WO2019153135A1

WO2019153135A1 - Poly(aryl ether sulfone)-ether imide copolymer and preparation method therefor

Info

Publication number: WO2019153135A1
Application number: PCT/CN2018/075552
Authority: WO
Inventors: 王贤文; 饶先花; 方倩; 罗志辉; 龚维; 黄文刚; 黄珊; 黄华鹏; 张志祥; 张健
Original assignee: 江门市优巨新材料有限公司
Priority date: 2018-02-07
Filing date: 2018-02-07
Publication date: 2019-08-15
Also published as: CN111788252B; CN111788252A

Abstract

Disclosed are a poly(aryl ether sulfone)-ether imide copolymer and a preparation method therefor. The poly(aryl ether sulfone)-ether imide copolymer is a random copolymer or a block copolymer, with an average molecular weight of 20000 - 100000. The poly(aryl ether sulfone)-ether imide copolymer combines the advantages of poly(aryl ether sulfone) and polyimide, and improves heat resistance and processibility. The preparation method for the copolymer has a simple process and the post-treatment therein is simple, and same is suitable for industrial production.

Description

Polyaryl ether sulfone-etherimide copolymer and preparation method thereof

Technical field

The invention belongs to the technical field of polymer materials, and in particular relates to a polyaryl ether sulfone-ether imide copolymer and a preparation method thereof.

Background technique

Polyaryl ether sulfone is a kind of special engineering plastic with excellent comprehensive physical properties. Industrially important polyaryl ether sulfones include polyethersulfone (PES) and polyphenylene sulfone (PPSU), bisphenol A polyaryl ether sulfone ( PSU). Because of their heat resistance (heat distortion temperature 200 ~ 220 ° C), hot water resistance (resistant to 150 ~ 160 ° C hot water or steam), creep resistance, dimensional stability, impact resistance, chemical resistance Excellent comprehensive performance such as non-toxicity and flame retardant has been widely used in electronics, electrical, mechanical, automotive, medical equipment, food processing and other fields for a long time. Polyarylether sulfones can be produced by a variety of methods, such as the preparation of polyaryl ethers and especially polyaryl ether sulfones, as described in U.S. Patents 4,108,837 and 4,175,175. Several one-step and two-step processes are described in these patents. The dibasic metal salt of a dihydric phenol is reacted with a dihalobenzene compound in the presence of a sulfone or sulfoxide solvent under substantially anhydrous conditions. In two steps, the dihydric phenol is first subjected to a polycondensation reaction with an alkali metal or an alkali metal compound in the presence of a sulfone or a sulfoxide. In the long-term application and promotion process, different application fields have continuously proposed the use of higher heat resistance levels. In some fields, such as aerospace, the use of pure polysulfone often fails to meet the temperature requirements.

Polyimide is the best class of special engineering plastics with high temperature resistance. It has: high temperature resistance, low temperature resistance, corrosion resistance, self-lubrication, low wear, excellent mechanical properties, good dimensional stability, high insulation, etc. In many cases, it replaces metals, ceramics, polytetrafluoroethylene and engineering plastics, and is widely used in petrochemical, mining machinery, precision machinery, automotive industry, microelectronic equipment, medical equipment and other fields. In particular, polyimides have long-term creep resistance at high temperatures and stresses that make them replace metals and other materials in many structural devices. Conventional polyimides generally employ a four-step process to form a polyamic acid using tetracarboxylic anhydride and a diamine, followed by dehydration to form an imide. Due to the limitation of the monomer raw materials, most of the polyimides tend to have a high glass transition temperature, or even melt and insoluble, and can only form a film product, which results in poor workability of the polyimide and high raw material cost, which is disadvantageous to Industrial production. High cost and difficult processing are still major problems in the production of polyimide. To date, only one type of polyetherimide (PEI) developed by Sabic has been widely used.

CN1243038C discloses a method for synthesizing polysulfone-polyimide copolymer, which uses transition metal nickel as a catalyst, triphenylphosphine as a complexing agent, and zinc powder as a reducing agent to be directly synthesized by a coupling reaction. This method can cause the metal catalyst nickel and the complexing agent triphenylphosphine to be removed in the reaction after the end of the reaction, which has an effect on the quality of the product such as color, and the high cost of such a catalyst is unfavorable for industrial production.

The present invention is intended to combine the advantages of both polyaryl ether sulfone and polyimide. On the one hand, the introduction of a phthalimide group into the polyaryl ether sulfone can improve the heat resistance of the poly(aryl ether sulfone), on the other hand, in the polymerization. The introduction of a polyaryl ether sulfone group in the imide can lower the melting temperature of the polyimide, improve its processability, and combine the advantages of both. At the same time, a process with simple process, easy post-processing and easy industrial production is developed.

Summary of the invention

The object of the present invention is to provide a polyaryl ether sulfone-etherimide copolymer and a preparation method thereof, and a polyarylene ether of the present invention, in view of the technical defects existing in the preparation of the existing polyaryl ether sulfone-etherimide copolymer. The sulfone-etherimide copolymer combines the advantages of polyarylether sulfone and polyimide to improve heat resistance and processability, and the preparation method of the present invention is simple in process, easy in post-treatment, and suitable for industrial production.

In order to achieve the object of the present invention, an aspect of the present invention provides a polyaryl ether sulfone-etherimide copolymer represented by the structural formulae (I) and (II) a block or random copolymer composed of structural units having an average molecular weight of 20,000 to 100,000.

Wherein Ar ₁ in the structural formula (I) is:

Or a structural formula of the structural formula; or a structure having a substituent of the above structural formula; or a polycyclic and heterocyclic structural compound and an isomer thereof; and R' in the structural formula (I) is:

And isomers thereof; Ar _{2 in the} formula (II) is:

Or a mixture similar to the foregoing structures, or an aromatic structure containing a substituent, or one or more of a polycyclic and heterocyclic structural compound and an isomer thereof, may also be a mixture of these.

The molar ratio of the structural unit represented by the structural formula (I) and the structural formula (II) is from 0 to 100:0 to 100, preferably from 30 to 70:30 to 70.

In particular, the polyaryl ether sulfone-etherimide copolymer has a glass transition temperature Tg of 200 to 320 ° C; an intrinsic viscosity of 0.2 to 1.0 dL/g; and a melt index of MI = 5 to 120 g/10 min (365.0). °C, 5KG).

In particular, the polyarylethersulfone-etherimide copolymer also contains functionally improved structural units.

In particular, the functionally improving structural unit is one of a chain extender structural unit for improving the strength of the copolymer, a transparency improver structural unit for improving the transparency of the copolymer, and a mobile phase improver structural unit for improving the fluidity of the copolymer. Kind or more.

In particular, the transparency improver structural unit selectively introduces a cycloalkanyl-substituted phenol; the mobile phase improver structural unit is an aromatic polyhydric phenol; the chain extender structural unit is an alkane containing carbon, silicon or titanium Base unit.

In particular, the polyaryl ether sulfone-etherimide copolymer further contains a terminal block structural unit which enhances the thermal stability of the copolymer.

In particular, the capping agent structural unit is selected to introduce a structural formula as

A structural unit containing a substituted aromatic group, wherein R represents -H, -benzene, or a benzene-containing, naphthalene ring, and fused ring aromatic derivative group includes, but is not limited to, the following structure:

Or an isomer or structurally similar compound wherein X' in the R substituent represents H, F, Cl, Br, I.

Another aspect of the invention provides a method for preparing a polyaryl ether sulfone-etherimide copolymer, comprising the steps of:

1) dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt, performing a salt formation reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt, thereby obtaining a bisphenol monomer salt solution;

2) adding a chlorine monomer to the prepared bisphenol monomer salt solution, and performing a prepolymerization reaction to obtain a sulfone prepolymer solution;

3) adding a phthalimide monomer to the prepared sulfone prepolymer solution to carry out a copolymerization reaction to obtain a copolymer solution;

4) The prepared copolymer solution is subjected to a purification treatment.

In particular, step 1) also includes adding a water-carrying agent after the addition of the alkali metal salt.

Wherein, the water-carrying agent is selected from one or more selected from the group consisting of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, p-diethylbenzene, diethylbenzene, and benzene.

In particular, the ratio of the volume of the water-carrying agent to the mass of the organic solvent mixture is 5 to 15:100 (mL/g), that is, 5 to 15 mL of the water-carrying agent is added per 100 g of the organic solvent mixture.

Wherein, the salt forming reaction of the bisphenol monomer is carried out under the protection of an inert gas.

In particular, the inert gas is selected from one or more of nitrogen, argon or carbon dioxide.

In particular, the bisphenol monomer salt formation reaction temperature is 150-210 ° C; the salt formation reaction time is 1-12 h, preferably 1-2 h.

In particular, the pressure of the bisphenol monomer during the salt formation reaction is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

According to still another aspect of the present invention, a method for preparing a polyaryl ether sulfone-etherimide copolymer includes the following steps:

1) Salt formation reaction

Dissolving the bisphenol monomer in the organic solvent mixture, adding the alkali metal salt and the water-carrying agent, heating under reflux under the protection of an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt. Bisphenol monomer salt solution;

2) Sulfone prepolymerization

Adding a chlorine monomer to the bisphenol monomer salt solution prepared in the step 1) to carry out a prepolymerization reaction to obtain a sulfone prepolymer solution;

3) Copolymerization

Adding a phthalimide monomer to the sulfone prepolymer solution prepared in the step 2) to carry out a copolymerization reaction to obtain a copolymer solution;

4) Purification treatment

The copolymer solution is cooled and then subjected to pulverization treatment; then, an extraction solvent is added to the powder, and the mixture is heated and boiled and then filtered, and repeated several times until the content of the alkali metal salt in the extraction solvent is less than 5 ppm; the powder is dried.

Wherein, the temperature of the salt formation reaction in the step 1) is 150-210 ° C; the salt formation reaction time is 1-12 h, preferably 1-2 h.

In particular, the organic solvent mixture is a mixed system of an aprotic polar solvent and a catalyst, wherein the mass ratio of the aprotic polar solvent to the catalyst is (90-100): (0-10), preferably (90) -99): (1-10).

