CN115028818A - A kind of high temperature resistant soluble polyester and preparation method thereof - Google Patents

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

A kind of high temperature resistant soluble polyester and preparation method thereof

technical field

The invention belongs to the technical field of polyester materials, and particularly relates to a class of polyester materials that satisfy high temperature resistance and have good solubility and a preparation method thereof.

Background technique

The currently marketed terephthalic acid homopolyester materials are polyethylene terephthalate (PET), polyethylene terephthalate (PTT), polyethylene terephthalate (PTT), and polyethylene terephthalate (PET) -Butylene glycol ester (PBT) and poly(1,4-cyclohexanedimethanol terephthalate) (PCT) are the main materials. The above semi-aromatic polyester materials are widely used in various fields in people's daily life, especially in fiber , film, container packaging, plastic four aspects. According to statistics, the PET production capacity in 2021 will reach 30 million tons, which is equivalent to the consumption of cotton in the same year. The above series of terephthalic acid homopolyester materials have good heat resistance, such as PET glass transition temperature of 76 °C, PTT glass transition temperature of 42 °C, PBT glass transition temperature of 25 °C, PCT glass transition temperature 106°C. However, due to the poor solubility of the above-mentioned semi-aromatic polyester materials in common chemical solvents, their application in the field of coatings is limited. At the same time, traditional all-aliphatic polyesters have good solubility and can be dissolved in common organic solvents, but their thermal stability is poor and their glass transition temperature is lower than room temperature. In order to ensure sufficient stability of the coating during storage, the glass transition temperature of the coating must be much higher than room temperature. It is difficult for traditional polyester coatings to meet the dual requirements of heat resistance and solubility at the same time, which restricts the popularization of polyester coatings.

Invention patent Br.Patent 604073,1948 discloses a new type of semi-aromatic polyester material polyethylene naphthalate (PEN), a new type of polyester prepared by using naphthalene dicarboxylic acid instead of terephthalic acid, glass transition The temperature can reach 120°C. However, due to the strong chemical solvent resistance of PEN, it is difficult to promote in the field of high temperature coatings.

课题组^[1]利用脂肪族环状二元醇Manx-OH代替脂肪族直链二元醇，制备的聚酯材料玻璃化转变温度高达130℃(参见Green Chem.,2014,16,1716)。Alain课题组利用一种三元环状二元醇与对苯二甲酸制备了一种新型聚酯，玻璃化转变温度可以达到116℃(参见ACS SustainableChem.Eng.2020,8,15199-15208)。上述研究侧重于利用新型的二元醇来制备对苯二甲酸类聚酯材料。上述研究在提高聚酯耐热性能的前提下，并未解决材料溶解性能的问题。In recent years, there have been many related studies on improving the heat resistance of polyester materials.

The research group ^[1] used the aliphatic cyclic diol Manx-OH to replace the aliphatic linear diol, and the glass transition temperature of the prepared polyester material was as high as 130 °C (see Green Chem., 2014, 16, 1716). Alain's group prepared a new type of polyester using a ternary cyclic diol and terephthalic acid, with a glass transition temperature of 116 °C (see ACS SustainableChem.Eng.2020,8,15199-15208). The above research focuses on the use of novel diols to prepare terephthalic acid-based polyester materials. The above research did not solve the problem of material solubility under the premise of improving the heat resistance of polyester.

Rodríguez et al. prepared a series of modified polyester coatings using 1,3-propanediol or 1,5-pentanediol, 2,5-furandicarboxylic acid, 1,4-succinic acid, and isosorbide (see Prog.Organ .Coat.2014, 77, 277–284). Only the storage problem of the coating is solved, but the modified polyester coating cannot be applied in the high temperature field.

To sum up, based on the prior art, there is a lack of polyester materials with high temperature resistance and good solubility.

SUMMARY OF THE INVENTION

In order to overcome the above problems, the present invention provides a novel high temperature resistant soluble polyester and a preparation method thereof. A series of new polyester materials are obtained by preparing a series of dibasic esters with new structures and polymerizing with aliphatic diols. The weight average molecular weight of the prepared new polyester material is 7000-136000 Da, and the excellent heat resistance and solubility of the material are obviously better than those of the prior art.

