CN115028818B - High-temperature-resistant soluble polyester and preparation method thereof - Google Patents
High-temperature-resistant soluble polyester and preparation method thereof Download PDFInfo
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- CN115028818B CN115028818B CN202210718332.8A CN202210718332A CN115028818B CN 115028818 B CN115028818 B CN 115028818B CN 202210718332 A CN202210718332 A CN 202210718332A CN 115028818 B CN115028818 B CN 115028818B
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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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- 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
- C08G63/78—Preparation processes
Abstract
The invention relates to high-temperature-resistant soluble polyester and a preparation method thereof, belonging to the technical field of polyester materials. The high temperature resistant soluble polyester hasThe following structural formula:
the preparation method comprises the following steps: pulping the raw materials, performing transesterification, performing polycondensation, discharging, crushing, drying and the like. The novel polyester material prepared by the invention has obviously improved heat resistance, good organic solvent solubility and potential application value in the field of paint.
Description
Technical Field
The invention belongs to the technical field of polyester materials, and particularly relates to a polyester material with high temperature resistance and good solubility and a preparation method thereof.
Background
The terephthalic acid-based polyester material in market at present is mainly polyethylene terephthalate (PET), poly (1, 3-propylene glycol terephthalate) (PTT), poly (1, 4-butylene terephthalate) (PBT) and poly (1, 4-cyclohexanedimethanol terephthalate) (PCT), and the semi-aromatic polyester material is widely applied to various fields in daily life of people, in particular to four aspects of fiber, film, container package and plastic. The PET productivity in 2021 is up to 3000 ten thousand tons, which is equivalent to the seed consumption of cotton in the same year. The series of terephthalic acid-based polyester materials have good heat resistance, for example, the PET glass transition temperature is 76 ℃, the PTT glass transition temperature is 42 ℃, the PBT glass transition temperature is 25 ℃, and the PCT glass transition temperature is 106 ℃. However, the semi-aromatic polyester material has poor dissolving capacity in common chemical solvents, so that the application of the semi-aromatic polyester material in the field of paint is limited. Meanwhile, the traditional full aliphatic polyester has good solubility, can be dissolved in common organic solvents, but has poor heat stability, and the glass transition temperature is lower than room temperature. In order to ensure adequate stability of the coating during storage, it is required that the glass transition temperature of the coating must be well above room temperature. The traditional polyester coating is difficult to meet the double requirements of heat resistance and solubility, and the popularization of the polyester coating is restricted.
Patent 604073,1948 discloses a novel semi-aromatic polyester material polyethylene naphthalate (PEN), which is prepared by using naphthalene dicarboxylic acid to replace terephthalic acid, wherein the glass transition temperature can reach 120 ℃. However, PEN is difficult to popularize in the field of high-temperature coatings due to the strong chemical solvent resistance.
There have been many researches in recent years for improving the heat resistance of polyester materials.
Subject group [1] The glass transition temperature of the prepared polyester material is up to 130 ℃ (see Green chem.,2014,16,1716) by using the aliphatic cyclic diol Manx-OH to replace the aliphatic linear diol. The Alain group uses a ternary cyclic diol and terephthalic acid to produce a novel polyester with a glass transition temperature of 116 ℃ (see ACS sustaiable chem. Eng.2020,8, 15199-15208). The above research has focused on the use of novel diols to prepare terephthalic polyester materials. The above research has not solved the problem of material solubility under the premise of improving the heat resistance of polyester.
Rodrii guez et al prepared a series of modified polyester coatings using 1, 3-propanediol or 1, 5-pentanediol, 2, 5-furandicarboxylic acid, 1, 4-butanedioic acid, isosorbide (see prog. Organ. Coat.2014,77, 277-284). Only solves the storage problem of the paint, but the modified polyester paint cannot be applied in the high-temperature field.
In conclusion, the prior art lacks a polyester material with high temperature resistance and good dissolution property.
Disclosure of Invention
In order to overcome the problems, the invention provides novel high-temperature-resistant soluble polyester and a preparation method thereof. A series of novel polyester materials are obtained by preparing a series of novel structural dibasic esters and polymerizing the dibasic esters with aliphatic dihydric alcohols. The prepared novel polyester material has a weight average molecular weight of 7000-136000 Da, and the excellent heat resistance and solubility of the material are obviously better than those of the prior art.