In particular, the aprotic polar solvent is selected from the group consisting of sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, diphenyl sulfone, N,N-dimethylformamide, N,N-dimethylacetamide, and adjacent Dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, anisole, o-dimethoxybenzene, acetic acid or dimethyl sulfoxide; the catalyst selected polyether, chain polyethylene glycol A cyclic crown ether or a quaternary ammonium salt, preferably a chain polyethylene glycol (PEG).

In particular, the chain polyethylene glycol is PEG200, PEG400, PEG600, preferably PEG400; the cyclic crown ether is selected from 18 crown 6, 15 crown 5, cyclodextrin, etc.; the quaternary ammonium salt is selected as benzyl group Triethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, and the like.

The alkali metal salt in the step 1) is sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate.

In particular, when the alkali metal salt is selected from sodium carbonate or potassium carbonate, the molar ratio of the bisphenol monomer to the alkali metal salt is 100: 100-130, preferably 100: 105-130; when the alkali metal salt is selected from carbonic acid Sodium hydrogen or potassium hydrogencarbonate, the molar ratio of the bisphenol monomer to the alkali metal salt is from 100:200 to 260, preferably from 100:210 to 240.

Wherein, the water-carrying agent in the step 1) is selected from one or more of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, p-diethylbenzene and benzene.

In particular, after the organic solvent mixture is heated to 60 to 90 ° C, preferably 80 ° C, the bisphenol monomer is added and stirred to dissolve.

Wherein the bisphenol monomer in the step 1) is a compound of the formula (III) and a derivative or structural analog thereof, and the structural formula (III) is: HO-Ar ₁ -OH (III), wherein the Ar1 is selected

Wherein the derivative is a substituent-containing compound of the structural compound of the formula (III); the structural analog is an isomer of the compound of the formula (III), or a polycyclic and heterocyclic structural compound One or several.

In particular, the bisphenol monomer is preferably biphenyldiol, 4,4'-dihydroxydiphenyl sulfone or bisphenol A.

The ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture is (10-45):100.

In particular, the alkali metal salt and the water-carrying agent are added while maintaining the temperature at 90 to 120 ° C, preferably 100 ° C.

In particular, the inert gas in step 1) is nitrogen, argon or carbon dioxide.

Wherein the chlorine monomer in the step 2) is a compound of the formula (IV) and a derivative or structural analog thereof, and the structural formula (IV) is:

Where the R' selection

And a isomer thereof; wherein the derivative is a substituent-containing compound of the structural compound of the formula (IV); the structural analog is an isomer of the compound of the formula (IV), or a polycyclic ring One or more of the heterocyclic structural compounds.

In particular, the chlorine monomer is preferably 4,4'-dichlorodiphenyl sulfone.

In particular, the molar ratio of the chlorine monomer in step 2) to the bisphenol monomer in step 1) is from 20 to 80:100, preferably from 20 to 74:100, further preferably from 35 to 45:100. .

Wherein, the temperature of the sulfone prepolymerization in the step 2) is from 180 to 280 ° C, preferably from 180 to 250 ° C; and the prepolymerization time is from 2 to 12 h, preferably from 5 to 8 h.

In particular, the pressure during the prepolymerization of the sulfone is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

In particular, the temperature at which the bisphenol monomer salt system is controlled during the addition of the chlorine monomer to the bisphenol monomer salt system is from 120 to 200 ° C, preferably from 150 to 200 ° C.

In particular, the chlorine monomer to be added is dissolved, and then the water-carrying agent is added, and the temperature is maintained at 180-200 ° C, and the mixture is heated and refluxed. The water-carrying agent carries water to remove the water in the reaction system, which is favorable for the water in the reaction system. Prepolymerization. Bring water until there is no water droplets in the water tank, and then carry out prepolymerization.

In particular, the water-carrying agent is one or more selected from the group consisting of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, p-diethylbenzene, and benzene.

In particular, the ratio of the volume of the water-carrying agent to the mass of the organic solvent mixture is (5-15): 100 (mL/g), that is, the water-carrying agent added without 100 g of the organic solvent mixture is 5- 15mL.

Wherein the diimide monomer in the step 3) is a compound represented by the structural formula (V) and a derivative or structural analog thereof, and the structural formula (V) is

Wherein the substitution position of z is 3- or / and 4-substituted, wherein Z is selected from chlorine, fluorine, bromine or nitro;

Or one or more of a derivative structure or a polycyclic and heterocyclic structure similar to or containing a substituent.

In particular, the diimideimide monomer is preferably bischlorodiphenylphthalimide, and its structural formula is

In particular, the molar ratio of the diimide monomer in step 3) to the bisphenol monomer in step 1) is (20-80):100, preferably (28-80):100, Further preferably (30-70): 100, more preferably (40-60): 100.

Wherein the temperature of the copolymerization reaction in step 3) is from 180 to 280 ° C, preferably from 180 to 220 ° C; and the reaction time is from 1 to 12 h, preferably from 2 to 8 h.

In particular, the pressure during the copolymerization reaction in step 3) is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

Specifically, after the temperature of the sulfone prepolymer solution prepared in the step 2) is lowered to 140 to 170 ° C, the diimide monomer is further added.

Wherein, the extraction solvent in the step 4) is selected from deionized water, acetone or ethanol.

In particular, it also includes the step 3A) adding a blocking agent to the copolymer solution, and performing end group blocking treatment to obtain a blocked copolymer.

Wherein the terminal blocking agent, that is, the terminal blocking agent, the compound of the formula (IX) or a derivative or structural analog thereof is selected, and the structural formula (IX) is:

Wherein the substituent X in the formula (IX) is -OH, F, Cl, Br or I, wherein -OH, F or Cl is preferred; wherein R represents -H, -benzene, or benzene, naphthalene ring or thick The cycloaromatic derivative groups include, but are not limited to, the following structures:

In particular, the blocking agent is preferably chlorobenzene.

In particular, the end group blocking treatment temperature is 180-280 ° C, preferably 200-220 ° C, further 215 ° C; the end group blocking treatment time is 1-3 h, preferably 2-3 h.

In particular, the pressure in the end closure treatment of step 3A) is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, ie from 0.1 to 3.0 MPa.

In particular, the molar ratio of the blocking agent in the step 3A) to the bisphenol monomer in the step 1) is 0 to 10:100, preferably (2 to 6):100, further preferably (3 to 6). ): 100.

In particular, it also includes a step 3B') in which a functional modifier is added to the copolymer solution to perform a function-improving treatment to obtain a functionally improved copolymer.

Wherein the functional modifier is one or more of a chain extender, a fluidity improver or a transparency improver.

In particular, the molar ratio of the functional modifier to the bisphenol monomer in step 1) is (0-10):100, preferably (1-6):100.

In particular, the temperature of the functional improvement treatment is from 180 to 280 ° C, and the treatment time is from 1 to 3 h, preferably from 2 to 3 h.

Specifically, the pressure in the functional improvement treatment of the step 3B') is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

In particular, the function improvement process is a chain extension process, a fluidity improvement process, or a transparency improvement process.

Specifically, it is further included that a chain extender is added to the copolymer solution of the step 3B), and a chain extension treatment is carried out to obtain an extended chain copolymer.

Wherein, the chain extender, that is, a chain extender, selectively selects a compound represented by the formula (VI) or a derivative or structural analog thereof, and the structural formula (VI) is:

Wherein M is carbon, silicon or titanium; and R ₁ and R _{2 are} each selected from the group consisting of chlorine, hydrogen, alkyl, alkoxy, cycloalkyl, phenyl, phenoxy, chloroalkyl.

In particular, in the chain extender of the formula (VI), R ₁ and R ₂ are a linear alkyl group having 1 to 18 carbon atoms; and the alkoxy group is 1 carbon atom. a linear alkoxy group of -20; the cycloalkyl group has a cycloalkyl group having 5 to 20 carbon atoms; the phenyl group has 6 to 18 carbon atoms; and the phenoxy group has a carbon number of 6 to 18; the chloroalkyl group has 1 to 17 carbon atoms.

In particular, the chain extender is preferably ethoxylated titanium trichloride, pentamethylocylferric trichloride, dimethyldichlorosilane, dichloromethane or the like.

In particular, the chain growth treatment temperature is from 180 to 280 ° C, preferably from 180 to 220 ° C, further preferably from 195 ° C; and the chain growth treatment time is from 1 to 3 h, preferably from 2 to 3 h.

In particular, the pressure in the chain growth treatment in step 3B) is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

In particular, the molar ratio of the chain extender in step 3B) to the bisphenol monomer in step 1) is (0-10):100, preferably (2-10):100, further preferably 2 :100.

Further, the step 3C) is carried out by adding a fluidity improver to the copolymer solution to carry out a fluidity-improving treatment to obtain a fluidity-improving copolymer.

Wherein, the fluidity improving agent selects an aromatic polyphenol represented by the formula (VII) or a derivative or structural analog thereof, and the structural formula (VII) is:

Wherein R ₁ is an alkyl group of 1 to 28 carbon atoms or an aromatic hydrocarbon group of 6 to 26 carbon atoms; R ₂ and R ₃ are hydrogen, a hydroxyl group, an alkyl group of 1 to 28 carbon atoms, and 5 to 25 carbons. An alicyclic group of an atom, an alkoxy group of 1 to 28 carbon atoms, an aryl group of 6 to 25 carbon atoms or an alicyclic group of 6 to 26 carbon atoms.

In particular, the fluidity improver selects a compound having the following chemical formula:

In particular, the fluidity improving treatment temperature is from 180 to 280 ° C, preferably from 200 to 250 ° C; and the fluidity improving treatment time is from 1 to 3 h, preferably from 2 to 3 h.

In particular, the pressure in the fluidity improving treatment in the step 3C) is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

In particular, the molar ratio of the fluidity improving agent in the step 3C) to the bisphenol monomer in the step 1) is from 0 to 10:100, preferably from 0 to 3:100, further preferably from 0 to 1: 100, still more preferably 1:100.

In particular, the method further includes the step 3D) of adding a transparency improving agent to the copolymer solution to carry out a transparency improving treatment to obtain a transparency improving copolymer.

