CN115028818A - 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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- CN115028818A CN115028818A CN202210718332.8A CN202210718332A CN115028818A CN 115028818 A CN115028818 A CN 115028818A CN 202210718332 A CN202210718332 A CN 202210718332A CN 115028818 A CN115028818 A CN 115028818A
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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
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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 has the following structural formula:
the preparation method comprises the following steps: pulping the raw materials, performing ester exchange reaction, performing polycondensation reaction, discharging, crushing, drying and the like. The novel polyester material prepared by the invention has obviously improved heat resistance, has good organic solvent solubility, and has potential application value in the field of coatings.
Description
Technical Field
The invention belongs to the technical field of polyester materials, and particularly relates to a polyester material meeting high temperature resistance and having good solubility and a preparation method thereof.
Background
The prior market-made terephthalic acid homopolyester materials mainly comprise polyethylene terephthalate (PET), 1, 3-propylene terephthalate (PTT), 1, 4-butylene terephthalate (PBT) and 1, 4-cyclohexane dimethanol terephthalate (PCT), and the semi-aromatic polyester materials are widely applied to various fields in daily life of people, particularly four aspects of fibers, films, container packages and plastics. The PET capacity reaches 3000 ten thousand tons in 2021 year according to statistics, which is equivalent to the seed consumption of cotton in the same year. The series of terephthalic acid homopolyester materials have good heat resistance, such as the glass transition temperature of PET is 76 ℃, the glass transition temperature of PTT is 42 ℃, the glass transition temperature of PBT is 25 ℃, and the glass transition temperature of PCT 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 coatings is limited. Meanwhile, the traditional full-aliphatic polyester has good solubility, can be dissolved in common organic solvents, but has poor thermal stability and glass transition temperature lower than room temperature. In order to ensure sufficient 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 simultaneously meet the dual 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 a novel polyester prepared by using naphthalene dicarboxylic acid to replace terephthalic acid, wherein the glass transition temperature of the novel polyester can reach 120 ℃. But PEN is difficult to popularize in the field of high-temperature coatings due to strong chemical solvent resistance.
In recent years, there have been many studies on improving the heat resistance of polyester materials.
Subject group [1] Aliphatic cyclic diol Manx-OH is used for replacing aliphatic linear diol, and the glass transition temperature of the prepared polyester material is as high as 130 ℃ (see Green chem.,2014,16, 1716). The Alain topic group utilizes a ternary cyclic diol and terephthalic acid to prepare a novel polyester with a glass transition temperatureThe degree can reach 116 deg.C (see ACS Sustainable chem. Eng.2020,8, 15199-. The above studies have focused on the use of novel diols for the preparation of terephthalic polyester materials. The research does not solve the problem of material solubility on the premise of improving the heat resistance of the polyester.
A series of modified polyester coatings were prepared using 1, 3-propanediol or 1, 5-pentanediol, 2, 5-furandicarboxylic acid, 1, 4-succinic acid, isosorbide by rodri j i guez et al (see prog. The storage problem of the coating is only solved, but the modified polyester coating cannot be applied to the high-temperature field.
In conclusion, polyester materials with high temperature resistance and good solubility properties are lacking in the prior art.