The specific technical scheme of the invention is as follows:
a high temperature resistant soluble polyester having the structural formula:
wherein x is an integer of 0 to 300, y is an integer of 0 to 100, and n is an integer of 0 to 4;
A preparation method of high-temperature-resistant soluble polyester comprises the following steps:
adding raw materials, a catalyst and an additive into a reactor, replacing with nitrogen, maintaining a nitrogen atmosphere at 50-100 ℃, pulping, when the raw materials, the catalyst and the additive are uniform, raising the temperature to 150-220 ℃, performing transesterification, slowly vacuumizing to lower the pressure in the reactor to below 100Pa after the transesterification rate reaches above 95%, raising the temperature to 230-260 ℃, maintaining the vacuum degree in the reactor to below 100Pa, carrying out polycondensation for 2-4 h, discharging, crushing particles, and drying to obtain the high-temperature-resistant soluble polyester;
the raw materials are dibasic ester, aliphatic linear dihydric alcohol and isosorbide which have both Cardo segment structures and phenyl ether bond segment structures; according to the mole ratio, the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure is prepared by the following steps: (aliphatic linear diol+isosorbide) =1:1.2 to 1.6;
the catalyst is selected from one or more of dimethyl tin oxide, tin acetate, tetraethoxy titanium, tetrabutyl titanate, tetraisopropyl titanate, ethylene glycol titanium, 1, 3-propylene glycol titanium, antimony trioxide, ethylene glycol antimony, butylene glycol antimony, 1, 3-propylene glycol antimony and hexylene glycol antimony;
the additive comprises a stabilizer and an antioxidant, wherein the stabilizer is selected from one or more of phosphoric acid, alkyl phosphate, triphenyl phosphate and alkyl diaryl phosphate; the antioxidant is one or more selected from antioxidant 1010 (pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 300 (4, 4' -thiobis (6-tert-butyl-3-methylphenol)), and antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite).
Preferably, the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure is 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, and the aliphatic linear dihydric alcohol is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol;
preferably, the catalyst is used in an amount of 0.1 to 0.5 per mill of the mole number of the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure: the dosage of the stabilizer is 0.1 to 0.5 per mill of the mole number of the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure; the dosage of the antioxidant is 0.1 to 0.5 per mill of the mole number of the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure.
Preferably, the slow vacuum is performed by reducing the vacuum degree in the reactor to 100Pa or less in 30 to 60 minutes.
The beneficial effects are that:
the invention prepares a series of novel polyester materials by using dibasic ester with a Cardo segment structure and a phenyl ether bond segment structure as raw materials. The heat resistance of the prepared novel polyester material is obviously improved, and the glass transition temperature is in the range of 142-180 ℃ and is obviously higher than the PEN (glass transition temperature is 120 ℃) of the polyester material with the highest heat resistance in the market at present. Meanwhile, the prepared novel polyester material has good organic solvent solubility and potential application value in the field of coatings. The novel polyester material has excellent heat resistance and good solubility, and is hopeful to expand the popularization in the field of high-temperature coating.
Description of the drawings:
FIG. 1 is a schematic diagram of example 4 1 H-NMR spectrum.
Fig. 2 is a DSC profile of example 4.
The specific embodiment is as follows:
the invention is further described below in connection with examples, but the conditions under which the invention is used are not limited to the following examples.
Example 1
The raw material (10 g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 1.6g of ethylene glycol) and catalyst (11 mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), additive (21 mg of triphenyl phosphate, 75mg of antioxidant 1010) were put into a reactor, and an overhead mechanical stirring device was used while being equipped with an air inlet and an air outlet. The air in the container is replaced by nitrogen for 3 to 5 times under the room temperature condition. And (3) maintaining a nitrogen atmosphere at 50-100 ℃ for pulping. When the catalyst, the additive and the raw materials are uniformly mixed, the reaction system is heated to 150-220 ℃ and enters the transesterification stage, and when the slurry of the reactor becomes clear and transparent, the reaction is maintained for 30-60 min, so that the esterification rate is ensured to reach more than 95%. When the transesterification rate reaches the requirement, slowly vacuumizing, gradually reducing the pressure in the reactor, after 30-60 min, heating to 230-260 ℃ when the vacuum degree in the reactor reaches below 100Pa, maintaining the vacuum degree in the reactor to reach below 100Pa, reacting for 2-4 h, wherein the polymer in the reactor has a winding paddle phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature-resistant soluble polyester.
