CN110698659B - Phthalic anhydride polyester polyol and preparation method thereof - Google Patents
Phthalic anhydride polyester polyol and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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Abstract
The invention provides a preparation method of phthalic anhydride polyester polyol, which comprises the following steps: 1) mixing an alcohol component and an anhydride component, heating to 180-220 ℃ to perform a first-stage reaction, wherein the first-stage reaction is performed until the acid value in the system is M1; 2) heating the system to 220-250 ℃ to carry out a second stage reaction, wherein the second stage reaction is carried out until the acid value in the system is M2, then continuously reacting under vacuum until the acid value in the system is M3 and the hydroxyl value is 10-600 mgKOH/g to obtain the phthalic anhydride polyester polyol, wherein the molar ratio of the alcohol component to the anhydride component in the step 1) is 1.3-7.0: 1, and M1 is more than 20mgKOH/g and less than or equal to 80 mgKOH/; in the step 2), the ratio of 5.0mgKOH/g to M2 is less than or equal to 20mgKOH/g, and the ratio of 0.01mgKOH/g to M3 is less than or equal to 5.0 mgKOH/g. The preparation method of the phthalic anhydride polyester polyol provided by the invention has the advantage of low content of phthalic anhydride cyclic lactone, and reduces the content of a migrating monomer.
Description
Technical Field
The invention belongs to the technical field of preparation of polyester polyol, and particularly relates to a preparation method of phthalic anhydride polyester polyol.
Background
The phthalic anhydride polyester polyol is an intermediate widely applied to the field of rigid foams, can partially replace polyether polyol, can endow the rigid foams with good flame retardant property due to the existence of benzene rings in the structure of the phthalic anhydride polyester polyol, and has the advantage that the polyether polyol is difficult to rival. In addition, the phthalic anhydride polyester polyol is widely applied to the fields of polyurethane such as coatings, elastomers, adhesives, sealants and the like.
The synthesis of the phthalic anhydride polyester polyol is usually accompanied by the formation of the phthalic anhydride cyclic lactone. The structure of the phthalic anhydride lactone does not contain a reactive functional group capable of reacting with isocyanate. Therefore, the phthalic anhydride lactone has mobility in polyurethane products and may have a plasticizing effect, thereby influencing the application of the polyurethane in some fields.
The patent US2014018458a1 discloses a method for synthesizing phthalic anhydride polyester polyol with low lactone content, which is obtained by reacting phthalic anhydride with PEG-200 or PEG-400, wherein PEG-200 and PEG-400 are oligomers, and the number of atoms in the main chain is far more than that of organic diol compounds, so cyclic lactone is difficult to form with phthalic anhydride. However, the structure of the phthalic anhydride polyester polyol synthesized by the scheme is relatively limited, and the requirements of different application fields on the phthalic anhydride polyester polyol differentiated structure products are difficult to meet. Therefore, the development of a synthetic method of the phthalic anhydride polyester polyol with low lactone content has practical significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the phthalic anhydride polyester polyol with low lactone content and the preparation method thereof, and the obtained phthalic anhydride polyester polyol has the advantage of low content of phthalic anhydride cyclic lactone, and the content of monomers with mobility is reduced.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of phthalic anhydride polyester polyol, which comprises the following steps:
1) mixing an alcohol component and an anhydride component, heating to 180-220 ℃ to perform a first-stage reaction, wherein the first-stage reaction is performed until the acid value in the system is M1;
2) heating the system in the step 1) to 220-250 ℃ for a second stage reaction, continuing the reaction in vacuum until the acid value in the system is M2, and the hydroxyl value is 10-600 mgKOH/g, so as to obtain the phthalic anhydride polyester polyol;
wherein the molar ratio of the alcohol component to the anhydride component in the step 1) is 1.3-7.0: 1, and the molar ratio of the alcohol component to the anhydride component is more than 20mgKOH/g and less than or equal to M1 and less than or equal to 80 mgKOH/;
in the step 2), the ratio of 5.0mgKOH/g to M2 is less than or equal to 20mgKOH/g, and the ratio of 0.01mgKOH/g to M3 is less than or equal to 5.0 mgKOH/g.
