CN109575263B - Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content - Google Patents
Preparation method of poly (butylene succinate-co-adipate-glycol) with low carboxyl end group content Download PDFInfo
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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
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Abstract
The invention relates to a preparation method of poly (butylene succinate) -co-adipate-butylene glycol ester with low terminal carboxyl content, which mainly solves the problem that the content of the terminal carboxyl of the poly (butylene succinate) -co-adipate-butylene glycol ester is higher in the prior art. The invention adopts a preparation method of poly (succinic acid) -co-adipic acid-butanediol ester with low-end carboxyl group content, which is characterized in that a polyol composition is added before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes; the technical scheme that the polyol composition is selected from trimethylolpropane and at least one other polyol better solves the problem, and can be used for preparing the poly (butylene succinate) -co-adipate-glycol ester with low carboxyl end group content.
Description
Technical Field
The invention relates to a preparation method of poly (butylene succinate) -co-adipate-butanediol ester with low carboxyl content.
Background
Polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and the like are important synthetic materials, and have a wide range of applications because they have various excellent properties and can be applied to the fields of synthetic fibers, engineering plastics, and the like. However, these polymers cannot be degraded in nature, and the white pollution caused by the polymers is a great problem which besets the world. In order to solve the harm of white pollution to the environment, the development of degradable materials is the trend of future development, and the use ratio of the degradable materials is increased day by day.
Poly succinic acid-co-adipic acid-butanediol ester (PBSA) obtained by copolymerizing succinic acid, adipic acid and 1, 4-butanediol is PBS-based resin with excellent degradation capability, has higher degradation capability than PBS, is easy to process and form, is a mainstream product of degradable film materials, is widely applied to the fields of packaging films, coating films of paper, medical supplies, foam materials, agricultural mulching films and the like, and has huge foreign market demands.
In the preparation of polybutylene succinate-co-adipate-butylene glycol, since butylene glycol is easily decomposed at a high temperature to generate byproducts of tetrahydrofuran and water, a high molecular weight polymer cannot be obtained using a catalyst for preparing an aromatic polyester.
Catalysts used in the prior art for preparing polymers copolymerized from succinic acid, adipic acid and butanediol are titanium alkoxides, tin alkoxides, germanium oxides, etc., as disclosed in patents CN101910245, CN1088945, CN1923872, CN101434689, JP2004018674a2, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin oxide, tin oxide, stannous chloride, germanium compounds, etc.
The titanium catalyst has high activity and no heavy metal, so that the titanium catalyst has no environmental pollution problem, and is particularly suitable for industrial production of aliphatic polyester. In the prior art, the titanate catalyst for preparing the poly (butylene succinate-co-adipate-butylene glycol) has the defects of easy hydrolysis and insoluble precipitation when meeting water, so that the activity of the catalyst is reduced, and the content of terminal carboxyl of a polymer is adversely affected. The high content of terminal carboxyl groups is not favorable for the heat resistance and the processability of the polymer and the stability in the storage process. Chinese patent CN103772683A solves the problem of mutual solubility of titanium compound and butanediol, but does not mention the method of preparing poly (butylene succinate-co-adipate-butylene glycol ester) with low carboxyl group content.
Disclosure of Invention
The invention aims to solve the technical problem of high content of terminal carboxyl of poly (succinic acid) -co-adipic acid-butanediol ester in the prior art, and provides a novel preparation method of poly (succinic acid) -co-adipic acid-butanediol ester with low content of terminal carboxyl. The method has the advantage of effectively reducing the content of the terminal carboxyl of the poly (succinic acid-co-adipic acid-butanediol ester).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content comprises the steps of adding a polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction is finished;
wherein the polyol composition is selected from trimethylolpropane and at least one other polyol.
In the above technical scheme, the polyol composition is trimethylolpropaneThe alkane is combined with at least one other polyol selected from C3～C6One of the polyhydric alcohols, further preferably at least one selected from pentaerythritol, neopentyl glycol, sorbitol, glycerol, xylitol, and mannitol.
In the above technical solution, the weight ratio of trimethylolpropane to other polyols in the polyol composition is preferably 1: (1-15), and more preferably the weight ratio of trimethylolpropane to other polyhydric alcohols is 1: (1-8).