Wherein the transparency improving agent selects an alkane-substituted phenol represented by the formula (VIII) or a derivative or structural analog thereof, and the structural formula (VIII) is:

Wherein R ₁ is an alkyl group of 1 to 28 carbon atoms, an alicyclic group of 5 to 26 carbon atoms, an alkoxy group of 1 to 28 carbon atoms, an aryl group of 6 to 26 carbon atoms, 6 to 26 Any one of an aryloxy group of a carbon atom or an alicyclic oxy group of 5 to 26 carbon atoms; R ₂ and R ₃ are hydrogen, an alkyl group of 1 to 28 carbon atoms, and 5 to 25 carbon atoms. An alicyclic group, an alkoxy group having 1 to 28 carbon atoms, an aryl group having 6 to 25 carbon atoms, an alicyclic group having 6 to 26 carbon atoms or a substituent having a phenol group.

In particular, the transparency improving agent is preferably a compound of the following formula:

In particular, the transparency improving treatment temperature is 180 to 280 ° C, preferably 200 to 220 ° C, more preferably 212 ° C; and the transparency improving treatment time is 1-3 h, preferably 2-3 h.

In particular, the pressure in the transparency improving treatment in the step 3D) is ≤ 3.0 MPa, preferably from atmospheric pressure to 3.0 MPa, that is, 0.1 to 3.0 MPa.

In particular, the molar ratio of the transparency improving agent in the step 3D) to the bisphenol monomer in the step 1) is (0-10):100, preferably (3-6):100, further preferably 6 :100.

1) Synthetic sulfone segment prepolymer

1A) Dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt and a water-carrying agent, heating under reflux under an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt Obtaining a bisphenol monomer salt solution for sulfone segment prepolymerization reaction;

1B) the sulfone segment prepolymerization step prepared in step 1A) is carried out by adding a chloro monomer to the bisphenol monomer salt solution to carry out sulfone prepolymerization to obtain a sulfone segment prepolymer solution;

2) Synthesis of ether phthalimide segment prepolymer

2A) Dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt and a water-carrying agent, heating under reflux under an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt Obtaining a bisphenol monomer salt solution for the etherimide segment prepolymerization reaction;

2B) adding the diimide monomer to the bisphenol monomer salt solution to the etherimide segment prepolymerization reaction prepared in the step 2A), and performing ether phthalimide prepolymerization to obtain the etherimide Segment prepolymer solution;

3) mixing the sulfone segment prepolymer solution prepared in step 1) and the etherimide segment prepolymer solution prepared in step 2), performing block copolymerization reaction to obtain a block copolymer solution;

4) The prepared block copolymer solution is subjected to a purification treatment.

1) Synthetic sulfone segment prepolymer

1A) salt formation reaction

Dissolving the bisphenol monomer in the organic solvent mixture, adding the alkali metal salt and the water-carrying agent, heating under reflux under the protection of an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt. a bisphenol monomer salt solution for sulfone segment prepolymerization;

1B) Sulfone prepolymerization

The sulfone segment prepolymerization step prepared by the step 1A) is carried out by adding a chloro monomer to the bisphenol monomer salt solution to carry out sulfone prepolymerization to obtain a sulfone segment prepolymer solution;

2) Synthesis of ether phthalimide segment prepolymer

2A) salt formation reaction

Dissolving the bisphenol monomer in the organic solvent mixture, adding the alkali metal salt and the water-carrying agent, heating under reflux under the protection of an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt. a bisphenol monomer salt solution for the etherimide segment prepolymerization reaction;

2B) phthalimide prepolymerization

To the etherimide segment prepared in step 2A), a diimide monomer is added to the bisphenol monomer salt solution to carry out ether phthalimide prepolymerization to obtain an etherimide segment. Prepolymer solution;

3) Block copolymerization

Mixing the sulfone segment prepolymer solution prepared in the step 1) and the ether imide segment prepolymer solution prepared in the step 2) to carry out block copolymerization reaction to obtain a block copolymer solution;

4) Purification treatment

The block copolymer solution is cooled and then subjected to a pulverization treatment; then, an extraction solvent is added to the powder, and the mixture is heated and boiled and then filtered, and repeated several times until the content of the alkali metal salt in the extraction solvent is less than 5 ppm; and then the powder is dried.

Wherein, the temperature of the salt formation reaction in the step 1A) is 150-210 ° C; the salt formation reaction time is 1-12 h, preferably 1-2 h.

In particular, the organic solvent mixture of 1A) and 2A) is a mixed system of an aprotic polar solvent and a catalyst, wherein the mass ratio of the aprotic polar solvent to the catalyst is (90-100): (0-10) Preferably, it is (90-99): (1-10).

The alkali metal salt in the steps 1A) and 2A) is sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate.

Wherein the ratio of the volume of the water-carrying agent to the mass of the organic solvent mixture in the steps 1A) and 2A) is (5-15): 100 (mL/g), that is, water is added per 100 g of the organic solvent mixture. 5-15mL.

The ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture mixture in the steps 1A) and 2A) is (10-45):100.

In particular, the inert gas described in steps 1A), 2A) is nitrogen, argon or carbon dioxide.

In particular, the molar ratio of the chlorine monomer in step 1B) to the bisphenol monomer in step 1A) is from 99 to 101:100:100, preferably 100:100.

In particular, the temperature of the sulfone prepolymerization in step 1B) is from 180 to 280 ° C, preferably from 180 to 250 ° C; and the prepolymerization time is from 2 to 12 h, preferably from 5 to 8 h.

Wherein the molar ratio of the diimide monomer in the step 2B) to the bisphenol monomer in the step 2A) is 99-101:100:100, preferably 100:100.

In particular, the temperature of the ether phthalimide prepolymerization in step 2B) is from 180 to 280 ° C, preferably from 180 to 250 ° C; and the prepolymerization time is from 2 to 12 h, preferably from 5 to 8 h.

In particular, the diimide monomer is added to the bisphenol monomer salt solution in the sulfone prepolymerization reaction at a temperature of 120 to 200 ° C in the step 2A); in the step 2B), the temperature is 120-200. The diimide monomer was added to the bisphenol monomer salt solution of the etherimide prepolymerization reaction at °C.

Wherein, in the block copolymerization reaction in the step 3), the molar ratio of the sulfone segment prepolymer solution prepared in the step 1) and the ether imide segment prepolymer solution prepared in the step 2) is (0.1). -99.9): (0.1-99.9); preferably (30-70): (30-70).

In particular, in the block copolymerization reaction, the molar ratio of the bisphenol monomer in the step 1A) to the bisphenol monomer in the step 2A) is (0.1-99.9): (0.1-99.9); For (30-70): (30-70).

Wherein, the block copolymerization reaction temperature in the step 3) is 180-280 ° C, preferably 200-210 ° C; the block copolymerization reaction time is 0.5-12 h, preferably 0.5-2 h.

Specifically, the sulfone segment prepolymer solution prepared in the step 1) and the etherimide segment prepolymer solution prepared in the step 2) are mixed at a temperature of 150 to 200 °C.

In particular, it further comprises the step of adding a blocking agent to the block copolymer mixture in step 3A), performing end group blocking treatment, and preparing the blocked mixture, followed by purification treatment.

Wherein the substituent X in the formula (IX) is -OH, F, Cl, Br or I, wherein -OH, F or Cl is preferred; wherein R represents -H, -benzene, or benzene, naphthalene ring and thick The cycloaromatic derivative groups include, but are not limited to, the following structures:

Or an isomer thereof or a structurally similar compound wherein X' in the R substituent in the formula (IX) represents H, F, Cl, Br, I.

In particular, the blocking agent is preferably chlorobenzene.

In particular, the end group blocking treatment temperature is 180-280 ° C, preferably 200-220 ° C; the end group blocking treatment time is 1-3 h, preferably 2-3 h.

In particular, the total molar ratio of the blocking agent in the step 3A) to the bisphenol monomer in the steps 1A), 2A) is (0-10):100, preferably (1-6):100, It is more preferably (3-6): 100, still more preferably 6:100.

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

1) The present invention employs a copolymer of a substituted phthalimide monomer and a polyaryl ether sulfone to achieve high temperature resistance of the polyimide and excellent processing properties of the polyaryl ether sulfone, and a high molecular weight copolymer is obtained.

2) The use of an alkane-substituted phenol in the present invention improves transparency.

3) The use of aromatic polyphenols improves fluidity.

4) Use halogenated chain extenders to increase the strength of the material.

5) The polymer is capped with a capping agent of a substituted structure to improve thermal stability. Thus, a series of molecular combination structures are obtained with excellent properties.

6) On the other hand, the method has low production cost of raw materials and is suitable for industrial production.

Detailed ways

The present invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.

The test method is as follows:

1. The glass transition temperature adopts DSC test; 2. The molecular weight is tested by GPC analysis; 3. The melting index is tested by melt finger test, the test condition is 365 ° C, 5Kg; 4. The thermal stability is TG tested with 5% initial thermal decomposition temperature. Evaluation; 5. Transmittance is measured by UV-Vis spectrophotometer.

In the embodiment of the present invention, A is a bisphenol monomer; B is a chlorine monomer; C: is a diimide monomer; D is a functional monomer; D1 is a chain extender; D2 is a mobile phase improving agent; D3 is a transparency improving agent; E is a blocking agent or a heat stability improving agent;

Example 1

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 1:99. Obtaining an organic solvent mixture;

The catalyst in the organic solvent mixture of the present invention is exemplified by polyethylene glycol. In addition to polyethylene glycol, polyether is also used; the molecular weight of chain polyethylene glycol is 200-600; cyclic crown ethers : 18 crown 6, 15 crown 5, cyclodextrin, etc.; quaternary ammonium salt: benzyl triethyl ammonium chloride (TEBA), tetrabutyl ammonium bromide (TBAB), tetrabutyl ammonium chloride and the like.