Disclosure of Invention
In order to overcome the problems, the invention provides a novel high-temperature-resistant soluble polyester and a preparation method thereof. A series of novel polyester materials are obtained by preparing a series of dibasic esters with novel structures and polymerizing the dibasic esters with aliphatic diol. The prepared novel polyester material has the weight average molecular weight of 7000-136000 Da, and the excellent heat resistance and dissolution performance 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 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:
putting raw materials, a catalyst and an additive into a reactor, performing nitrogen replacement, maintaining a nitrogen atmosphere at 50-100 ℃, pulping, raising the temperature to 150-220 ℃ when the raw materials, the catalyst and the additive are uniform, performing ester exchange reaction, slowly vacuumizing to reduce the pressure in the reactor to be less than 100Pa when the ester exchange rate reaches more than 95%, raising the temperature to 230-260 ℃, maintaining the vacuum degree in the reactor to be less than 100Pa, performing polycondensation reaction for 2-4 h, discharging, crushing and drying after the polycondensation reaction is finished to obtain the high-temperature-resistant soluble polyester;
the raw materials are dibasic ester with a Cardo fragment structure and a phenylate bond fragment structure, aliphatic straight-chain dihydric alcohol and isosorbide; according to the molar ratio, the dibasic ester has a Cardo fragment structure and a phenylate bond fragment structure: (aliphatic linear diol + isosorbide) 1: 1.2-1.6;
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 selected from one or more of antioxidant 1010 (pentaerythritol tetrakis [ 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 fragment structure and the phenylate bond fragment structure is 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, and the aliphatic linear dihydric alcohol is one or more selected from ethylene glycol, 1, 3-propylene glycol, 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 both the Cardo segment structure and the phenyl ether linkage segment structure: the dosage of the stabilizer is 0.1-0.5 per mill of the mole number of the dibasic ester with both a Cardo fragment structure and a phenylate bond fragment structure; the using amount of the antioxidant is 0.1-0.5 per mill of the mole number of the dibasic ester with both a Cardo segment structure and a phenylate bond segment structure.
Preferably, the slow vacuum pumping is performed by reducing the vacuum degree in the reactor to less than 100Pa within 30-60 minutes.
Has the beneficial effects that:
the invention prepares a series of novel polyester materials by using binary ester which has both a Cardo segment structure and a phenylate bond segment structure as raw materials. The heat resistance of the prepared novel polyester material is obviously improved, the glass transition temperature range of the novel polyester material is 142-180 ℃, and the novel polyester material is obviously higher than PEN (the glass transition temperature is 120 ℃) which is the highest polyester material in the current market and has the highest heat resistance. Meanwhile, the prepared novel polyester material has good organic solvent solubility and has potential application value in the field of coatings. The novel polyester material has excellent heat resistance and good solubility, and is expected to expand the popularization of the novel polyester material in the field of high-temperature coatings.
Description of the drawings:
FIG. 1 is a drawing of example 4 1 H-NMR spectrum.
FIG. 2 is a DSC chart of example 4.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, but the conditions for use of the present invention are not limited to the following examples.
Example 1
Raw materials (10g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 1.6g of ethylene glycol), a catalyst (11mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate), and an additive (21mg 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. And performing nitrogen replacement on the air in the container for 3-5 times at room temperature. And (3) keeping the nitrogen atmosphere at 50-100 ℃ and pulping. When the catalyst, the additive and the raw materials are uniformly mixed, heating the reaction system to 150-220 ℃, entering an ester exchange stage, and when the slurry of the reactor becomes clear and transparent, maintaining for 30-60 min, ensuring that the esterification rate reaches more than 95%. And (3) slowly vacuumizing after the ester exchange rate meets the requirement, gradually reducing the pressure in the reactor, after 30-60 min, enabling the vacuum degree in the reactor to reach below 100Pa, heating to 230-260 ℃, maintaining the vacuum degree of the reactor to reach below 100Pa, reacting for 2-4 h, enabling the polymer in the reactor to have a paddle winding phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature resistant soluble polyester.
Example 2
Raw materials (5g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 2.3g of 1, 4-butanediol) and a catalyst (11mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate) and an additive (21mg 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. And performing nitrogen replacement on the air in the container for 3-5 times at room temperature. And (3) keeping the nitrogen atmosphere at 50-100 ℃ and pulping. When the catalyst, the additive and the raw materials are uniformly mixed, heating the reaction system to 150-220 ℃, entering an ester exchange stage, and when the slurry of the reactor becomes clear and transparent, maintaining for 30-60 min, ensuring that the esterification rate reaches more than 95%. And (3) slowly vacuumizing after the ester exchange rate meets the requirement, gradually reducing the pressure in the reactor, after 30-60 min, enabling the vacuum degree in the reactor to reach below 100Pa, heating to 230-260 ℃, maintaining the vacuum degree of the reactor to reach below 100Pa, reacting for 2-4 h, enabling the polymer in the reactor to have a paddle winding phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature resistant soluble polyester.
