material to 230 ℃, controlling the temperature of a reflux tower at 100 +/-3 ℃, preserving heat for two hours, gradually vacuumizing, sampling and testing an acid value until the acid value is reduced to 2.0mg KOH/g, stopping vacuumizing, reducing the temperature, and barreling when the acid value is reduced to 90 ℃.
Claims (5)
1. A production method of polyester polyol for hard foam is characterized in that: the method comprises the following steps:
(1) adding melamine and dicarboxylic acid or anhydride into a reaction kettle, heating to 260-class temperature 270 ℃, dehydrating, carrying out melt reaction for 2-3 hours, and cooling to 100-class temperature 120 ℃ to obtain an intermediate;
(2) under the action of a catalyst, adding micromolecular polyalcohol and dicarboxylic acid or anhydride into the intermediate, raising the material temperature to 160-170 ℃, preserving the temperature for two hours, and then carrying out post-treatment;
wherein: in the step (1), when the melamine reacts with the dicarboxylic acid or the anhydride for modification, the raw materials are as follows in parts by weight: 15-30 parts of melamine and 70-85 parts of dicarboxylic acid or anhydride;
in the step (2), the mass parts of the intermediate, the small molecular polyol, the dicarboxylic acid or anhydride and the catalyst are as follows: 10-20 parts of an intermediate, 40-60 parts of micromolecular polyhydric alcohol, 20-50 parts of dicarboxylic acid or anhydride and 0.01-0.02 part of a catalyst;
in the step (1) and the step (2), the dicarboxylic acid or the anhydride is one or two of phthalic anhydride, terephthalic acid or isophthalic acid;
the small molecular polyol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, glycerol or pentaerythritol.
2. The method for producing a polyester polyol for hard foam according to claim 1, wherein: the catalyst is one of organic titanium or organic tin.
3. The method for producing a polyester polyol for hard foam according to claim 1, wherein: the organic tin is T-9 and T-12, and the organic titanium catalyst is n-butyl titanate and isopropyl titanate.
4. The method for producing a polyester polyol for hard foam according to claim 1, wherein: and (2) performing post-treatment, namely keeping the temperature for 2-3 hours, then heating the material to 225-230 ℃, controlling the temperature of the reflux tower to be 97-103 ℃ during the period, keeping the temperature for 2-3 hours, vacuumizing, sampling and testing the acid value, stopping vacuumizing and cooling until the acid value is reduced to 1.0-2.0mg KOH/g, and reducing the temperature to 90 ℃ to obtain the polyester polyol for the hard foam.
5. The method for producing a polyester polyol for hard foam according to any one of claims 1 to 4, wherein: the hydroxyl value of the polyester polyol for hard foam produced by the method is between 200 and 500mg KOH/g, and the acid value is less than 2.0mg KOH/g.
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| WO2023083442A1 (en) | 2021-11-10 | 2023-05-19 | Norchem Limited | Process for producing a triazine ring containing compound, addition product, triazine ring containing polyol, use of the addition product, use of the triazine ring containing polyol and pu/pir foam obtained by using the triazine ring containing polyol |
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| US8592623B2 (en) * | 2008-11-06 | 2013-11-26 | Bayer Materialscience Ag | Method for producing polyester polyols having low amounts of dioxane waste |
| CN102718957A (en) * | 2012-06-27 | 2012-10-10 | 淄博德信联邦化学工业有限公司 | Aromatic polyester polyol for preparing polyurethane foam and preparation method thereof |
| CN103642009B (en) * | 2013-12-09 | 2016-03-09 | 山东一诺威聚氨酯股份有限公司 | Polyester polyol and its preparation method and application |
| CN105367774A (en) * | 2015-11-19 | 2016-03-02 | 滕州市科米特新材料有限责任公司 | Nitrogen heterocyclic castor oil-based polyester polyol and preparation method and use thereof |
| CN106243335B (en) * | 2016-08-01 | 2018-07-13 | 常州聚博节能科技有限公司 | Inorganic hybridization polyester polyol etherified melamine polyimide resin and preparation method thereof |
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