In some preferred embodiments, in step 1), the molar ratio of the alcohol component to the anhydride component is 1.3 to 4.2:1, more preferably 1.45 to 3.5:1, such as 1.6:1, 3: 1.
In some preferred embodiments, in step 2), the reaction is continued under vacuum until the acid value in the system is M3, 0.2mgKOH/g < M3. ltoreq.2 mgKOH/g.
In the present invention, the alcohol component includes a diol and/or a polyol; the alcohol component is selected from aromatic polyol or aliphatic dihydric alcohol or aliphatic polyol with 2-20 carbon atoms; in some preferred embodiments, the aliphatic diol is selected from one or more of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, 2-methyl-1, 3 propanediol, 2-methyl-2, 4-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, or cyclohexanedimethanol; the aliphatic polyhydric alcohol is selected from one or more of glycerol, trimethylolpropane or pentaerythritol; in a further preferred embodiment, the alcohol component is selected from diethylene glycol.
In the present invention, the anhydride component is selected from an anhydride or a mixture of the anhydride and a dibasic acid; the acid anhydride is selected from phthalic anhydride or halogenated phthalic anhydride; the halogenated phthalic anhydride is selected from one or more of 3-bromobenzoic anhydride, 4-bromobenzoic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3, 6-dichlorophthalic anhydride or tetrachlorophthalic anhydride; the dibasic acid is selected from aliphatic dibasic acid or aromatic dibasic acid with 2-20 carbon atoms; the dibasic acid is selected from one or more of succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, isophthalic acid or terephthalic acid; in a further preferred embodiment, the anhydride component is selected from phthalic anhydride.
In the preparation process, the acid value is lower after the alcohol component and the anhydride component are mixed, and the acid value can gradually rise along with the first-stage reaction of the alcohol component and the anhydride component until the maximum value appears; thereafter, the carboxyl group produced by the reaction of the anhydride component with the alcohol component undergoes further esterification reaction, and the acid value gradually decreases. When the acid value in the first stage reaction is M1 and the M1 is more than or equal to 20mgKOH/g and less than or equal to 80mgKOH/g, the temperature is continuously increased to carry out the second stage reaction; meanwhile, in the reaction system, the hydroxyl value is in a continuously decreasing trend until the target hydroxyl value of the product is reached.
In the preparation processes of steps 1) and 2) of the invention, when the acid value in the system is M4 and M4 is not less than 10mgKOH/g and not more than 22mgKOH/g, a catalyst can be added into the system to accelerate the reaction efficiency; the addition amount of the catalyst is 0-600 ppm, preferably 40-200 ppm, based on the total amount of the alcohol component and the anhydride component; in the present invention, the catalyst may be one or more selected from an antimony-based catalyst, a titanium-based catalyst, a tin-based catalyst, and a germanium-based catalyst; preferably a titanium-based catalyst.
In some preferred embodiments, the antimony-based catalyst is selected from the group consisting of antimony acetate, antimony trioxide, ethylene glycol antimony; the titanium catalyst is selected from tetraisobutyl titanate, tetraisopropyl titanate and titanium dioxide; the tin catalyst is selected from stannous chloride, stannic acetate and butyl tin hydroxide oxide; the germanium-based catalyst is selected from germanium dioxide.
In the preparation process of the invention, the adding time of the catalyst is determined by the acid value of the system in the reaction process; meanwhile, the addition or absence of the catalyst does not affect the structure and formation of the target product, and is not a step necessarily included in the preparation method of the invention.
In the step 1) of the preparation method, before the alcohol component and the anhydride component are mixed for the first-stage reaction, the alcohol component and the anhydride component are heated to 130-160 ℃ for pre-reaction until the system is clear and transparent, and then the first-stage reaction is carried out. In the specific production process of the present invention, the above pre-reaction may be included or may not be included.