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 500 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). 93 g of biphenyldiol and 144 g of 4,4'-dichlorodiphenyl sulfone were added in sequence, and the mixture was stirred until all the monomers were dissolved. The ratio of the mass of the bisphenol monomer to the mass of the organic solvent mixture was 18.6:100. ;

1C) Under stirring, the temperature is raised to 100 ° C (usually 90-120 ° C), 120 g of sodium carbonate and 120 ml of xylene are added to the system, and the temperature is raised and maintained at 200-210 under nitrogen protection. Under the condition of °C, the salt formation reaction is carried out, the water formed in the system is azeotroped with xylene, the cooling water is started to be condensed in the condenser, and the layer is separated in the water separator. The upper layer of xylene is changed from turbid to clarified and then refluxed. Twenty minutes to ensure complete salt formation reaction, reflux reaction with water for 1-2 hours, after the water and p-xylene are discharged, the salt formation reaction is completed, and the biphenyldiol reacts with sodium carbonate to form a salt, which makes the biphenyldiol formation. a biphenyl monomer salt system, wherein a molar ratio of sodium carbonate to biphenyldiol is 125:100;

2. Polymerization reaction (copolymerization reaction)

Under stirring, the bisphenol monomer salt-forming system was further heated to 215 ° C, and the polymerization was carried out under the condition of maintaining the temperature at 215 ° C, and the reaction was continued at a constant temperature for 3.5 hours to ensure that the polymerization reaction was completed and then stopped to obtain a polymer mucilage. , that is, a polymerization system;

In the present embodiment, the operating pressure during the copolymerization reaction is normal pressure, and other atmospheric pressures up to 3.0 MPa are applicable to the present invention.

3, post processing

Stirring was stopped, and the polymer mucilage was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue masher, and then added to the powder by adding new deionized water for boiling for 1 hour, followed by filtration, and then into the powder. The deionized water was boiled and filtered, and the mixture was repeated 8 to 10 times until the salt content in the water was 5 ppm or less. The filtered polymer powder was vacuum dried to a moisture content of less than 0.5% to obtain polyphenylene sulfone.

In the present invention, the catalyst polyethylene glycol is both an organic solvent and a phase transfer catalyst, and the two incompatible systems can be more homogeneous. The bisphenol monomer of the present invention is insoluble in a solvent after salt formation, and is not easily reacted. By using the phase transfer catalyst of polyethylene glycol, it can become more homogeneous and easily react.

The glass transition temperature (Tg, ° C) of the prepared polymer was tested by DSC method; the molecular weight of the prepared polymer was measured by GPC method (Gel Permeation Chromatography); the prepared polymer was tested by a melt finger tester. Melt index; the thermal stability of the prepared polymer was evaluated by TG test 5% initial thermal decomposition temperature; the transmittance of the prepared polymer was tested by an ultraviolet-visible spectrophotometer, and the test results are shown in Table 1.

Example 2

1, salt formation reaction

1A) mixing sulfolane (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) uniformly, wherein the mass ratio of polyethylene glycol to sulfolane is 10:90, to prepare an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1000 g of an organic solvent mixture is first added, and then the temperature is raised and maintained at 80 ° C, and 250 g of 4, 4' is sequentially added. - dihydroxydiphenyl sulfone, 293 g of 4,4'-dichlorodiphenyl sulfone, stirred until the monomer is completely dissolved, wherein the mass ratio of the bisphenol monomer to the organic solvent mixture is 25:100;

1C) Under stirring, while maintaining the temperature at 100 ° C (usually 90-120 ° C), add 120 g of sodium carbonate and 120 ml of xylene to the system, and raise the temperature at 200-210 ° C under nitrogen protection. Under the conditions of the salt formation reaction, the water formed in the system is azeotroped with xylene, and the cooling tube begins to have cooling water droplets, and is layered in the water separator. The upper layer of xylene is changed from turbid to clarified and then refluxed. Ten minutes to ensure complete salt formation reaction, reflux reaction with water for 1-2 hours, after the water and p-xylene are discharged, the salt formation reaction is completed, and 4,4'-dihydroxydiphenyl sulfone reacts with sodium carbonate to form a salt. 4,4'-dihydroxydiphenyl sulfone to form 4,4'-dihydroxydiphenyl sulfone salt, to obtain a bisphenol monomer salt system, wherein the molar ratio of sodium carbonate to 4,4'-dihydroxydiphenyl sulfone Is 113:100;

2. Polymerization reaction (copolymerization reaction)

Under stirring, the bisphenol monomer salt-forming system is further heated and maintained at a temperature of 235 ° C, and the reaction is continued at a constant temperature for 2 hours to ensure that the polymerization reaction is completely stopped, and a polymer mucilage is obtained. Polymerization system

3, post processing

Stirring was stopped, and the polymer mucilage of the polymerization system was directly injected into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then added to the powder by adding new deionized water for boiling for 1 hour, followed by filtration, and then The powder was boiled and filtered by deionized water, and this was repeated 8 to 10 times until the salt content in the water was 5 ppm or less, and the filtered polymer powder was vacuum-dried to a moisture content of less than 0.5% to obtain a polyethersulfone.

The glass transition temperature, molecular weight, melt index, thermal stability, and transmittance test results of the prepared polymer are shown in Table 1.

Example 3

1, salt formation reaction

1A) mixing sulfolane (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) uniformly, wherein the mass ratio of polyethylene glycol to sulfolane is 5:95, to prepare an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1000 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). 228 g of bisphenol A and 286 g of 4,4'-dichlorodiphenyl sulfone were sequentially added, and the mixture was stirred until the monomers were completely dissolved, and the mass ratio of the bisphenol monomer to the organic solvent mixture was 22.8:100. ;

1C) Under stirring, 120 g of sodium carbonate and 120 ml of xylene are added to the system under the conditions of heating to 100 ° C (usually 90-120 ° C), and the temperature is raised and maintained at 150-200 under the protection of nitrogen. Under the condition of °C, the salt formation reaction is carried out, the water formed in the system is azeotroped with xylene, the cooling water is started to be condensed in the condenser, and the water is stratified in the water separator. The reflux reaction takes water for 1-2 hours, and the water is discharged. After p-xylene, the salt formation reaction is completed, and the upper layer of xylene is changed from turbidity to clarification and then refluxing for 20 minutes to ensure complete salt formation reaction. Bisphenol A reacts with sodium carbonate to form a salt, so that bisphenol A forms bisphenol. A salt, a bisphenol monomer salt formation system, wherein the molar ratio of sodium carbonate to bisphenol A is 113:100;

2. Polymerization reaction (copolymerization reaction)

Under stirring, the bisphenol monomer salt-forming system is further heated and maintained at a temperature of 215 ° C, and the reaction is continued at a constant temperature for 3 hours to ensure that the polymerization reaction is completely stopped, and a polymer mucilage is obtained. Polymerization system

3, post processing

Stirring was stopped, and the polymer mucilage was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue masher, and then added to the powder by adding new deionized water for boiling for 1 hour, followed by filtration, and then into the powder. The deionized water was boiled and filtered, and the mixture was repeated 8 to 10 times until the salt content in the water was 5 ppm or less. The filtered polymer powder was vacuum dried to a moisture content of less than 0.5% to obtain a polysulfone.

Example 4

1, salt formation reaction

1A) mixing ortho-dichlorobenzene (aprotic polar solvent) with polyethylene glycol (PEG400) (catalyst), wherein the mass ratio of polyethylene glycol to sulfolane is 3:97, and an organic solvent mixture is obtained. ;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1000 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). Adding 228 g of bisphenol A monomer (bisphenol monomer), stirring until the monomer is completely dissolved, wherein the mass ratio of the bisphenol monomer to the organic solvent mixture is 22.8:100;

1C) Under stirring, the temperature is raised to 100 ° C (usually 90-120 ° C), 115 g of potassium carbonate and 120 ml of toluene are added to the system, and the temperature is raised and maintained at 150-180 ° C under the protection of nitrogen. Under the conditions, the salt formation reaction is carried out, and the toluene of the upper layer is changed from turbidity to clarification and then refluxed for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and after the water and toluene are discharged, the salt formation reaction is completed. The bisphenol A is formed into a bisphenol A salt to obtain a bisphenol monomer salt system, wherein the molar ratio of potassium carbonate to bisphenol A is 120:100;

2. Polymerization reaction (copolymerization reaction)

Under stirring, 438 g of dichloroisophthalimide monomer (diimide monomer) was added to the bisphenol monomer salt system at a temperature of 180 ° C (usually 170-190 ° C). , the structural formula is as shown in the formula a), and the polymerization is carried out for 2-8 hours under the condition of heating and maintaining at 190 ° C (usually 180-280 ° C) to obtain a polymerization system;

3, post processing

Stirring was stopped, and the polymer mucilage of the polymerization system was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then added to the powder by adding solvent ethanol, boiled for 1 hour, filtered, and then transferred to the powder. The mixture was boiled and filtered, and repeated 8 to 10 times until the alkali metal salt content in the water was lowered to 5 ppm or less, and then the obtained polymer powder was dried to obtain the polyarylsulfone-etherimide copolymer.

Example 5

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 10:90. Obtaining an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1000 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). Adding 186 g of the biphenyldiol monomer to the total dissolution of the monomer, wherein the mass ratio of the bisphenol monomer to the organic solvent mixture is 18.6:100;

1C) Add 159 g of potassium carbonate and 50 ml of p-diethylbenzene to the system while heating to a temperature of 100 ° C (usually 90-120 ° C) under stirring, and raise the temperature at 180 ° C under nitrogen protection ( Usually, the salt formation reaction is carried out under the conditions of 150-210 ° C., until the upper layer of p-diethylbenzene changes from turbidity to clarification and then reflux for 20 minutes to ensure complete salt formation reaction, and the reflux reaction takes water for 1-2 hours. After water and p-diethylbenzene, the salt formation reaction is completed, and the biphenyldiol reacts with potassium carbonate to form a salt, so that the biphenyldiol forms a biphenyldiol salt solution, and a bisphenol monomer salt solution is obtained, wherein potassium carbonate and The molar ratio of biphenyldiol is 115:100;

2. Sulfone prepolymerization

Under nitrogen protection and stirring, 158 g of 4,4'-dichlorodiphenyl sulfone (chlorine monomer) was added to the bisphenol monomer salt solution at a temperature of 160 ° C (usually 120-200 ° C). After stirring until all of the solution is dissolved, and then heated to 180 ° C (usually 170-200 ° C), p-diethylbenzene is added to the system, heated to reflux, and the second time with p-diethylbenzene After discharging the water and the water-carrying agent, heating is continued, and the temperature is raised and maintained at 205 to 207 ° C for pre-polymerization for 5-8 hours to obtain a sulfone prepolymer solution (ie, a sulfone prepolymer), wherein: the chlorine monomer The molar ratio of (i.e., B) to the bisphenol monomer (i.e., A) is 55:100.