In the above technical solution, the preparation method preferably comprises the following steps: the method comprises the following steps of taking succinic acid, adipic acid and butanediol as raw materials, carrying out esterification reaction by adopting a liquid titanium catalyst under the conditions that the reaction temperature is 150-230 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain an esterification product, and then carrying out polycondensation reaction under the vacuum condition that the reaction temperature is 230-250 ℃ and the reaction pressure is less than 120Pa to obtain the poly (succinic acid) -co-adipic acid-butanediol ester, wherein the used liquid titanium catalyst comprises the reaction product of the following raw materials:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one aliphatic organic acid selected from organic acids;
(D) at least one metal compound selected from IA of the periodic table;
adding the polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes;
wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-20): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-10): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (0-10): 1, the weight ratio of the polyol composition to the copolyester is 0.01-0.4%.
In the above technical solution, it is further preferable that: the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-10): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-5): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (2-6): 1, the weight ratio of the polyol composition to the copolyester is 0.03-0.3%. Based on the weight of the generated poly (butylene succinate) -co-adipate, the addition amount of the catalyst is 50-120 mg/kg in terms of titanium atoms.
In the above-mentioned embodiment, the titanium compound (a) is preferably at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetrabutyl titanate. The diol (B) is preferably at least one selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol. The aliphatic organic acid (C) is preferably at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, and lactic acid. The aliphatic organic acid (C) is an anhydride or a crystalline hydrate. The preferable embodiment of the group IA metal compound (D) is at least one selected from lithium, sodium or potassium.
The preparation method of the liquid titanium catalyst comprises the following steps:
a) reacting a titanium compound with a dihydric alcohol containing 2 to 10 carbon atoms at 20 to 250 ℃ for 0.5 to 25 hours, wherein the titanium compound is Ti (OR)4R is alkyl with 1-10 carbon atoms, white precipitate is separated out, the product is separated after reaction, the residue is washed by distilled water, and the product is dried in vacuum to obtain white powdery substance;
b) adding aliphatic organic acid and IA group metal compound into the white powdery substance obtained in the step a), reacting at the temperature of 30-250 ℃ for 0.5-25 hours to obtain the liquid titanium catalyst for producing the poly (succinic acid) -co-adipic acid-butanediol ester.
According to the invention, the composition formed by combining trimethylolpropane and at least one polyol is added, so that the end-capping probability of terminal hydroxyl is increased, the content of terminal carboxyl of the copolyester is reduced, functional groups which are not contained in a molecular chain of the copolymer are not introduced, and the green environmental protection property of the copolymer is not influenced.
The preparation method of the poly (butylene succinate-co-adipate-glycol ester) with low carboxyl content comprises the following steps:
the known polyester preparation method can be adopted, and succinic acid, adipic acid and butanediol are subjected to esterification reaction at the temperature of 150-230 ℃ and under the reaction pressure of normal pressure-0.5 MPa. And then carrying out polycondensation reaction under the vacuum condition, wherein the reaction temperature is 230-250 ℃, and the reaction pressure is less than 120 Pa. The liquid titanium catalyst is added into the reaction system after the esterification reaction is finished, and the dosage is 50-120 mg/kg (based on the mass of the polycondensation product). The polyol composition of trimethylolpropane in combination with at least one polyol may be added before the start of the esterification reaction, or may be added after the end of the esterification reaction before the start of the polycondensation reaction. And (4) after the polycondensation reaction is finished, casting a belt and granulating to obtain a polymer product.
In the present invention, the intrinsic viscosity and the terminal carboxyl group content of the polybutylene succinate-co-adipate with a low terminal carboxyl group content were measured by the following methods:
a) intrinsic viscosity: the mixture of phenol and tetrachloroethane is used as solvent, and the measurement is carried out at 25 ℃ by using an Ubbelohde viscometer.
b) Content of terminal carboxyl groups: the carboxyl end group content X is calculated according to the following formula and is calculated in units of moles per ton (mol/t).