In a preferred embodiment of the invention, when the acid value in the system in step 2) is M2 (i.e. the second stage reaction is completed), the system is placed under vacuum and continuously reacted until the acid value in the system is M3 and the hydroxyl value is 10-600 mgKOH/g, so as to obtain the phthalic anhydride polyester polyol, wherein 0.01mgKOH/g < M3 ≤ 5.0mgKOH/g, preferably 0.2mgKOH/g < M3 ≤ 2 mgKOH/g. In some preferred embodiments, the pressure of the reaction under vacuum is between-0.080 and-0.095 MPa, preferably between-0.090 and-0.095 MPa. After the second-stage reaction is finished, the reaction system is placed in vacuum to continue the reaction, so that on one hand, small molecules generated by the polycondensation reaction can be removed, and the residual quantity of the residual monomers is further reduced, thereby promoting the reaction; on the other hand, the intermediate with low molecular weight in the system can be removed, and the hydroxyl value of the product is reduced.
The second aspect of the invention provides phthalic anhydride polyester polyol, wherein the acid value of the phthalic anhydride polyester polyol is 0.01-5.0 mgKOH/g, and the hydroxyl value is 10-600 mgKOH/g; more preferably, the acid value of the phthalic anhydride polyester polyol is 0.01-1.0 mgKOH/g, and the hydroxyl value is 56-300 mgKOH/g.
By adopting the technical scheme, the method has the following technical effects:
the phthalic anhydride polyester polyol prepared by the preparation method has low lactone content; meanwhile, the obtained phthalic anhydride polyester polyol has different structural compositions and products with different molecular weights by adjusting the structure of the alcohol component, and the requirements of different application fields on the differential structural products of the phthalic anhydride polyester polyol are met.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Raw material source information in the following examples:
phthalic anhydride was purchased from korea;
diethylene glycol, neopentyl glycol, hexylene glycol, and the like are available from Waals chemical.
The starting materials used in the examples or comparative examples were all commercially available if not otherwise specified.
The content of the phthalic anhydride lactone in the examples of the present invention and the comparative examples: quantitative testing by a liquid chromatography external standard method;
measurement of acid value: reference standard HG/T2708-;
measurement of hydroxyl value: reference is made to standard HG/T2709-.
Example 1
1) Adding 9.0kg of phthalic anhydride, 1.0kg of adipic acid and 9.4kg of diethylene glycol into a reaction kettle, heating the system to 140 ℃ for reaction until the system is clear and transparent, heating the system to 210 ℃ from room temperature, and carrying out a first-stage reaction at the temperature for 2.0h until the acid value in the system is 40 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 15mgKOH/g, starting a vacuum device when the acid value in the system is 10mgKOH/g, reacting for 2h under the vacuum of-0.095 MPa until the acid value in the system is 0.98mgKOH/g and the hydroxyl value is 57.22mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol A.
The polyester polyol A has a hydroxyl value of 57.22mgKOH/g, an acid value of 0.98mgKOH/g and an average molecular weight of 2000.
Example 2
1) Adding 10.0kg of phthalic anhydride and 10.2kg of diethylene glycol into a reaction kettle, heating the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 2.0 hours at the temperature until the acid value in the system is 30 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 19mgKOH/g, starting a vacuum device when the acid value in the system is 10mgKOH/g, reacting for 3 hours under the vacuum of-0.095 MPa until the acid value in the system is 0.98mgKOH/g and the hydroxyl value is 57.22mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol B.
The polyester polyol B has a hydroxyl value of 57.22mgKOH/g, an acid value of 0.98mgKOH/g and an average molecular weight of 2000.
Example 3
1) Adding 10.0kg of phthalic anhydride and 11.6kg of diethylene glycol into a reaction kettle, heating the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 2.0h at the temperature until the acid value in the system is 20 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 12mgKOH/g, starting a vacuum device when the acid value in the system is 10mgKOH/g, reacting for 4.5h under the vacuum of-0.095 MPa until the acid value in the system is 0.43mgKOH/g and the hydroxyl value is 55.60mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol C.