3. Copolymerization reaction

The sulfone prepolymer solution was cooled to 170 ° C, and 197 g of a dichloroisophthalamide monomer (diimide monomer having a structural formula of the formula a) was added; after the dissolution, the temperature was raised and maintained ( 215±5) ° C (210-220 ° C), copolymerization reaction under constant temperature conditions for 6h (usually 2-8h), to obtain a polymer mucilage, that is, a copolymer solution; wherein, the diimide monomer (ie, C single The molar ratio of the body to the bisphenol monomer (ie, A monomer) is 45:100.

4, post processing

Stirring was stopped, and the copolymer solution (ie, polymer mucilage) was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then the solvent was extracted into the powder and boiled for 1-2 h. Thereafter, the mixture is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the ethanol is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-etherimide copolymer.

Example 6

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 2:98. Obtaining an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, first add 1500 g of an organic solvent mixture, and then stir to a temperature of 80 ° C (usually 60-90 ° C). Adding 250 g of 4,4'-dihydroxydiphenyl sulfone monomer to the bisphenol monomer, wherein the mass ratio of the bisphenol monomer to the organic solvent mixture is 16.7:100;

1C) Add 150g of potassium carbonate and 50ml of p-diethylbenzene to the system under the condition of heating to 100 ° C (usually 90-120 ° C) under stirring, and raise to 210 ° C under nitrogen protection. (usually 150 ~ 210 ° C), the salt formation reaction, until the upper layer of p-diethylbenzene from turbidity to clarification and then continue to reflux for 20 minutes to ensure complete salt formation reaction, reflux reaction with water for 1-2 hours, After the water and p-diethylbenzene are discharged, the salt formation reaction is completed, and 4,4'-dihydroxydiphenyl sulfone is reacted with potassium carbonate to form a salt, thereby preparing a bisphenol monomer salt solution, wherein potassium carbonate and 4, 4'- The molar ratio of dihydroxydiphenyl sulfone is 109:100;

2. Sulfone prepolymerization

Under nitrogen gas, add 189 g of 4,4'-dichlorodiphenyl sulfone to the bisphenol monomer salt solution under stirring at a temperature of 120 ° C (usually 120-200 ° C), and stir until After all the dissolution, then the temperature is raised to 180 ° C (usually 180-200 ° C) to add p-diethylbenzene to the system, heated to reflux, the second time with p-diethylbenzene, water and water After the watering agent is added, the reaction is continued to be heated, and the temperature is raised and maintained at 210 ° C (usually 180-280 ° C) for pre-polymerization for 5 h (usually 5-8 h) to prepare a sulfone prepolymer solution (ie, a sulfone prepolymer). Wherein: the molar ratio of the chlorine monomer (i.e., B) to the bisphenol monomer (i.e., A) is 68.5:100.

3. Copolymerization reaction

Cooling the sulfone prepolymer solution to 160 ° C (usually 140-170 ° C), adding 153 grams of bis-dichlorom-benzoimide monomer (diimide monomer, its structural formula is shown in formula a); After dissolving, the temperature is raised and maintained at 212 ° C, and the copolymerization reaction is carried out under constant temperature for 6 h (usually 2-8 h) to obtain a polymer mucilage, that is, a copolymer solution in which a diimide monomer (ie, a C monomer) is The molar ratio of the bisphenol monomer (i.e., A monomer) was 35:100.

4, post processing

Stirring was stopped, and the copolymer solution (ie, polymer mucilage) was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and a solvent extractant (acetone) was added to the filtered powder. After boiling for 1-2 hours, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-ether. Imide copolymer.

Example 7

1, salt formation reaction

1A) Mixing o-dichlorobenzene (aprotic polar solvent) with polyethylene glycol (PEG400) (catalyst), wherein the mass ratio of polyethylene glycol to o-dichlorobenzene is 4:96, and organic Solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 800 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). Adding 228 g of bisphenol A monomer, stirring until the bisphenol monomer is dissolved, wherein the mass ratio of the added bisphenol monomer to the organic solvent mixture is 28.5:100;

1C) Add 145 g of potassium carbonate and 100 ml of p-diethylbenzene to the system while raising the temperature to 100 ° C (usually 90-120 ° C) under stirring, and raise the temperature to 180 ° C under nitrogen protection ( Usually, the salt formation reaction is carried out under the conditions of 150-210 ° C., until the upper layer of p-diethylbenzene changes from turbidity to clarification and then reflux for 20 minutes to ensure complete salt formation reaction, and the reflux reaction takes water for 1-2 hours. After water and p-diethylbenzene, the salt formation reaction is completed, and bisphenol A is reacted with potassium carbonate to form a salt, thereby preparing a bisphenol monomer salt solution, wherein the molar ratio of potassium carbonate to bisphenol A is 105:100;

2. Sulfone prepolymerization

Under stirring, 100 g of 4,4'-dichlorodiphenyl sulfone is added to the bisphenol monomer salt system under the conditions of a temperature of 120 ° C (usually 120-200 ° C), and the mixture is stirred until completely dissolved. Then, the temperature was raised to 170 ° C, 100 ml of p-diethylbenzene was added to the system, and the mixture was heated to reflux. The second time the water was taken with p-diethylbenzene, the water and the water-carrying agent were discharged, and the reaction was further heated, and the temperature was raised. Maintaining at 190 ° C, prepolymerization for 5-8 hours, to obtain a sulfone prepolymer solution (ie, sulfone prepolymer), wherein: the molar ratio of chlorine monomer (ie B) to bisphenol monomer (ie A) The ratio is 35:100.

3. Copolymerization reaction

The sulfone prepolymer solution was cooled to 150 ° C, and 197 g of dichloroisophthalamide (diimide monomer, the structural formula is shown in formula a) was added; after dissolution, the temperature was raised and maintained at 180 ° C. The copolymerization reaction is carried out under constant temperature for 8 h (usually 2-8 h) to obtain a polymer mucilage, that is, a copolymer solution in which a diimide monomer (ie, a C monomer) and a bisphenol monomer (ie, a monomer) are obtained. The molar ratio is 65:100.

4, post processing

Stirring was stopped, and the copolymer solution was directly poured into deionized water at room temperature to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then added to the filtered powder by boiling acetone for 1-2 hours, and then filtered. Then, the mixture is boiled and filtered, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-etherimide copolymer.

Example 8

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 4:96. Obtaining an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1150 g of an organic solvent mixture is first added, and then stirred and heated to 80 ° C (usually 60-90 ° C). 186 g of a biphenyldiol monomer (bisphenol monomer) was added to stir until the monomer was completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture was 16.2:100;

1C) Add 152 g of potassium carbonate and 50 ml of p-diethylbenzene to the system while stirring to a temperature of 100 ° C (usually 90-120 ° C), and raise the temperature at 150 ° C under nitrogen protection. (usually 150 ~ 210 ° C), the salt formation reaction, until the upper layer of p-diethylbenzene from turbidity to clarification and then continue to reflux for 20 minutes to ensure complete salt formation reaction, reflux reaction with water for 1-2 hours, After the water and p-diethylbenzene are discharged, the salt formation reaction is completed, and the biphenyldiol reacts with potassium carbonate to form a salt, so that the biphenyldiol produces a biphenyldiol salt to prepare a bisphenol monomer salt solution, wherein the potassium carbonate The molar ratio with the biphenol is 110:100;

2. Sulfone prepolymerization

Under stirring and nitrogen protection, 127 g of 4,4'-dichlorodiphenyl sulfone (chlorine monomer) was added to the bisphenol monomer salt system at a temperature of 150 ° C (usually 120-200 ° C). After stirring until all of the solution is dissolved, and then heated to 180 ° C (usually 180-200 ° C), 100 ml of p-diethylbenzene is added to the system, heated to reflux, and the second band of p-diethylbenzene is used. After the water, the water and the water-carrying agent are heated, the heating is continued, the temperature is raised and maintained at 190 ° C (usually 180-250 ° C), and pre-polymerization is carried out for 5-8 hours to prepare a sulfone prepolymer solution (ie, a sulfone prepolymer). Wherein: the molar ratio of the chlorine monomer (i.e., B) to the bisphenol monomer (i.e., A) is 44:100.

The ratio of the volume of the water-carrying agent to the mass of the organic solvent mixture to be added in the present invention is 5 to 15:100 (mL/g), that is, 5 to 15 mL of the water-carrying agent is added per 100 g of the organic solvent mixture.

3. Copolymerization reaction

The sulfone prepolymer solution is cooled to 160 ° C (usually 140-170 ° C), and 153 g of a dichloroisophthalamide monomer (diimide monomer) having a structural formula of a formula is added under stirring. After the dissolution, the temperature is further increased and maintained at 210 ° C (usually 180-280 ° C), and the copolymerization reaction is carried out under constant temperature for 4 hours (usually 2-8 hours) to obtain a polymer mucilage, that is, a copolymer solution; The molar ratio of the diimide monomer (i.e., C monomer) to the bisphenol monomer (i.e., A monomer) was 53:100.

4, end closure treatment

Under stirring, 3.4 g of chlorobenzene (blocking agent, E monomer) was added to the copolymer solution, and the temperature was raised by heating and maintained at 215 ° C (usually 180-280 ° C) to carry out polymer end group blocking treatment for 2.5 hours. (copolymerization reaction, usually 1-3 hours), adjusting the molecular weight, obtaining a higher molecular weight mucilage, that is, obtaining a blocked copolymer solution, wherein the blocking agent (E monomer) and the bisphenol monomer (A monomer) The molar ratio is 3:100.

