阅读说明：本技术 一种热塑性聚醚砜酰亚胺共聚物及其制备方法 (Thermoplastic polyether sulfone imide copolymer and preparation method thereof ) 是由 方省众 蒋鸿宇 张峰 陈国飞 于 2020-05-22 设计创作，主要内容包括：本发明公开了一种热塑性聚醚砜酰亚胺共聚物及其制备方法,所述热塑性聚醚砜酰亚胺共聚物的结构通式如式(I)所示。所述热塑性聚醚砜酰亚胺共聚物的制备方法为：以式(II)所示二氯二苯砜、式(III)所示的混合的双氯代酰亚胺单体以及式(IV)所示双羟基单体作为原料,在碱性催化剂存在条件下发生共聚反应制得式(I)所示聚醚砜酰亚胺共聚物；所述式(III)所示的混合的双氯代酰亚胺单体为3,4位构型、3,3位构型、4,4位构型中至少两种的混合物。所述聚醚砜酰亚胺共聚物材料采用混合的双氯代酰亚胺单体作为原料,使热塑性聚醚砜酰亚胺共聚物具有优异的加工性能。<Image he="278" wi="700" file="DDA0002504432920000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a thermoplastic polyether sulfone imide copolymer and a preparation method thereof, wherein the structural general formula of the thermoplastic polyether sulfone imide copolymer is shown as a formula (I). The preparation method of the thermoplastic polyether sulfone imide copolymer comprises the following steps: taking dichlorodiphenyl sulfone shown in a formula (II), mixed bischloroimide monomer shown in a formula (III) and dihydroxy monomer shown in a formula (IV) as raw materials, and carrying out copolymerization reaction in the presence of an alkaline catalyst to obtain a polyether sulfone imide copolymer shown in a formula (I); the mixed bischloroimide monomer shown in the formula (III) is a mixture of at least two of 3, 4-position configuration, 3-position configuration and 4, 4-position configuration. The polyether sulfone imide copolymer material adopts mixed bischloroimide monomers as raw materials, so that the thermoplastic polyether sulfone imide copolymer has excellent processing performance.)

1. The polyether sulfone imide copolymer is characterized in that the structural general formula is shown as the formula (I):

wherein m and n are the number of the structural units respectively, m is an integer greater than or equal to 1, and n is an integer greater than or equal to 1;

Ar₁is an aromatic group or a substituted aromatic group; ar (Ar)₂Is an aromatic group or a substituted aromatic group, the aromatic group is selected from C₆～C₃₀An aromatic group of (a); the substituent of the substituted aromatic group is C_1～3An alkyl group;

the above-mentionedIs composed of At least two of them.

2. The polyethersulfoneimide copolymer of claim 1, wherein the ratio of m to n is 1:0.1 to 20.

3. The polyethersulfoneimide copolymer of claim 1, wherein Ar is selected from the group consisting of₁Is one or at least two of the following groups connected by C-C bond:

4. the polyethersulfoneimide copolymer of claim 1, wherein Ar is selected from the group consisting of₂Is one or at least two of the following groups connected by C-C bond:

5. the polyethersulfoneimide copolymer of claim 1, wherein the polyethersulfoneimide copolymer has an inherent viscosity of 0.2 to 1.5dL/g and a glass transition temperature of 190 to 250 ℃.

6. The method for preparing the polyethersulfoneimide copolymer according to any one of claims 1-5, characterized by comprising the following steps: taking dichlorodiphenyl sulfone shown in a formula (II), mixed bischloroimide monomer shown in a formula (III) and dihydroxy monomer shown in a formula (IV) as raw materials, and carrying out copolymerization reaction in the presence of an alkaline catalyst to obtain a polyether sulfone imide copolymer shown in a formula (I);

wherein Ar is₁、Ar₂M, n are as defined in any one of claims 1 to 5;

the molar ratio of the mixed bischloroimide monomer shown in the formula (III), the dichlorodiphenyl sulfone shown in the formula (II) and the dihydroxy monomer shown in the formula (IV) is 1: 0.1-20: 1.1-21.