The polyester polyol C has a hydroxyl value of 55.60mgKOH/g, an acid value of 0.43mgKOH/g, and an average molecular weight of 2000.
Example 4
1) Adding 10.0kg of phthalic anhydride and 21.8kg of diethylene glycol into a reaction kettle, heating the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 2.0h at the temperature until the acid value in the system is 25 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 10mgKOH/g, then starting a vacuum device, reacting for 3.0h under the vacuum of-0.095 MPa until the acid value in the system is 0.30mgKOH/g and the hydroxyl value is 320.10mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol D.
The polyester polyol D was found to have a hydroxyl value of 320.10mgKOH/g, an acid value of 0.30mgKOH/g, and an average molecular weight of 320.
Example 5
1) Adding 10.0kg of phthalic anhydride, 50.8kg of diethylene glycol and 0.2kg of trimethylolpropane into a reaction kettle, raising the temperature of the system from room temperature to 210 ℃, and carrying out a first-stage reaction for 2.0h at the temperature until the acid value in the system is 28 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 12mgKOH/g, starting a vacuum device when the acid value in the system is 8mgKOH/g, reacting for 5.0h under the vacuum of-0.095 MPa until the acid value in the system is 0.22mgKOH/g and the hydroxyl value is 499.80mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol E.
The polyester polyol E was found to have a hydroxyl value of 499.80mgKOH/g, an acid value of 0.22mgKOH/g, and an average molecular weight of 225.
Example 6
1) Adding 10.0kg of phthalic anhydride and 13.0kg of hexanediol into a reaction kettle, raising the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 2.0 hours at the temperature until the acid value in the system is 22 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, starting a vacuum device when the acid value in the system is 16mgKOH/g, reacting for 3.5 hours under the vacuum of-0.095 MPa until the acid value in the system is 0.20mgKOH/g and the hydroxyl value is 56.03mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol F.
The polyester polyol F was determined to have a hydroxyl value of 56.03mgKOH/g, an acid value of 0.20mgKOH/g, and an average molecular weight of 2000.
Comparative example 1
Adding 10.0kg of phthalic anhydride and 10.2kg of diethylene glycol into a reaction kettle, raising the temperature of the system from room temperature to 200 ℃, and adding 2.1g of tetraisopropyl titanate when the temperature is reacted until the acid value is 15 mgKOH/g; and continuously reacting until the acid value is 10mgKOH/G, starting vacuum, reacting for 2h under the vacuum of-0.095 MPa until the acid value is 0.75mgKOH/G and the hydroxyl value is 56.65mgKOH/G, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol G.
The polyester polyol G was found to have a hydroxyl value of 56.65mgKOH/G, an acid value of 0.75mgKOH/G, and an average molecular weight of 2000.
Comparative example 2
1) Adding 10.0kg of phthalic anhydride and 8.7kg of diethylene glycol into a reaction kettle, heating the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 1.5h at the temperature until the acid value in the system is 30 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 15mgKOH/g, starting a vacuum device when the acid value in the system is 10mgKOH/g, reacting for 2H under the vacuum of-0.095 MPa until the acid value in the system is 1.00mgKOH/g and the hydroxyl value is 56.36mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol H.
The polyester polyol H was determined to have a hydroxyl value of 56.36mgKOH/g, an acid value of 1.00mgKOH/g, and an average molecular weight of 2000.
Comparative example 3
1) Adding 10.0kg of phthalic anhydride and 9.7kg of hexanediol into a reaction kettle, raising the temperature of the system from room temperature to 210 ℃, and carrying out the first-stage reaction for 2.0 hours at the temperature until the acid value in the system is 40 mgKOH/g;
2) and continuously heating to 230 ℃, carrying out second-stage reaction at the temperature, adding 2.1g of tetraisopropyl titanate for continuous reaction when the acid value in the reaction system is 15mgKOH/g, starting a vacuum device when the acid value in the system is 6mgKOH/g, reacting for 2h under the vacuum of-0.095 MPa until the acid value in the system is 0.65mgKOH/g and the hydroxyl value is 55.38mgKOH/g, cooling the system to 160 ℃, discharging and packaging to obtain the polyester polyol I.