In the process of the terminal blocking treatment, the terminal blocking treatment is carried out in the present invention, and the molar ratio of the blocking agent to the bisphenol monomer is 3:100, and the molar ratio of the blocking agent to the bisphenol monomer is excluded. In addition to 3:100, other ratios of 0-3:100 are also suitable for use in the present invention. The purpose and effect of the end-blocking treatment of the present invention after the copolymerization reaction is to control the molecular weight of the polymer not to increase too much, and to ensure that the prepared polyaryl ether sulfone-etherimide copolymer has an average molecular weight of 20,000 to 100,000.

In the end group sealing treatment of the present invention, the treatment temperature is preferably from 200 to 220 °C.

5, post processing

Stirring was stopped, and the blocked copolymer solution (ie, higher molecular weight mucilage) was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then acetone was added to the powder to extract the solvent. After 1-2 h, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-ether amide. Amine copolymer.

Example 9

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 3:97. Obtaining an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, first add 1500 g of an organic solvent mixture, then stir to a temperature of 90 ° C, and add 186 g of biphenyldiphenol. The body (bisphenol monomer) is stirred until the bisphenol monomer is dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture is 12.4:100;

1C) 240 gram of potassium hydrogencarbonate and 100 ml of toluene were added to the system while stirring to a temperature of 120 ° C (usually 90-120 ° C), and the temperature was raised to and maintained at 150 ° C under nitrogen atmosphere ( Usually, the salt formation reaction is carried out under the conditions of 150-210 ° C., until the upper layer of toluene changes from turbidity to clarification and then reflux for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and the water and toluene are discharged. After completion, the salt formation reaction is completed, and the biphenyldiol is reacted with potassium hydrogencarbonate to form a salt, and a bisphenol monomer salt system is obtained, wherein the molar ratio of potassium hydrogencarbonate to biphenyldiol is 240:100;

2. Sulfone prepolymerization

Nitrogen protection under agitation, adding 57 g of 4,4'-dichlorodiphenyl sulfone to the bisphenol monomer salt solution at a temperature of 160 ° C (usually 120-200 ° C ° C), stirring to all After dissolving, then heating to a temperature of (190 ± 2) ° C, adding 100 ml of toluene to the system, heating to reflux, using toluene for the second time with water, discharging water and watering agent, continuing the heating reaction, The sulfone prepolymerization reaction is carried out for 5 h (usually 5-8 h) at a temperature of (210 ± 2) ° C to prepare a sulfone prepolymer solution (ie, a sulfone prepolymer), wherein: the chlorine monomer (ie, B) and the double The molar ratio of phenolic monomer (ie A) is 20:100.

3. Copolymerization reaction

The sulfone prepolymer solution was cooled to (168±2) ° C, and 153 g of a dichloroisophthalamide monomer (diimide monomer, the structural formula is shown in formula a) was added under stirring; After dissolving, the temperature is raised and maintained at 190 ° C, and the copolymerization reaction is carried out under constant temperature for 7 h (usually 2-8 h) to obtain a polymer mucilage, that is, a copolymer solution; wherein the diimide monomer (ie, C monomer) The molar ratio to the bisphenol monomer (i.e., A monomer) is 80:100.

4, chain growth processing

4 g of ethoxylated titanium trichloride (chain extender, D1 monomer) was added to the copolymer solution under stirring under a nitrogen atmosphere, and the temperature was raised by heating and maintained at 195 ° C (usually 180-220 ° C). Chain growth treatment for 3h (copolymerization reaction, usually 2-3h), obtaining a higher molecular weight mucilage, that is, obtaining a chain extended copolymer solution in which a chain extender (D1 monomer) and a bisphenol monomer (A monomer) are obtained. The molar ratio is 2:100.

In the process of chain extension treatment in the present invention, the molar ratio of the chain extender to the bisphenol monomer is 2:100, and the molar ratio of the chain extender to the bisphenol monomer is 2, Other than :100, other ratios of 0-10:100 are also applicable to the present invention. The purpose and effect of the chain growth treatment of the present invention after the copolymerization reaction is to control the molecular weight of the polymer to ensure that the average molecular weight of the prepared polyaryl ether sulfone-etherimide copolymer is from 20,000 to 100,000.

The chain growth treatment temperature of the present invention is exemplified by 195 ° C, and other temperatures such as 180 to 280 ° C are also suitable for the present invention. The chain extender of the present invention is exemplified by ethoxylated titanium trichloride, and other chain extenders such as: ethoxylated titanium trichloride, pentamethylocyl-titanium trichloride, dimethyldichlorosilane, dichloro Methane or similar compounds are also suitable for use in the present invention.

5, post processing

Stop stirring, directly melt the polymer solution of the chain-extended copolymer solution into room temperature deionized water to cool into a strip of solid, filter it into a powder by a tissue pulverizer, and then add the solvent extractant (acetone) to the powder and repeatedly boil. After -2h, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-etherimide. Copolymer.

Example 10

1, salt formation reaction

1A) mixing sulfolane (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) uniformly, wherein the mass ratio of polyethylene glycol to sulfolane is 3:97, to prepare an organic solvent mixture;

The catalyst polyethylene glycol in the invention is both an organic solvent and a phase transfer catalyst, and the two incompatible systems can be more homogeneous. The bisphenol monomer of the invention is insoluble in a solvent after salt formation, and is not easy. The reaction, which can be more homogeneous by the action of a phase transfer catalyst of polyethylene glycol, can promote the polymerization reaction.

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, first add 1250 g of an organic solvent mixture, then stir to a temperature of 60 ° C, and add 228 g of bisphenol A monomer. (bisphenol monomer) is stirred until the monomer is completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture is 18.2:100;

1C) Add 179 g of potassium carbonate and 50 ml of diethylbenzene to the system while stirring to a temperature of 90 ° C, and raise to 160 ° C (usually 150-210 ° C) under nitrogen atmosphere. Under the conditions of the salt formation reaction, until the upper layer of diethylbenzene changed from turbidity to clarification and then continue to reflux for 20 minutes to ensure complete salt formation reaction, reflux reaction with water for 1.5h (usually 1 ~ 2h), discharge water and two After ethylbenzene, the salt formation reaction is completed, and bisphenol A is reacted with potassium carbonate to form a salt, thereby preparing a bisphenol monomer salt solution, wherein the molar ratio of potassium carbonate to bisphenol A is 114:100;

2. Sulfone prepolymerization

Nitrogen protection under agitation, adding 212 g of 4,4'-dichlorodiphenyl sulfone to the bisphenol monomer salt formation system at a temperature of 150 ° C, stirring until all dissolved, and then heating up to and maintaining Add 100 ml of diethylbenzene to the system at 180 ° C, heat to reflux, use diethylbenzene for the second time with water, drain water and water-carrying agent, continue heating reaction, keep the temperature at 220 ° C (usually 180- 280 ° C, preferably 180-250 ° C), prepolymerization for 6 h (usually 5-8 h), to obtain a sulfone prepolymer solution (ie sulfone prepolymer), wherein: chlorine monomer (ie B) and double The molar ratio of phenolic monomer (i.e., A) was 74:100.

3. Copolymerization reaction

The sulfone prepolymer solution is cooled to 140 ° C (usually 140-170 ° C), 122 grams of bis-dichlorom-benzoimide monomer (the structural formula is shown in formula a) is added; after dissolution, the temperature is raised and maintained ( 215±5) ° C (usually 180-280 ° C, preferably 180-220 ° C), copolymerization reaction under constant temperature conditions for 6h (usually 2-8h), to obtain a polymer mucilage, that is, a copolymer solution; The molar ratio of the imide monomer (i.e., C monomer) to the bisphenol monomer (i.e., A monomer) was 28:100.

4. Liquidity improvement treatment

4.25 g of 4-[4-[1,1-bis(4-hydroxyphenyl)ethyl]]-α,α-dimethylbenzylphenol was added to the copolymer solution under stirring under a nitrogen atmosphere. a fluidity improver, a D2 monomer having a structural formula as shown in formula b), heated to a temperature of 250 ° C (usually 180-280 ° C, preferably 220-250 ° C), and fluidity-improving treatment for 2.5 h (copolymerization) The reaction, usually 2-3 h), adjusts the molecular weight to obtain a higher molecular weight mucilage, that is, obtains a fluidity improving copolymer solution in which the fluidity improver (D2 monomer) and the bisphenol monomer (A monomer) are moles The ratio is 1:100.

In the present invention, the fluidity improving agent is added to perform the branching reaction improving treatment, and the molar ratio of the fluidity improving agent to the bisphenol monomer is 1:100, and the fluidity improving agent and the bisphenol monomer are described. In addition to 1:100 molar ratio, other ratios of 0-10:100 (preferably 0-3:100) are also suitable for use in the present invention. The purpose and effect of the present invention for carrying out the fluidity improving treatment after the copolymerization reaction is to improve the melt flowability of the polymer by improving the degree of branching of the polymer by the branched structure.

The fluidity improving treatment temperature of the present invention is described by taking 250 ° C as an example, and other temperatures such as 180 to 280 ° C are also suitable for the present invention. The fluidity improving agent of the present invention is described by taking a compound represented by the formula (b) as an example, and other fluidity improving agents such as P, P', P", P"'-[1,4-phenylene secondary benzyl group Tetraphenol, the structural formula is

It is also applicable to the present invention.

5, post processing

The stirring is stopped, and the fluidity improving copolymer solution (ie, the higher molecular weight mucilage) is directly injected into the deionized water at room temperature to be cooled into a strip solid, which is filtered and pulverized into a powder by a tissue pulverizer, and then the solvent acetone is extracted into the powder. After boiling for 1-2 h, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-ether acyl group. Imine copolymer.