Example 3
Raw materials (10g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 3.0g of 1, 6-hexanediol) and catalysts (11mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate) and additives (21mg 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. And performing nitrogen replacement on the air in the container for 3-5 times at room temperature. And (3) pulping at 50-100 ℃ under the condition of maintaining nitrogen atmosphere. When the catalyst, the additive and the raw materials are uniformly mixed, heating the reaction system to 150-220 ℃, entering an ester exchange stage, and when the slurry of the reactor becomes clear and transparent, maintaining for 30-60 min, ensuring that the esterification rate reaches more than 95%. And (3) slowly vacuumizing after the ester exchange rate meets the requirement, gradually reducing the pressure in the reactor, after 30-60 min, enabling the vacuum degree in the reactor to reach below 100Pa, heating to 230-260 ℃, maintaining the vacuum degree of the reactor to reach below 100Pa, reacting for 2-4 h, enabling the polymer in the reactor to have a paddle winding phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature resistant soluble polyester.
Example 4
Starting material (10g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl)]Fluorene, 2.1g1, 4-butanediol, 0.37g isosorbide), catalyst (11mg dimethyltin oxide, 12mg zinc acetate anhydrous, 22mg tetrabutyl titanate), additive (21mg triphenyl phosphate, 75mg antioxidant 1010) were put into a reactor, using an overhead mechanical stirring device, equipped with one air inlet and one air outlet at the same time. The atmosphere in the container was replaced with nitrogen 3 to 5 times at room temperature. And (3) keeping the nitrogen atmosphere at 50-100 ℃ and pulping. When the catalyst, the additive and the raw materials are uniformly mixed, heating the reaction system to 150-220 ℃, entering an ester exchange stage, and when the slurry of the reactor becomes clear and transparent, maintaining for 30-60 min, ensuring that the esterification rate reaches more than 95%. And (3) slowly vacuumizing after the ester exchange rate meets the requirement, gradually reducing the pressure in the reactor, after 30-60 min, enabling the vacuum degree in the reactor to reach below 100Pa, heating to 230-260 ℃, maintaining the vacuum degree of the reactor to reach below 100Pa, reacting for 2-4 h, enabling the polymer in the reactor to have a paddle winding 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 graph is shown in FIG. 2.
Example 5
Raw materials (10g of 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, 2.7g of 1, 6-hexanediol, 0.37g of isosorbide) and a catalyst (11mg of dimethyltin oxide, 12mg of anhydrous zinc acetate, 22mg of tetrabutyl titanate) and an additive (21mg 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. And performing nitrogen replacement on the air in the container for 3-5 times at room temperature. And (3) keeping the nitrogen atmosphere at 50-100 ℃ and pulping. When the catalyst, the additive and the raw materials are uniformly mixed, heating the reaction system to 150-220 ℃, entering an ester exchange stage, and when the slurry of the reactor becomes clear and transparent, maintaining for 30-60 min, ensuring that the esterification rate reaches more than 95%. And (3) slowly vacuumizing after the ester exchange rate meets the requirement, gradually reducing the pressure in the reactor, after 30-60 min, enabling the vacuum degree in the reactor to reach below 100Pa, heating to 230-260 ℃, maintaining the vacuum degree of the reactor to reach below 100Pa, reacting for 2-4 h, enabling the polymer in the reactor to have a paddle winding phenomenon, and finishing the polycondensation reaction. Discharging, powdering and drying to obtain the novel high-temperature resistant soluble polyester.
Example 6
And (3) carrying out a thermal performance test on the products prepared in the embodiments 1-5, wherein the temperature is increased to 700 ℃ at a heating rate of 10 ℃/min with 50 ℃ as an initial temperature. The resulting thermal performance parameters are shown in table 1.