Example 2
The raw material (5 g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 2.3g of 1, 4-butanediol) and catalyst (11 mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), additive (21 mg of triphenyl phosphate, 75mg of antioxidant 1010) were charged into a reactor, and an overhead mechanical stirring device was used while being equipped with an air inlet and an air outlet. The air in the container is replaced by nitrogen for 3 to 5 times under the room temperature condition. And (3) maintaining a nitrogen atmosphere at 50-100 ℃ for pulping. When the catalyst, the additive and the raw materials are uniformly mixed, the reaction system is heated to 150-220 ℃ and enters the transesterification stage, and when the slurry of the reactor becomes clear and transparent, the reaction is maintained for 30-60 min, so that the esterification rate is ensured to reach more than 95%. When the transesterification rate reaches the requirement, slowly vacuumizing, gradually reducing the pressure in the reactor, after 30-60 min, heating to 230-260 ℃ when the vacuum degree in the reactor reaches below 100Pa, maintaining the vacuum degree in the reactor to reach below 100Pa, reacting for 2-4 h, wherein the polymer in the reactor has a winding paddle phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature-resistant soluble polyester.
Example 3
The starting material (10 g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 3.0g of 1, 6-hexanediol) and catalyst (11 mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), additive (21 mg of triphenyl phosphate, 75mg of antioxidant 1010) were charged into a reactor, and an overhead mechanical stirring apparatus was used, while equipped with an air inlet and an air outlet. The air in the container is replaced by nitrogen for 3 to 5 times under the room temperature condition. And (3) maintaining nitrogen atmosphere at 50-100 ℃ for pulping. When the catalyst, the additive and the raw materials are uniformly mixed, the reaction system is heated to 150-220 ℃ and enters the transesterification stage, and when the slurry of the reactor becomes clear and transparent, the reaction is maintained for 30-60 min, so that the esterification rate is ensured to reach more than 95%. When the transesterification rate reaches the requirement, slowly vacuumizing, gradually reducing the pressure in the reactor, after 30-60 min, heating to 230-260 ℃ when the vacuum degree in the reactor reaches below 100Pa, maintaining the vacuum degree in the reactor to reach below 100Pa, reacting for 2-4 h, wherein the polymer in the reactor has a winding paddle phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature-resistant soluble polyester.
Example 4
The starting material (10 g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl)]Fluorene, 2.1g of 1, 4-butanediol, 0.37g of isosorbide), catalyst (11 mg of dimethyl tin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), additive (21 mg of triphenyl phosphate, 75mg of antioxidant 1010) were put into a reactor, and an overhead machine was usedThe mechanical stirring device is provided with an air inlet and an air outlet. The air in the container is replaced by nitrogen at room temperature for 3 to 5 times. And (3) maintaining a nitrogen atmosphere at 50-100 ℃ for pulping. When the catalyst, the additive and the raw materials are uniformly mixed, the reaction system is heated to 150-220 ℃ and enters the transesterification stage, and when the slurry of the reactor becomes clear and transparent, the reaction is maintained for 30-60 min, so that the esterification rate is ensured to reach more than 95%. When the transesterification rate reaches the requirement, slowly vacuumizing, gradually reducing the pressure in the reactor, after 30-60 min, heating to 230-260 ℃ when the vacuum degree in the reactor reaches below 100Pa, maintaining the vacuum degree in the reactor to reach below 100Pa, reacting for 2-4 h, wherein the polymer in the reactor has a winding paddle phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain novel high-temperature-resistant soluble polyester 1 The H-NMR spectrum is shown in FIG. 1, and the DSC curve is shown in FIG. 2.
Example 5
The starting material (10 g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 2.7g of 1, 6-hexanediol, 0.37g of isosorbide) and catalyst (11 mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), additives (21 mg of triphenyl phosphate, 75mg of antioxidant 1010) were charged into a reactor, and an overhead mechanical stirring apparatus was used while equipped with an air inlet and an air outlet. The air in the container is replaced by nitrogen for 3 to 5 times under the room temperature condition. And (3) maintaining a nitrogen atmosphere at 50-100 ℃ for pulping. When the catalyst, the additive and the raw materials are uniformly mixed, the reaction system is heated to 150-220 ℃ and enters the transesterification stage, and when the slurry of the reactor becomes clear and transparent, the reaction is maintained for 30-60 min, so that the esterification rate is ensured to reach more than 95%. When the transesterification rate reaches the requirement, slowly vacuumizing, gradually reducing the pressure in the reactor, after 30-60 min, heating to 230-260 ℃ when the vacuum degree in the reactor reaches below 100Pa, maintaining the vacuum degree in the reactor to reach below 100Pa, reacting for 2-4 h, wherein the polymer in the reactor has a winding paddle phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature-resistant soluble polyester.
Example 6
The products prepared in examples 1 to 5 were subjected to thermal performance testing at a temperature of 50℃as an initial temperature and at a temperature rise rate of 10℃per minute to 700 ℃. The resulting thermal properties are shown in Table 1.