7. The method for preparing the polyethersulfoneimide copolymer as claimed in claim 6, wherein said mixed bischloroimide monomer represented by formula (III) isA mixture of at least two of (1).

8. The method for preparing the polyethersulfoneimide copolymer according to claim 6, wherein the reaction solvent of the copolymerization reaction is N, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and the like, and a water-carrying agent is added into the reaction system, and the water-carrying agent is toluene, chlorobenzene, xylene or dichlorobenzene.

9. The method for preparing the polyethersulfoneimide copolymer according to claim 6, wherein said basic catalyst is carbonate, bicarbonate, hydroxide, organic base, alkali metal salt of alcohol, metal hydride, pyridine, isoquinoline or triethylamine; the adding amount of the alkaline catalyst is 100 to 150 percent of the molar amount of the dihydroxy monomer shown in the formula (IV).

10. The method for preparing the polyether sulfone imide copolymer according to claim 6, wherein the copolymerization reaction is carried out in an inert gas protective atmosphere; the temperature of the copolymerization reaction is 130-250 ℃.

Technical Field

The invention relates to the field of polymers, and particularly relates to a thermoplastic polyether sulfone imide copolymer and a preparation method thereof.

Background

Polyimide is a resin material with excellent comprehensive performance, has the advantages of good thermal stability, excellent mechanical performance, good dimensional stability, excellent chemical stability, high breakdown voltage, low dielectric constant, high flame retardance, low expansion coefficient and the like, and is widely applied to the high-tech fields of electronic and electrical products, aerospace, automobiles, chemical machinery and the like. However, most polyimide resins have molecular chains with high rigidity, which makes them difficult to melt or dissolve, and as in the last 60 th century, the basic structure of Vespel polyimide engineering plastics developed by DuPont is PMDA/ODA, the glass transition temperature (Tg) of the polyimide is 385 ℃, and the polyimide must be sintered by a special isostatic pressing method to obtain a shaped product, which requires a lot of labor and expensive equipment.

Polysulfones containing hydrocarbon radicals-SO-in the main chain of the molecule₂The thermoplastic resin of the hydrocarbyl chain link has the advantages of excellent mechanical property, high rigidity, wear resistance, high strength, high thermal stability, hydrolysis resistance, good dimensional stability, small molding shrinkage, no toxicity, radiation resistance, flame resistance, extinguishment and the like. The method is widely applied to the fields of electronics, electrics, food, daily necessities, automobiles, aviation, medical treatment, general industry and the like.

Polysulfone structural units have more flexible units and are linear structures, so that polysulfone resin has the advantages of good melt processability, solubility and the like, and introduction of polysulfone structural units into polyimide structural units with stronger rigidity is beneficial to improving the processability of polyimide and can reduce the cost, and U.S. general company patent WO2005023928A1, Sauter Saber basic Innovative plastics Limited patent US20080119610A1, CN1493603 and the like disclose polyimide and polysulfone blending modified copolymers and preparation methods thereof. However, the copolymer obtained by the above method still has a problem of difficult processing.

Disclosure of Invention

The invention provides an easily-processed thermoplastic polyether sulfone imide copolymer, which adopts mixed bischloroimide monomers as raw materials, and introduces a linear polysulfone structural unit into a rigid main chain of polyimide, so that the obtained thermoplastic polyether sulfone imide copolymer has excellent processing performance.

The technical scheme provided by the invention for solving the technical problems is as follows:

a polyethersulfone imide copolymer having a general structural formula as shown in formula (I):

wherein m and n are the number of each structural unit, m is an integer greater than or equal to 1, and n is an integer greater than or equal to 1;

Ar₁is a substituted or unsubstituted aromatic group; ar (Ar)₂Is a substituted or unsubstituted aromatic group selected from C₆～C₃₀An aromatic group of (a);

the above-mentionedIs composed of At least two of them.