The concrete technical scheme of the present invention is as follows:

A high-temperature-resistant soluble polyester has the following structural formula:

Wherein, x is an integer from 0 to 300, y is an integer from 0 to 100, and n is an integer from 0 to 4;

代表新型二元酯片段，结构为

represents a novel dibasic ester fragment with a structure of

A preparation method of high temperature resistant soluble polyester, comprising the following steps:

Put the raw materials, catalysts and additives into the reactor, replace with nitrogen, maintain a nitrogen atmosphere at 50-100 °C, and carry out beating. When the raw materials, catalysts and additives are uniform, the temperature is raised to 150-220 °C, and transesterification is carried out. Reaction, when the transesterification rate reaches more than 95%, slowly vacuumize to reduce the pressure in the reactor to below 100Pa, then heat up to 230-260°C, maintain the vacuum degree in the reactor below 100Pa, polycondensation reaction 2～4h, polycondensation reaction After finishing, discharging, crushing and drying to obtain the high temperature resistant soluble polyester;

The raw material is a dibasic ester, aliphatic straight-chain diol, isosorbide having both Cardo fragment structure and phenyl ether bond fragment structure; according to the molar ratio, the described material has both Cardo fragment structure and phenyl ether bond fragment Dibasic ester of structure: (aliphatic straight-chain diol+isosorbide)=1:1.2～1.6;

The catalyst is selected from dimethyl tin oxide, tin acetate, titanium tetraethoxide, tetrabutyl titanate, tetraisopropyl titanate, ethylene glycol titanium, 1,3-propanediol titanium, antimony trioxide , one or more of ethylene glycol antimony, butanediol antimony, 1,3-propanediol antimony, hexanediol antimony;

Described additive comprises stabilizer and antioxidant, wherein stabilizer is selected from one or more of phosphoric acid, alkyl phosphate, triphenyl phosphate, alkyl diaryl phosphate; antioxidant is selected from antioxidant 1010 ( Tetrakis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester), antioxidant 300 (4,4'-thiobis(6-tert-butyl-3-methyl) phenol)), one or more of antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite).

Preferably, the dibasic ester having both a Cardo segment structure and a phenyl ether bond segment structure is 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, and the aliphatic The straight-chain diol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol;

Preferably, the dosage of the catalyst is 0.1‰～0.5‰ of the mole number of the dibasic ester having both the Cardo segment structure and the phenyl ether bond segment structure: the stabilizer dosage is both the Cardo segment structure and the phenyl ether bond segment structure. The amount of the antioxidant is 0.1‰～0.5‰ of the mole number of the dibasic ester; the amount of the antioxidant is 0.1‰～0.5‰ of the mole number of the dibasic ester having both the Cardo fragment structure and the phenyl ether bond fragment structure.

Preferably, in the slow evacuation, the degree of vacuum in the reactor is reduced to below 100 Pa within 30 to 60 minutes.

Beneficial effects:

The present invention prepares a series of novel polyester materials by using dibasic ester having both Cardo segment structure and phenyl ether bond segment structure as raw materials. The heat resistance of the prepared new polyester material has been significantly improved, and its glass transition temperature is in the range of 142 to 180 ° C, which is significantly higher than that of the currently marketed polyester material with the highest heat resistance PEN (glass transition temperature of 120 ° C). ). At the same time, the prepared new polyester material has both good organic solvent solubility, and has potential application value in the field of coatings. The excellent heat resistance and good solubility of the new polyester material are expected to expand its promotion in the field of high temperature coatings.

Description of drawings:

FIG. 1 is a ¹ H-NMR spectrum of Example 4. FIG.

FIG. 2 is a DSC graph of Example 4. FIG.

Detailed ways:

The present invention will be further described below in conjunction with the examples, but the conditions of use of the present invention are not only applicable to the following examples.

Example 1

Raw material (10g 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, 1.6g ethylene glycol) and catalyst (11mg dimethyl tin oxide, 12mg anhydrous zinc acetate, 22mg tetrabutyl titanate), additives (21mg triphenyl phosphate, 75mg antioxidant 1010) were put into the reactor, an overhead mechanical stirring device was used, and an air inlet and an air outlet were also equipped. The air in the container was replaced with nitrogen 3 to 5 times at room temperature. Under the condition of 50 to 100°C, beating was performed while maintaining a nitrogen atmosphere. When the catalyst, additives and raw materials are evenly mixed, the reaction system is heated up to 150-220°C and enters the transesterification stage. When the slurry in the reactor becomes clear and transparent, it is maintained for 30-60min to ensure that the esterification rate reaches more than 95%. When the transesterification rate reaches the requirement, the vacuum is slowly evacuated, and the pressure in the reactor is gradually reduced. After 30-60 minutes, the vacuum degree in the reactor reaches below 100Pa, and the temperature is raised to 230-260℃, and the vacuum degree of the reactor is maintained below 100Pa, and the reaction is carried out. After 2 to 4 hours, the polymer in the reactor appears to be entangled, and the polycondensation reaction ends. The material is discharged, powdered and dried to obtain a new type of high temperature resistant soluble polyester.