Example 11

The molar ratio of each component in this embodiment is A:B:C:D ₁ :D ₂ :D ₃ :E=100:85:21:0:0:6:0

1, salt formation reaction

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1100 g of an organic solvent mixture was first added, and then the temperature was raised and maintained at 80 ° C, and 186 g of biphenyldiphenol was added. The body (bisphenol monomer) is stirred until the monomer is completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture is 16.9:100;

1C) Under stirring, 100 g of potassium carbonate and 50 ml of diethylbenzene were added to the system while heating to 100 ° C, and the temperature was raised and maintained at 170 ° C (usually 150-210 ° C) under nitrogen protection. Under the conditions, the salt formation reaction is carried out, and the upper layer of diethylbenzene is changed from turbidity to clarification and then refluxed for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and the water and diethylbenzene are discharged. In the salt formation reaction, the biphenyldiol reacts with potassium carbonate to form a salt, so that the biphenyldiol produces a biphenyldiol salt solution, wherein the molar ratio of potassium carbonate to biphenyldiol is 120. :100;

2. Sulfone prepolymerization

Nitrogen protection under agitation, adding 244 g of 4,4'-dichlorodiphenyl sulfone (chlorine monomer) to the bisphenol monomer salt formation system at a temperature of 190 ° C (usually 120-200 ° C) After stirring until all the solution is dissolved, and then heating to 190 ° C, 80 ml of diethylbenzene is added to the system, and the mixture is heated to reflux, and the second time with diethylbenzene, water is discharged, and the water and the water-carrying agent are discharged. The heating reaction is continued, and the prepolymerization is carried out for 5-8 hours while maintaining the temperature at (210 ± 5) ° C to obtain a sulfone prepolymer solution (ie, a sulfone prepolymer), wherein: the chlorine monomer (ie, B) The molar ratio to the bisphenol monomer (i.e., A) is 85:100.

3. Copolymerization reaction

The sulfone prepolymer solution was cooled to 150 ° C, and 91.8 g of dichloroisophthalamide (the structural formula is shown in formula a) was added under stirring; after dissolution, the temperature was raised and maintained at 210 ° C (usually 180-280). °C, preferably 180-220 ° C), copolymerization reaction under constant temperature conditions for 6.5h (usually 2-8h), to obtain a polymer mucilage, that is, a copolymer solution; wherein, the diimide monomer (ie, C monomer) The molar ratio of the bisphenol monomer (ie, A monomer) is 21:100.

4, transparency improvement treatment (fatty cyclic phenol)

Under stirring, nitrogen gas was added to the copolymer solution to add 18.6 g of bisphenol (TMC monomer) (transparency improver, D3 monomer, the structural formula is shown in formula c), and the temperature was raised by heating and maintained at 212 ° C ( Usually, it is 190-280 ° C, preferably 200-220 ° C), and the transparency is improved for 2-3 hours (copolymerization reaction) to obtain a higher molecular weight mucilage, that is, a transparency improving copolymer solution is obtained, wherein the transparency improving agent is obtained. The molar ratio of (D3 monomer) to bisphenol monomer (A monomer) was 6:100.

In the process of improving the transparency in the transparency improving agent of the present invention, the molar ratio of the transparency improving agent to the bisphenol monomer is 6:100, and the transparency improving agent and the bisphenol monomer are described. In addition to the ratio of 6:100, other ratios of 0-10:100 are also suitable for use in the present invention. The purpose and effect of the present invention for improving the transparency after the copolymerization reaction is to improve the transparency of the polymer.

The transparency improving treatment temperature of the present invention is described by taking 212 ° C as an example, and other temperatures such as 190-280 ° C are also suitable for the present invention. The transparency improving agent of the present invention is described by taking the compound of the formula c as an example, and other transparency improving agents such as:

The same applies to the present invention.

5, post processing

Stop stirring, and directly inject the transparency improving system (ie, the higher molecular weight mucilage) into the deionized water at room temperature to cool into a strip of solid. After filtering, pulverize into a powder with a tissue masher, and then add the extraction solvent acetone to the powder to boil. After -2h, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the acetone is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the polyarylsulfone-etherimide. Copolymer.

In the preparation process of the copolymer of the present invention, after the copolymerization reaction, the terminal group blocking treatment, the chain growth treatment, the fluidity improvement treatment or the transparency improvement treatment may be performed, or at least one or more of them may be carried out after the copolymerization reaction. deal with.

Example 12

1, salt formation reaction

1A) N-methylpyrrolidone (aprotic polar solvent) and polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of polyethylene glycol to N-methylpyrrolidone is 5:95. Obtaining an organic solvent mixture;

1B) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 1500 g of an organic solvent mixture was first added, and then the temperature was raised to 80 ° C with stirring, and 186 g of biphenol was added. The bisphenol monomer) is stirred until the monomer is completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture is 12.4:100;

1C) Under stirring, 145 g of potassium carbonate and 50 ml of diethylbenzene were added to the system while raising the temperature to 100 ° C, and the temperature was raised and maintained at 160 ° C (usually 150-210 ° C) under the protection of nitrogen. Under the conditions, the salt formation reaction is carried out, and the upper layer of diethylbenzene is changed from turbidity to clarification and then refluxed for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and the water and diethylbenzene are discharged. In the salt formation reaction, the biphenyldiol reacts with potassium carbonate to form a salt, so that the biphenyldiol produces a biphenyldiol salt solution, wherein a molar ratio of potassium carbonate to biphenyldiol is 105. :100;

2. Sulfone prepolymerization

Nitrogen protection under agitation, adding 109 g of 4,4'-dichlorodiphenyl sulfone (chlorine monomer) to the bisphenol monomer salt system at a temperature of 160 ° C (usually 120-200 ° C) After stirring until all the solution is dissolved, and then heating to 180 ° C (usually 180-200 ° C), 90 ml of diethylbenzene is added to the system, heated to reflux, and the second time with diethylbenzene, water is discharged. After the water and the water-carrying agent, the heating reaction is continued, the temperature is raised and maintained at 190 ° C (usually 180-250 ° C, preferably 180-220 ° C), and pre-polymerization is carried out for 8 h (usually 5-8 h) to prepare a sulfone pre- A solution of a polymer (i.e., a sulfone prepolymer) wherein the molar ratio of the chlorine monomer (i.e., B) to the bisphenol monomer (i.e., A) is 38:100.

3. Copolymerization reaction

The sulfone prepolymer solution was cooled to 160 ° C (usually 140-170 ° C), and 328 g of bischlorodiphenyl ether phthalimide (having a structural formula of the formula d, having a molecular weight of 529 g/mol) was added under stirring. ;

After dissolving, the temperature is raised again and maintained at 200 ° C (usually 180-280 ° C), and the copolymerization reaction is carried out under constant temperature for 8 h (usually 2-8 hours) to obtain a polymer mucilage, that is, a copolymer solution; wherein, diterpene The molar ratio of amine monomer (i.e., C monomer) to bisphenol monomer (i.e., A monomer) is 62:100.

4, post processing

Stirring was stopped, and the polymer solution of the copolymer solution was directly poured into deionized water at room temperature to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then boiled into a powder of acetone for 1-2 h, filtered, and then filtered. After boiling in a solvent, filtration, and repeated several times until the salt content in acetone is reduced to 5 ppm or less, the obtained polymer powder is dried to obtain the polyarylsulfone-etherimide copolymer.

Example 13

1. Preparation of an organic solvent mixture

The sulfolane (aprotic polar solvent) and the polyethylene glycol (PEG400) (catalyst) are uniformly mixed, wherein the mass ratio of the polyethylene glycol to the sulfolane is 1:99, and the organic solvent mixture is prepared and used;

2. Preparation of sulfone segment prepolymer

2A, salt formation reaction

2A-1) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 200 g of the organic solvent mixture prepared in the step 1) was first added, and then the mixture was heated to 80 ° C with stirring, and added. 70.68 g (0.38 mol) of biphenyldiol (bisphenol monomer) was stirred until the monomer was completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture was 35.3:100;

2A-2) 52.4 g of sodium carbonate and 20 ml of toluene were added to the system under stirring while maintaining the temperature at 100 ° C, and the temperature was raised and maintained at 150 ° C (usually 150 to 210 ° C) under the protection of nitrogen. Under the conditions, the salt formation reaction is carried out, and the toluene of the upper layer is changed from turbidity to clarification and then refluxed for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and after the water and toluene are discharged, the salt formation reaction is completed. The biphenyldiol reacts with sodium carbonate to form a salt, so that the biphenyldiol produces a biphenyldiol salt, and a bisphenol monomer salt solution for the sulfone segment prepolymerization reaction is prepared, wherein the sodium carbonate and the biphenol are mixed. The ratio is 120:100;

2B, sulfone prepolymerization

Nitrogen protection under agitation, adding 109 g (287*0.38)) 4 to the bisphenol monomer salt system for the sulfone segment prepolymerization at a temperature of 150 ° C (usually 120-200 ° C). 4'-dichlorodiphenyl sulfone (chlorine monomer), after stirring until completely dissolved, 20 ml of toluene was added to the system, heated to reflux, and water was taken with toluene for the second time. After the water and the water-carrying agent were discharged, the reaction was continued. Warming up and maintaining at 180 ° C (usually 180-250 ° C, preferably 180-220 ° C), pre-polymerization for 8 h (usually 5-8 h), to obtain a sulfone segment prepolymer solution (ie sulfone segment pre- Polymer) wherein the molar ratio of chlorine monomer (i.e., B) to bisphenol monomer (i.e., A) is 100:100.

The molar ratio of the chlorine monomer added in the "sulfone prepolymerization reaction" in the step 2B) to the bisphenol monomer in the step 2A) is 99-101:100, preferably 100:100.

3. Preparation of etherimide segment prepolymer

3A, salt formation reaction

3A-1) In a three-necked flask equipped with a thermometer, a nitrogen gas tube, a condensing water separator, and a stirrer, 600 g of the organic solvent mixture prepared in the step 1) was first added, and then the mixture was heated to 80 ° C with stirring, and added. 115.32 (0.62 mol) of biphenol (bisphenol monomer) was stirred until the monomer was completely dissolved, wherein the ratio of the mass of the bisphenol monomer to the total mass of the organic solvent mixture was 19.2:100;

3A-2) 78.8 g of sodium carbonate and 60 ml of toluene were added to the system under stirring while maintaining the temperature at 100 ° C, and the temperature was raised under nitrogen protection and maintained at 160 ° C (usually 150 to 210 ° C). Under the conditions, the salt formation reaction is carried out, and the toluene of the upper layer is changed from turbidity to clarification and then refluxed for 20 minutes to ensure complete salt formation reaction. The reflux reaction takes water for 1-2 hours, and after the water and toluene are discharged, the salt formation reaction is completed. The biphenyldiol reacts with sodium carbonate to form a salt, so that the biphenyldiol produces a biphenyldiol salt, and a bisphenol monomer salt solution for the etherimide segment prepolymerization reaction is prepared, wherein sodium carbonate and biphenyldiol The molar ratio is 120:100;

3B, etherimide prepolymerization (copolymerization)

Nitrogen protection under agitation, adding 271.56 (0.62 mol) of dichloroethylene to the bisphenol monomer salt system for prepolymerization of etherimide segments at a temperature of 150 ° C (usually 120-200 ° C)酞imide (diimide monomer, structural formula such as formula a), after stirring until all dissolved, 50 ml of toluene was added to the system, heated to reflux, and water was taken with toluene for the second time. After draining water and watering agent Continue to heat the reaction, raise the temperature and maintain at 205 ° C (usually 180-250 ° C, preferably 180-220 ° C), and carry out prepolymerization for 8 h (usually 5-8 h) to prepare the etherimide segment prepolymerization. a solution in which the molar ratio of the diimide monomer (i.e., C) to the bisphenol monomer (i.e., A) is 100:100.