The polyether sulfone imide copolymer has the characteristics that a linear polysulfone structural unit is introduced into a rigid main chain of polyimide, and an imide co-block is a mixture of at least two of 3, 4-position configuration, 3-position configuration and 4, 4-position configuration, so that the solubility of the polyether sulfone imide copolymer is improved, the cost of the polyimide is reduced, the hydrolysis resistance stability of the polyimide can be improved, and the like; the processing property is good, the method is suitable for injection molding, extrusion, die pressing, melt spinning and solution spinning processing, and the method has good application prospect in the related fields of high-temperature resistant engineering plastics, films, fibers, adhesives, coatings, advanced composite materials and the like.

The ratio of m to n is 1:0.1 to 20.

Ar is₁Is one or at least two of the following groups connected by C-C bond:

ar is₂Is in the following groupOr at least two groups formed by C-C bond connection:

the inherent viscosity of the polyether sulfone imide copolymer is between 0.2dL/g and 1.5 dL/g; preferably 0.3dL/g to 1.2dL/g, more preferably 0.4dL/g to 0.8 dL/g.

The inherent viscosity is too high, the thermoplastic processability is poor, and the inherent viscosity is too low, the mechanical properties are reduced.

The glass transition temperature of the polyether sulfone imide copolymer is 190-250 ℃.

The invention also provides a preparation method of the polyether sulfone imide copolymer, which comprises the following steps:

taking dichlorodiphenyl sulfone shown in a formula (II), mixed bischloroimide monomer shown in a formula (III) and dihydroxy monomer shown in a formula (IV) as raw materials, and carrying out copolymerization reaction in the presence of an alkaline catalyst to obtain a polyether sulfone imide copolymer shown in a formula (I);

wherein Ar is₁、Ar₂M and n are defined as the invention.

The mixed bischloroimide monomer shown as the formula (III) isA mixture of at least two of (1).

The molar ratio of the mixed bischloroimide monomer shown in the formula (III), the dichlorodiphenyl sulfone shown in the formula (II) and the dihydroxy monomer shown in the formula (IV) is 1: 0.1-20: 1.1-21.

The reaction solvent of the copolymerization reaction is N, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and the like, and a water-carrying agent is added into the reaction system, wherein the water-carrying agent can be toluene, chlorobenzene, xylene or dichlorobenzene.

The basic catalyst includes but is not limited to carbonate, bicarbonate, hydroxide, organic base, alkali metal salt of alcohol, metal hydride, pyridine, isoquinoline, triethylamine and other compounds.

Preferably, the addition amount of the basic catalyst is 100 to 150 percent of the molar amount of the dihydroxy monomer shown in the formula (IV).

The copolymerization is carried out under an inert gas atmosphere, such as nitrogen or argon.

Preferably, the temperature of the copolymerization reaction is 130 ℃ to 250 ℃.

And after the copolymerization reaction is finished, cooling the reaction product, pouring the reaction product into a precipitator, filtering, collecting the precipitate, fully washing and drying to obtain the polyether sulfone imide copolymer.

The precipitant may be selected from, but not limited to, ethanol, acetone, deionized water, etc., or a mixed solution thereof.

Compared with the prior art, the invention has the advantages that:

(1) the mixed bischloroimide monomer is adopted as a raw material, so that the obtained thermoplastic polyether sulfone imide copolymer has excellent processing performance.

(2) By introducing the sulfone structural unit, the processability of the polyimide is improved, and the cost can be reduced.

(3) Compared with the original introduction mode which needs the difluoride imide monomer, the method adopts the difluoride imide monomer to carry out the reaction, and has lower cost.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which should be noted that the present invention is only illustrative and should not be construed as limiting the scope of the present invention. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.