The polyester polyol I has a hydroxyl value of 55.38mgKOH/g, an acid value of 0.65mgKOH/g and an average molecular weight of 2000.
The polyester polyol A-I is subjected to phthalic anhydride cyclic lactone content measurement, and the results are shown in the following table.
Remarking: the "molar ratio of alcohol to anhydride" in the above table is the molar ratio of alcohol component to anhydride component.
As can be seen by comparing polyol C (example 3) and polyol F (example 6) in the above table, the molar ratios of the alcohol component and the anhydride component are the same during the reaction, and the cyclic lactone contents of phthalic anhydride of the polyester polyols obtained are different due to the different tendency of the different alcohol components to undergo intramolecular cyclic lactone with the anhydride component.
As can be seen from the data in the table above, when the alcohol component is diethylene glycol, the determination results of the polyol A (example 1) and the polyol B (example 2) show that the content of the cyclic lactone of phthalic anhydride in the polyester polyol prepared in example 1 is reduced from 60030ppm to 51300ppm by controlling the molar ratio of the alcohol component to the anhydride component in the reaction to be 1.3:1 and 1.4:1 (1.3-7: 1); meanwhile, the proportion of the alcohol component to the anhydride component is further improved, and the determination results of the polyols C to E (examples 3 to 5) show that the content of the cyclic lactone of phthalic anhydride in the obtained polyester polyol can be further reduced, and the content of the cyclic lactone of phthalic anhydride is reduced from 35622ppm to 8260 ppm.
When the alcohol component is hexanediol, as can be seen from the polyol F (example 6) and the polyol I (comparative example 3) in the table above, the molar ratio of the alcohol component to the anhydride component in the reaction is controlled to be 1.6:1 (1.3-7: 1), so that the content of the cyclic lactone of phthalic anhydride in the prepared polyester polyol is reduced from 26300ppm to 14665 ppm.
Meanwhile, compared with the preparation method adopting the 'one-step method' heating mode in the comparative example 1, the content of the generated phthalic anhydride cyclic lactone in the system is further reduced to 51300ppm by adopting the mode of heating the reaction raw materials in stages in the invention in the example 2.
In conclusion, the synthesis method of the phthalic anhydride polyester polyol provided by the invention can effectively reduce the content of the phthalic anhydride cyclic lactone in the phthalic anhydride polyester polyols with different compositions.
Claims (16)
1. A preparation method of phthalic anhydride polyester polyol is characterized by comprising the following steps:
1) mixing an alcohol component and an anhydride component, heating to 180-220 ℃ to perform a first-stage reaction, wherein the first-stage reaction is performed until the acid value in the system is M1;
2) heating the system in the step 1) to 220-250 ℃ for a second stage reaction, continuing the reaction in vacuum until the acid value in the system is M2, and the hydroxyl value is 10-600 mgKOH/g, so as to obtain the phthalic anhydride polyester polyol;
wherein the molar ratio of the alcohol component to the anhydride component in the step 1) is 1.3-7.0: 1, and the molar ratio of the alcohol component to the anhydride component is more than 20mgKOH/g and less than or equal to M1 and less than or equal to 80 mgKOH/g;
in the step 2), the ratio of 5.0mgKOH/g to M2 is less than or equal to 20mgKOH/g, the ratio of 0.01mgKOH/g to M3 is less than or equal to 5.0 mgKOH/g;
wherein the anhydride component is selected from anhydride or a mixture of anhydride and dibasic acid, and the anhydride is selected from phthalic anhydride or halogenated phthalic anhydride.
2. The method of claim 1, wherein in step 1), the molar ratio of the alcohol component to the anhydride component is 1.3 to 4.2: 1.
3. The method of claim 2, wherein the molar ratio of the alcohol component to the anhydride component is 1.45 to 3.50: 1.