X＝(V-V0)×c×103/m
In the formula:
v: the volume of the potassium hydroxide-ethanol standard titration solution consumed by the sample solution is a numerical value in milliliters (mL);
V0: the volume of the potassium hydroxide-ethanol standard titration solution consumed by the blank solution is a numerical value in milliliters (mL);
c: the concentration of the potassium hydroxide-ethanol standard titration solution is expressed in mol per liter (mol/L);
m: the sample is weighed in grams (g).
The technical scheme of the invention is that the polyol composition which is formed by adding trimethylolpropane and at least one other polyol and has a general formula of Ti (OR)4Is obtained by the reaction of titanium compound, dihydric alcohol, aliphatic organic acid and IA group metal compoundThe prepared poly (butylene succinate) -co-adipic acid-butylene glycol ester has lower carboxyl end group content which can be less than 10 mol/t; and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Preparation of liquid titanium catalyst A
In a reactor equipped with a stirrer, a condenser and a thermometer, 18.6 g (0.3 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 80 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 27 g (0.3 mol) of lactic acid and 18 g (0.2 mol) of butanediol were added and reacted at 100 ℃ for 3 hours to obtain a pale yellow transparent liquid as catalyst A.
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. Adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 50mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.63dL/g and the content of terminal carboxyl groups to be 29 mol/t.
[ example 1 ]
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. After the esterification, adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 50mg/kg) and a composition of trimethylolpropane and pentaerythritol (the weight ratio of the composition to the copolyester is 0.03%), vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting polycondensation, stopping the reaction after the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling and granulating, and measuring the intrinsic viscosity to be 1.96dL/g and the terminal carboxyl group content to be 12 mol/t.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of liquid titanium catalyst B
In a reactor equipped with a stirrer, a condenser and a thermometer, 18.6 g (0.3 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 100 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was put into a reactor equipped with a stirrer, a condenser and a thermometer, and 18 g (0.2 mol) of lactic acid, 96 g of a 25% aqueous solution (0.6 mol) of sodium hydroxide and 27 g (0.3 mol) of butanediol were added and reacted at 120 ℃ for 4 hours to obtain a colorless transparent liquid as catalyst B.
Preparation of poly (butylene succinate-co-adipate)
Mixing 280 g of succinic acid, 87 g of adipic acid and 348 g of butanediol to prepare slurry, adding the slurry into a polymerization kettle for esterification reaction at the esterification temperature of 160-200 ℃, and discharging water generated by the reaction through a rectification device. Adding a catalyst B (based on the mass of the generated polymer, the weight of titanium atoms is 70mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.84dL/g and the content of terminal carboxyl groups to be 30 mol/t.
[ example 2 ]
Preparation of poly (butylene succinate-co-adipate)
280 g of succinic acid, 87 g of adipic acid, 348 g of butanediol, a composition of trimethylolpropane and neopentyl glycol (the weight ratio of the composition to the copolyester is 0.08%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst B (based on the mass of the generated polymer, the weight of titanium atoms is 70mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.98dL/g and the content of terminal carboxyl groups to be 9 mol/t.
[ COMPARATIVE EXAMPLE 3 ]
Preparation of liquid titanium catalyst C
In a reactor equipped with a stirrer, a condenser and a thermometer, 37.2 g (0.6 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 42 g (0.2 mol) of citric acid monohydrate, 48 g of a 25% aqueous sodium hydroxide solution (0.3 mol) and 54 g (0.6 mol) of butanediol were added thereto to react at 90 ℃ for 4 hours to obtain a colorless transparent liquid as catalyst C.
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid and 374 g of butanediol are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst C (based on the mass of the generated polymer, the weight of titanium atoms is 120mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.01dL/g and the content of terminal carboxyl groups to be 35 mol/t.
[ example 3 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 374 g of butanediol, trimethylolpropane and mannitol (the weight ratio of the composition to the copolyester is 0.3%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. Adding a catalyst C (based on the mass of the generated polymer, the weight of titanium atoms is 120mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.17dL/g and the content of terminal carboxyl groups to be 8 mol/t.