Example 2

Raw materials (5g 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, 2.3g 1,4-butanediol) and catalyst (11mg dimethyltin oxide, 12mg anhydrous acetic acid) Zinc, 22 mg of tetrabutyl titanate), additives (21 mg of triphenyl phosphate, 75 mg of antioxidant 1010) were put into the reactor, an overhead mechanical stirring device was used, and an air inlet and an air outlet were also provided. The air in the container was replaced with nitrogen 3 to 5 times at room temperature. Under the condition of 50 to 100°C, beating was performed while maintaining a nitrogen atmosphere. When the catalyst, additives and raw materials are evenly mixed, the reaction system is heated up to 150-220°C and enters the transesterification stage. When the slurry in the reactor becomes clear and transparent, it is maintained for 30-60min to ensure that the esterification rate reaches more than 95%. When the transesterification rate reaches the requirement, the vacuum is slowly evacuated, and the pressure in the reactor is gradually reduced. After 30-60 minutes, the vacuum degree in the reactor reaches below 100Pa, and the temperature is raised to 230-260℃, and the vacuum degree of the reactor is maintained below 100Pa, and the reaction is carried out. After 2 to 4 hours, the polymer in the reactor appears to be entangled, and the polycondensation reaction ends. The material is discharged, powdered and dried to obtain a new type of high temperature resistant soluble polyester.

Example 3

The raw materials (10 g of 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, 3.0 g of 1,6-hexanediol) and the catalyst (11 mg of dimethyl tin oxide, 12 mg of anhydrous acetic acid) were combined Zinc, 22 mg of tetrabutyl titanate), additives (21 mg of triphenyl phosphate, 75 mg of antioxidant 1010) were put into the reactor, an overhead mechanical stirring device was used, and an air inlet and an air outlet were also provided. The air in the container was replaced with nitrogen 3 to 5 times at room temperature. Under the condition of 50-100 ℃, keep the nitrogen atmosphere for beating. When the catalyst, additives and raw materials are evenly mixed, the reaction system is heated up to 150-220°C and enters the transesterification stage. When the slurry in the reactor becomes clear and transparent, it is maintained for 30-60min to ensure that the esterification rate reaches more than 95%. When the transesterification rate reaches the requirement, the vacuum is slowly evacuated, and the pressure in the reactor is gradually reduced. After 30-60 minutes, the vacuum degree in the reactor reaches below 100Pa, and the temperature is raised to 230-260℃, and the vacuum degree of the reactor is maintained below 100Pa, and the reaction is carried out. After 2 to 4 hours, the polymer in the reactor appears to be entangled, and the polycondensation reaction ends. The material is discharged, powdered and dried to obtain a new type of high temperature resistant soluble polyester.

Example 4

The starting materials (10 g of 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, 2.1 g of 1,4-butanediol, 0.37 g of isosorbide) and the catalyst (11 mg of dimethyl oxide Tin, 12 mg of anhydrous zinc acetate, 22 mg of tetrabutyl titanate), additives (21 mg of triphenyl phosphate, 75 mg of antioxidant 1010) were put into the reactor, and an overhead mechanical stirring device was used, equipped with an air inlet and an air outlet. . The air in the container was replaced by nitrogen for 3-5 times at room temperature. Under the condition of 50 to 100°C, beating was performed while maintaining a nitrogen atmosphere. When the catalyst, additives and raw materials are evenly mixed, the reaction system is heated to 150-220°C, and enters the transesterification stage. When the slurry in the reactor becomes clear and transparent, it is maintained for 30-60 minutes to ensure that the esterification rate reaches more than 95%. When the transesterification rate reaches the requirement, slowly vacuumize, and the pressure in the reactor gradually decreases. After 30-60 minutes, the vacuum degree in the reactor reaches below 100Pa, and the temperature is raised to 230-260℃, and the vacuum degree of the reactor is maintained below 100Pa, and the reaction After 2 to 4 hours, the polymer in the reactor appears to be entangled, and the polycondensation reaction ends. The material is discharged, powdered, and dried to obtain a new type of high-temperature-resistant soluble polyester. The ¹ H-NMR spectrum of the product is shown in FIG. 1 , and the DSC curve is shown in FIG. 2 .

Example 5

The starting materials (10 g of 9,9-bis[4-(4-methoxycarbonylphenoxy)phenyl]fluorene, 2.7 g of 1,6-hexanediol, 0.37 g of isosorbide) and the catalyst (11 mg of dimethyl oxide Tin, 12 mg of anhydrous zinc acetate, 22 mg of tetrabutyl titanate), additives (21 mg of triphenyl phosphate, 75 mg of antioxidant 1010) were put into the reactor, and an overhead mechanical stirring device was used, equipped with an air inlet and an air outlet. . The air in the container was replaced with nitrogen 3 to 5 times at room temperature. Under the condition of 50 to 100°C, beating was performed while maintaining a nitrogen atmosphere. When the catalyst, additives and raw materials are evenly mixed, the reaction system is heated up to 150-220°C and enters the transesterification stage. When the slurry in the reactor becomes clear and transparent, it is maintained for 30-60min to ensure that the esterification rate reaches more than 95%. When the transesterification rate reaches the requirement, the vacuum is slowly evacuated, and the pressure in the reactor is gradually reduced. After 30-60 minutes, the vacuum degree in the reactor reaches below 100Pa, and the temperature is raised to 230-260℃, and the vacuum degree of the reactor is maintained below 100Pa, and the reaction is carried out. After 2 to 4 hours, the polymer in the reactor appears to be entangled, and the polycondensation reaction ends. The material is discharged, powdered and dried to obtain a new type of high temperature resistant soluble polyester.