4. The method according to claim 1, wherein the reaction is continued under vacuum in step 2) until the acid value in the system is M3, 0.2mgKOH/g < M3. ltoreq.2 mgKOH/g.
5. The production method according to any one of claims 1 to 4, characterized in that the alcohol component includes a diol and/or a polyol.
6. The method according to claim 5, wherein the alcohol component is selected from aromatic polyols or from aliphatic diols or polyols having 2 to 20 carbon atoms.
7. The production method according to claim 6, wherein the aliphatic diol is selected from one or more of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, 2-methyl-1, 3 propanediol, 2-methyl-2, 4-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and cyclohexanedimethanol; the aliphatic polyhydric alcohol is selected from one or more of glycerol, trimethylolpropane or pentaerythritol.
8. The method according to claim 5, wherein the halogenated phthalic anhydride is selected from one or more of 3-bromobenzoic anhydride, 4-bromobenzoic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3, 6-dichlorophthalic anhydride and tetrachlorophthalic anhydride.
9. The method according to claim 5, wherein the dibasic acid is selected from an aliphatic dibasic acid or an aromatic dibasic acid having 2 to 20 carbon atoms.
10. The method according to claim 9, wherein the dibasic acid is one or more selected from succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, isophthalic acid, and terephthalic acid.
11. The production method according to any one of claims 1 to 4 and 6 to 10, wherein a catalyst is added to the system when the acid value in the system is M4 and 10mgKOH/g or more and M4 or less and 22mgKOH/g or less in the production processes of steps 1) and 2);
the addition amount of the catalyst is 0-600 ppm based on the total mass of the alcohol component and the anhydride component;
the catalyst is selected from one or more of antimony catalyst, titanium catalyst, tin catalyst or germanium catalyst.
12. The method according to claim 11, wherein the catalyst is added in an amount of 40 to 200 ppm.
13. The method according to claim 11, wherein the antimony-based catalyst is selected from antimony acetate, antimony trioxide and ethylene glycol antimony, the titanium-based catalyst is selected from tetraisobutyl titanate, tetraisopropyl titanate and titanium dioxide, the tin-based catalyst is selected from stannous chloride, tin acetate and butyltin hydroxide oxide, and the germanium-based catalyst is selected from germanium dioxide.
14. The preparation method of claim 11, wherein in the step 1), after the alcohol component and the anhydride component are mixed, the temperature is raised to 130-160 ℃ to carry out pre-reaction until the system is clear and transparent, and then the first-stage reaction is carried out.
15. The method according to claim 14, wherein the pressure for continuing the reaction under vacuum in step 2) is from-0.080 to-0.095 MPa.
16. The method of claim 15, wherein the pressure for continuing the reaction under vacuum is-0.090 MPa to-0.095 MPa.
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| CN110698659B true CN110698659B (en) | 2022-04-22 |
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| JP2012505941A (en) * | 2008-10-15 | 2012-03-08 | ビーエーエスエフ ソシエタス・ヨーロピア | Polyester polyol based on terephthalic acid |
| CN108690185A (en) * | 2017-04-10 | 2018-10-23 | 上海东大化学有限公司 | Modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof |
| CN108774313A (en) * | 2018-06-27 | 2018-11-09 | 吉林博尔士兰新材料科技有限公司 | A kind of synthesis technology of low coloration polyester polyol |
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| JP2012505941A (en) * | 2008-10-15 | 2012-03-08 | ビーエーエスエフ ソシエタス・ヨーロピア | Polyester polyol based on terephthalic acid |
| CN108690185A (en) * | 2017-04-10 | 2018-10-23 | 上海东大化学有限公司 | Modified benzoic anhydride polyester polyol, combined polyether, polyurethane foam feedstock composition, polyurethane foam and preparation method thereof |
| CN108774313A (en) * | 2018-06-27 | 2018-11-09 | 吉林博尔士兰新材料科技有限公司 | A kind of synthesis technology of low coloration polyester polyol |
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