[ COMPARATIVE EXAMPLE 4 ]
Preparation of liquid titanium catalyst D
In a reactor equipped with a stirrer, a condenser and a thermometer, 24.8 g (0.4 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 105 g (0.5 mol) of citric acid monohydrate, 32 g of a 25% aqueous solution (0.2 mol) of sodium hydroxide and 54 g (0.6 mol) of butanediol were added thereto to react at 100 ℃ for 3 hours to obtain a colorless transparent liquid as catalyst D.
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid and 400 g of butanediol are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.86dL/g and the content of terminal carboxyl groups to be 33 mol/t.
[ COMPARATIVE EXAMPLE 5 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 400 g of butanediol and sorbitol (the weight ratio of the sorbitol to the copolyester is 0.25%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 1.84dL/g and the terminal carboxyl group content to be 31 mol/t.
[ example 4 ]
Preparation of poly (butylene succinate-co-adipate)
245 g of succinic acid, 130 g of adipic acid, 400 g of butanediol, a composition of trimethylolpropane and sorbitol (the weight ratio of the composition to the copolyester is 0.25%) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 160-200 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst D (based on the mass of the generated polymer, the weight of titanium atoms is 100mg/kg), vacuumizing and reducing the pressure of the system to be lower than 100Pa, gradually raising the reaction temperature to 240 ℃, starting the polycondensation reaction, stopping the reaction when the reaction time reaches 180 minutes, continuously extruding the reaction product from a casting belt at the bottom of a polymerization kettle, cooling, granulating, and measuring the intrinsic viscosity to be 2.23dL/g and the content of terminal carboxyl groups to be 10 mol/t.
Claims (7)
1. A preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content is characterized in that a polyol composition is added before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction is finished;
wherein the polyol composition is selected from trimethylolpropane and at least one other polyol;
the other polyhydric alcohol is selected from at least one of pentaerythritol, neopentyl glycol, sorbitol, glycerol, xylitol or mannitol; the weight ratio of trimethylolpropane to other polyols is 1: (1-15).
2. The method of claim 1, wherein the weight ratio of trimethylolpropane to other polyols is 1: (1-8).
3. The preparation method of poly (butylene succinate) -co-adipate-glycol ester with low terminal carboxyl content according to claim 1 or 2, characterized by comprising the following steps of taking succinic acid, adipic acid and butanediol as raw materials, carrying out esterification reaction by using a liquid titanium catalyst under the conditions that the reaction temperature is 150-230 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain an esterification product, and carrying out polycondensation reaction under the vacuum conditions that the reaction temperature is 230-250 ℃ and the reaction pressure is less than 120Pa to obtain poly (butylene succinate-co-adipate-glycol ester), wherein the used liquid titanium catalyst comprises the reaction product of the following raw materials:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one aliphatic organic acid selected from organic acids;
(D) at least one metal compound selected from IA of the periodic table;
adding the polyol composition before the esterification reaction starts or before the polycondensation reaction starts after the esterification reaction finishes;
wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-20): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-10): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (0-10): 1, the weight ratio of the polyol composition to the copolyester is 0.01-0.4%.
4. The method for preparing poly (butylene succinate-co-adipate) with low carboxyl end group content according to claim 3, wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-10): 1, the molar ratio of the aliphatic organic acid (C) to the titanium compound (A) is (1-5): 1, the molar ratio of the metal compound (D) to the titanium compound (A) is (2-6): 1.
5. the method of claim 3, wherein the weight ratio of the polyol composition to the copolyester is 0.03-0.3%.
6. The method of claim 3, wherein the titanium compound (A) is at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; the dihydric alcohol (B) is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol; the aliphatic organic acid (C) is at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid or lactic acid; the group IA metal compound (D) is at least one selected from lithium, sodium and potassium.
7. The method for preparing low-end carboxyl group content olybuthylenesuccinate-co-adipate-butylene glycol ester according to claim 3, wherein the amount of the catalyst added is 50-120 mg/kg in terms of titanium atom based on the weight of the produced olybuthylenesuccinate-co-adipate-butylene glycol ester.
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| TWI800748B (en) * | 2020-08-20 | 2023-05-01 | 南亞塑膠工業股份有限公司 | Method for manufacturing polyester polyhydric alcohol |
| CN112542296B (en) * | 2020-12-04 | 2021-10-29 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
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