TABLE 1 thermal Properties of the products prepared in examples 1-5
As can be seen from Table 1, the novel high-temperature-resistant polyester can be prepared by the method disclosed by the invention, in the examples 1-5, the glass transition temperature is all as high as more than 140 ℃, and 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 1-5
| 1,1,2, 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 1,1,2, 2-tetrachloroethane and trichloromethane at room temperature, and has good organic solvent solubility.
Claims (5)
1. A high temperature resistant soluble polyester having the following 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;
2. A method for preparing the high temperature resistant soluble polyester of claim 1, comprising the steps of: putting raw materials, a catalyst and an additive into a reactor, performing nitrogen replacement, maintaining a nitrogen atmosphere at 50-100 ℃, pulping, raising the temperature to 150-220 ℃ when the raw materials, the catalyst and the additive are uniform, performing ester exchange reaction, slowly vacuumizing to reduce the pressure in the reactor to be less than 100Pa when the ester exchange rate reaches more than 95%, raising the temperature to 230-260 ℃, maintaining the vacuum degree in the reactor to be less than 100Pa, performing polycondensation reaction for 2-4 h, discharging, crushing and drying after the polycondensation reaction is finished to obtain the high-temperature-resistant soluble polyester;
the raw materials are dibasic ester with a Cardo fragment structure and a phenylate bond fragment structure, aliphatic straight-chain dihydric alcohol and isosorbide; according to the molar ratio, the dibasic ester has a Cardo fragment structure and a phenylate bond fragment structure: (aliphatic linear diol + isosorbide) 1: 1.2-1.6;
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 selected from one or more of antioxidant 1010, antioxidant 300 and antioxidant 168.
3. The method for preparing high temperature resistant soluble polyester as claimed in claim 2, wherein said dibasic ester having both Cardo segment structure and phenylate bond segment structure is 9, 9-bis [4- (4-methoxycarbonylphenoxy) phenyl ] fluorene, and said aliphatic linear diol is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.
4. The method for preparing the high temperature resistant soluble polyester as claimed in claim 2, wherein the amount of the catalyst is 0.1 to 0.5 per mill of the mole number of the dibasic ester having both the Cardo segment structure and the phenylene ether bond segment structure: the dosage of the stabilizer is 0.1-0.5 per mill of the mole number of the dibasic ester with both a Cardo fragment structure and a phenylate bond fragment structure; the using amount of the antioxidant is 0.1-0.5 per mill of the mole number of the dibasic ester with both a Cardo fragment structure and a phenylate bond fragment structure.
5. The method for preparing the high temperature resistant soluble polyester according to claim 2, wherein the slow vacuum pumping is performed by reducing the vacuum degree in the reactor to below 100Pa within 30-60 minutes.
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Citations (6)
| 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 |
| US20040092703A1 (en) * | 2002-11-13 | 2004-05-13 | Germroth Ted Calvin | Method for making isosorbide containing polyesters |
| JP2011190349A (en) * | 2010-03-15 | 2011-09-29 | Unitika Ltd | Soluble copolymerized polyester resin |
| JP2014040517A (en) * | 2012-08-22 | 2014-03-06 | Toyobo Co Ltd | 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 |
| CN113667105A (en) * | 2021-09-08 | 2021-11-19 | 吉林大学 | High-heat-resistance PTT modified based on isosorbide and benzyl diol and preparation method thereof |
-
2022
- 2022-06-23 CN CN202210718332.8A patent/CN115028818B/en active Active
Patent Citations (6)
| 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 |
| US20040092703A1 (en) * | 2002-11-13 | 2004-05-13 | Germroth Ted Calvin | Method for making isosorbide containing polyesters |
| JP2011190349A (en) * | 2010-03-15 | 2011-09-29 | Unitika Ltd | Soluble copolymerized polyester resin |
| JP2014040517A (en) * | 2012-08-22 | 2014-03-06 | Toyobo Co Ltd | 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 |
| CN113667105A (en) * | 2021-09-08 | 2021-11-19 | 吉林大学 | High-heat-resistance PTT modified based on isosorbide and benzyl diol and preparation method thereof |
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