Table 1 thermal parameters of the products prepared in examples 1 to 5
As can be seen from Table 1, the novel high-temperature-resistant polyester can be prepared by the method, and the glass transition temperatures of examples 1 to 5 are all up to 140 ℃ or more, so that the novel high-temperature-resistant polyester has excellent heat resistance.
The products prepared in examples 1 to 5 were subjected to solubility test, and the test results are shown in Table 2.
TABLE 2 solubility in organic solvents of the products prepared in examples 1 to 5
| 1, 2-tetrachloroethane | Trichloromethane | |
| Example 1 | Soluble at room temperature | Soluble at room temperature |
| Example 2 | Soluble at room temperature | Soluble at room temperature |
| Example 3 | Soluble at room temperature | Soluble at room temperature |
| Example 4 | Soluble at room temperature | Soluble at room temperature |
| Example 5 | Soluble at room temperature | Soluble at room temperature |
As can be seen from Table 2, the novel high-temperature-resistant polyester prepared by the method can be dissolved in 1, 2-tetrachloroethane and trichloromethane at room temperature, and has good solubility in organic solvents.
Claims (5)
1. The high temperature resistant soluble polyester has a weight average molecular weight of 7000-136000 Da and has the following structural formula:
wherein x is an integer of 0 to 300, y is an integer of 0 to 100, and x and y are not simultaneously 0; n is an integer of 0 to 4;
2. A process for the preparation of the high temperature resistant soluble polyester of claim 1 comprising the steps of: adding raw materials, a catalyst and an additive into a reactor, replacing with nitrogen, maintaining a nitrogen atmosphere at 50-100 ℃, pulping, when the raw materials, the catalyst and the additive are uniform, raising the temperature to 150-220 ℃, performing transesterification, slowly vacuumizing to lower the pressure in the reactor to below 100Pa after the transesterification rate reaches above 95%, raising the temperature to 230-260 ℃, maintaining the vacuum degree in the reactor to below 100Pa, carrying out polycondensation for 2-4 h, discharging, crushing particles, and drying to obtain the high-temperature-resistant soluble polyester;
the raw materials are dibasic ester, aliphatic linear dihydric alcohol and isosorbide which have both Cardo segment structures and phenyl ether bond segment structures; according to the mole ratio, the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure is prepared by the following steps: (aliphatic linear diol+isosorbide) =1:1.2 to 1.6;
the catalyst is selected from one or more of dimethyl tin oxide, tin acetate, tetraethoxy titanium, tetrabutyl titanate, tetraisopropyl titanate, ethylene glycol titanium, 1, 3-propylene glycol titanium, antimony trioxide, ethylene glycol antimony, butylene glycol antimony, 1, 3-propylene glycol antimony and hexylene glycol antimony;
the additive comprises a stabilizer and an antioxidant, wherein the stabilizer is selected from one or more of phosphoric acid, alkyl phosphate, triphenyl phosphate and alkyl diaryl phosphate; the antioxidant is one or more selected from antioxidant 1010, antioxidant 300 and antioxidant 168.
3. The method for preparing the high-temperature-resistant soluble polyester according to claim 2, wherein the diester having both a Cardo segment structure and a phenyl ether bond structure is 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, and the aliphatic linear diol is one or more selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.
4. The method for preparing the high-temperature-resistant soluble polyester according to claim 2, wherein the catalyst is used in an amount of 0.1 to 0.5 per mill of the mole number of the dibasic ester with both Cardo segment structure and phenyl ether bond segment structure: the dosage of the stabilizer is 0.1 to 0.5 per mill of the mole number of the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure; the dosage of the antioxidant is 0.1 to 0.5 per mill of the mole number of the dibasic ester with the Cardo segment structure and the phenyl ether bond segment structure.
5. The method for preparing high temperature resistant soluble polyester according to claim 2, wherein the slow vacuum pumping is to reduce the vacuum degree in the reactor to below 100Pa in 30-60 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5959066A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
| US6914120B2 (en) * | 2002-11-13 | 2005-07-05 | Eastman Chemical Company | Method for making isosorbide containing polyesters |
| JP2011190349A (en) * | 2010-03-15 | 2011-09-29 | Unitika Ltd | Soluble copolymerized polyester resin |
| JP6036004B2 (en) * | 2012-08-22 | 2016-11-30 | 東洋紡株式会社 | Polyester resin |
| JP2019026738A (en) * | 2017-07-31 | 2019-02-21 | 三菱瓦斯化学株式会社 | Polyester resin, and polyester resin solution, paint and coating agent based on the same |
| CN113667105B (en) * | 2021-09-08 | 2022-05-31 | 吉林大学 | High-heat-resistance PTT modified based on isosorbide and benzyl diol and preparation method thereof |
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