Example 6

The thermal properties of the products prepared in Examples 1 to 5 were tested, and the temperature was 50°C as the initial temperature, and the temperature was increased to 700°C at a heating rate of 10°C/min. The obtained thermal performance parameters are shown in Table 1.

Table 1 Thermal performance parameters of the products prepared in Examples 1-5

It can be seen from Table 1 that a new type of high temperature resistant polyester can be prepared by the method of the present invention. In Examples 1 to 5, the glass transition temperatures are all as high as 140°C or more, and have excellent heat resistance.

The products prepared in Examples 1-5 were tested for solubility, and the test results are shown in Table 2.

The solubility of the products prepared in Table 2 Examples 1 to 5 in organic solvents

1,1,2,2-Tetrachloroethane Trichloromethane Example 1 room temperature soluble room temperature soluble Example 2 room temperature soluble room temperature soluble Example 3 room temperature soluble room temperature soluble Example 4 room temperature soluble room temperature soluble Example 5 room temperature soluble room temperature soluble

It can be seen from Table 2 that a new type of high-temperature resistant polyester prepared by the method of the present invention can be dissolved in 1,1,2,2-tetrachloroethane and chloroform 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 from 0 to 300, y is an integer from 0 to 100, and n is an integer from 0 to 4;

represents a novel dibasic ester fragment with a structure of

2. A method for preparing a high temperature resistant soluble polyester according to claim 1, comprising the steps of: throwing raw materials, catalysts and additives into a reactor, replacing with nitrogen, and maintaining a nitrogen atmosphere at 50 to 100° C. to carry out Beating, when the raw materials, catalysts and additives are uniform, the temperature is raised to 150-220 ° C, and the transesterification reaction is carried out. When the transesterification rate reaches more than 95%, the vacuum is slowly drawn to reduce the pressure in the reactor to below 100Pa, and then the temperature rises. At 230-260°C, the vacuum degree in the reactor is maintained below 100Pa, and the polycondensation reaction is carried out for 2-4 hours. After the polycondensation reaction is completed, the material is discharged, broken into particles, and dried to obtain the high temperature-resistant soluble polyester; The raw material is a dibasic ester, aliphatic straight-chain diol, isosorbide having both Cardo fragment structure and phenyl ether bond fragment structure; according to the molar ratio, the described material has both Cardo fragment structure and phenyl ether bond fragment Dibasic ester of structure: (aliphatic straight-chain diol+isosorbide)=1:1.2～1.6; The catalyst is selected from dimethyl tin oxide, tin acetate, titanium tetraethoxide, tetrabutyl titanate, tetraisopropyl titanate, ethylene glycol titanium, 1,3-propanediol titanium, antimony trioxide , one or more of ethylene glycol antimony, butanediol antimony, 1,3-propanediol antimony, hexanediol antimony; Described additive comprises stabilizer and antioxidant, wherein stabilizer is selected from one or more of phosphoric acid, alkyl phosphate, triphenyl phosphate, alkyl diaryl phosphate; antioxidant is selected from antioxidant 1010, One or more of antioxidant 300 and antioxidant 168. 3. The preparation method of a high-temperature-resistant soluble polyester according to claim 2, wherein the dibasic ester having both a Cardo segment structure and a phenyl ether bond segment structure is 9,9-bis[4 -(4-methoxycarbonylphenoxy)phenyl]fluorene, the aliphatic straight-chain diol is selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- One or more of pentanediol and 1,6-hexanediol. 4. the preparation method of a kind of high temperature resistant soluble polyester according to claim 2, is characterized in that, described catalyst dosage is 0.1‰ of the mole number of the dibasic ester having both Cardo segment structure and phenyl ether bond segment structure ~0.5‰: the dosage of the stabilizer is 0.1‰～0.5‰ of the mole number of the dibasic ester having both the Cardo fragment structure and the phenyl ether bond fragment structure; the antioxidant dosage is the Cardo fragment structure and the phenyl ether bond. 0.1‰～0.5‰ of the mole number of dibasic ester of fragment structure. 5 . The method for preparing a high temperature resistant soluble polyester according to claim 2 , wherein the slow vacuuming is to reduce the vacuum degree in the reactor to below 100 Pa in 30 to 60 minutes. 6 .

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