In the "etherimide prepolymerization" step in the step 3B) of the present embodiment, the molar ratio of the phthalimide monomer monomer to the bisphenol monomer in the step 3A) is 99-101:100. It is preferably 100:100.

4, block copolymerization

The sulfone segment prepolymer solution prepared in step 2 (ie, sulfone pre-segment polymer) and the etherimide segment prepared in step 3 are pre-polymerized under a nitrogen atmosphere under a nitrogen atmosphere at 150-200 ° C. The solution (ie, the etherimide segment prepolymer) is uniformly mixed, and the block copolymerization reaction is carried out under the condition of maintaining the temperature at 205 ° C (usually 200-210 ° C) to obtain a block copolymer solution, wherein the step 2 The molar ratio of the prepared sulfone segment prepolymer to the etherimide segment prepolymer prepared in step 3 is 38:62; that is, the bisphenol monomer added in step 2A-1) and step 3A-1 The molar ratio of bisphenol monomer added was 38:62.

The molar ratio of the bisphenol monomer used in the synthesis of the sulfone segment prepolymer to the bisphenol monomer used in the synthesis of the etherimide segment prepolymer in the embodiment of the present invention is 38:62, that is, step 2A) The molar ratio of the bisphenol monomer to the bisphenol monomer in the step 3A) is 38:62, except that the molar ratio is 38:62, and the ratio is usually (0.1-99.9): (0.1-99.9) Preferably, 30-70:30-70 are suitable for use in the present invention.

5, end group blocking treatment (copolymerization reaction)

After block copolymerization for 1 h (usually 0.5-2 h), 7.5 g of chlorobenzene (blocking agent, E monomer) is added to the copolymer solution, and the temperature is maintained at 210 ° C (usually 180-280 ° C). Polymer end group capping reaction (copolymerization reaction) for 2-3 hours, that is, a blocked copolymer solution is obtained, wherein the total amount of the capping agent (E monomer) and the bisphenol monomer (A monomer) in steps 2 and 3 The molar ratio is 6:100 (usually 0-10:100).

6, post processing

Stirring was stopped, and the blocked copolymer solution (ie, higher molecular weight mucilage) was directly poured into room temperature deionized water to cool into a strip of solid. After filtration, it was pulverized into a powder by a tissue pulverizer, and then the solvent was added to the powder to boil. After 1-2 h, it is filtered, and then boiled and filtered in a solvent, and repeated several times until the salt content in the ethanol is lowered to 5 ppm or less, and the obtained polymer powder is dried to obtain the block polyarylsulfone-ether amide. Amine copolymer.

In the preparation process of the block copolymer of the present invention, the pressure of the sulfone prepolymerization reaction, the etherimide prepolymerization reaction, the block copolymerization reaction, the terminal group blocking treatment, the chain growth treatment, the mobile phase improvement treatment, and the transparency improvement treatment is Atmospheric pressure, in addition to normal pressure, other operating pressures from atmospheric pressure to 3.0 MPa are suitable for use in the present invention.

Table 1 Polymer performance test results

The invention adopts the principle of molecular structure design, and prepares the toughness of the block or random polyarylsulfone-imide copolymer by using phenoxy, phenylsulfone and bis(phthalimide) as main chain structures. Good, high strength, excellent electrical properties, high thermal stability and flame retardancy. On the one hand, the introduction of a phthalimide group into the polyarylsulfone can improve the heat resistance, flame retardancy and electrical properties of the polysulfone. On the other hand, the introduction of a polysulfone group into the polyimide can lower the melting temperature of the polyimide, improve its processability, and combine the advantages of both. The product has broad application prospects and can be applied to aerospace components, steam sterilization medical components, food and beverage containers, including hot beverage storage containers, baby bottles and optical components. The copolymer of the present invention can also be copolymerized by adding an appropriate amount of functional monomers, the chain extension technology is used to improve the strength of the material, the introduction of a cycloalkanyl-substituted phenol to improve the transparency, the use of aromatic polyphenols to improve the fluidity, and the use of a blocking agent for the polymer. The capping is carried out to improve thermal stability, and thereby a series of molecular compositions having excellent properties are obtained.

Claims

A polyaryl ether sulfone-etherimide copolymer characterized in that the polyaryl ether sulfone-etherimide copolymer is composed of structural units represented by structural formulas (I) and (II). a copolymer or block copolymer having an average molecular weight of 20,000 to 100,000.

Wherein Ar 1 in the structural formula (I) is:

Or a structural formula of the structural formula; or a structure having a substituent of the above structural formula; or a polycyclic and heterocyclic structural compound and an isomer thereof; and R' in the structural formula (I) is:

Or an isomer of the structure or a derivatized structure containing a substituent;

In the formula (II), Ar2 is:

Or a similar structural formula of the structural formula; or a structure having a substituent of the above structural formula; or a polycyclic and heterocyclic structural compound and an isomer thereof.
The polyaryl ether sulfone-etherimide copolymer according to claim 1, wherein the molar ratio of the structural unit represented by the structural formula (I) and the structural formula (II) is (0 to 100): (0) ～100), preferably (30 to 70): (30 to 70).
The polyaryl ether sulfone-etherimide copolymer according to claim 1, wherein the polyaryl ether sulfone-etherimide copolymer has a glass transition temperature Tg of 200 to 320 ° C, preferably 225-290 ° C; viscosity is 0.2-1.0 dL / g; melt index is MI = 5 ~ 120g / 10min (365.0 ° C, 5KG).
A method for preparing a polyaryl ether sulfone-etherimide copolymer, comprising the steps of:

1) dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt, performing a salt formation reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt, thereby obtaining a bisphenol monomer salt system;

2) adding a chlorine monomer to the prepared bisphenol monomer salt system, and performing a prepolymerization reaction to obtain a sulfone prepolymer solution;

3) adding a phthalimide monomer to the prepared sulfone prepolymer solution to carry out a copolymerization reaction to obtain a copolymer solution;

4) The prepared copolymer solution is subjected to a purification treatment.
The preparation method according to claim 4, further comprising the step of: adding a blocking agent to the copolymer solution in step 3A), performing end group blocking treatment to obtain a blocked polymer.
The process according to claim 4, further comprising the step of 3B') adding a functional modifier to the copolymer solution for functional improvement treatment to obtain a functionally improved copolymer.
The method according to claim 6, wherein the functional modifier has a molar ratio of the bisphenol monomer in the step 1) of from 0 to 10:100.
The preparation method according to claim 4, further comprising the step of: step 3B) adding a chain extender to the copolymer solution, performing chain extension treatment to obtain an extended chain copolymer.
The production method according to claim 4, further comprising the step of: (3) adding a fluidity improving agent to the copolymer solution, and performing a fluidity improving treatment to obtain a fluidity improving copolymer.
The production method according to claim 4, further comprising the step of: adding a transparency improving agent to the copolymer solution in step 3D), and performing a transparency improving treatment to obtain a transparency improving copolymer.
The preparation method according to any one of claims 4 to 10, wherein the bisphenol monomer in the step 1) is a compound of the formula (III) and a derivative or structural analog thereof, and the structural formula (III) is :HO-Ar 1 -OH(III), wherein the Ar1 selection

Wherein the derivative is a substituent-containing compound of the structural compound of the formula (III); the structural analog is an isomer of the compound of the formula (III), or a polycyclic and heterocyclic structural compound One or several.
The method according to any one of claims 4 to 10, wherein in the step 2), the chlorine monomer is a compound of the formula (IV) and a derivative or structural analog thereof, and the structural formula (IV) is:

Where the R' selection

Wherein the derivative is a substituent-containing compound of the structural compound of the formula (IV); the structural analog is an isomer of the compound of the formula (IV), or a polycyclic and heterocyclic structural compound One or several.
The preparation method according to any one of claims 4 to 10, wherein the diimide monomer in the step (3) is a compound represented by the formula (V) and a derivative or structural analog thereof, and has a structural formula ( V) is:
Wherein the substitution position of z is 3- or / and 4-substituted, wherein Z is selected from chlorine, fluorine, bromine or nitro;

Or one or more of an aromatic structure or a polycyclic and heterocyclic structural compound similar to or having a substituent, or a mixture of these.
The method according to claim 5, wherein the blocking agent selectively selects a compound represented by the formula (IX) or a derivative or structural analog thereof, and the structural formula (IX) is:
Wherein the substituent X in the formula (IX) is -OH, F, Cl, Br or I, wherein -OH, F or Cl is preferred; wherein R represents -H, -benzene, or benzene, naphthalene ring and thick The cycloaromatic derivative groups include, but are not limited to, the following structures:

Or an isomer or structurally similar compound wherein X' in the R substituent represents H, F, Cl, Br, I.
The method according to claim 8, wherein the chain extender selects a compound of the formula (VI) or a derivative or structural analog thereof, and the structural formula (VI) is:
Wherein M is carbon, silicon or titanium; and R 1 and R 2 are each selected from the group consisting of chlorine, hydrogen, alkyl, alkoxy, cycloalkyl, phenyl, phenoxy, chloroalkyl.
The process according to claim 15, wherein the alkyl group is a linear alkyl group having 1 to 18 carbon atoms; and the alkoxy group is a linear alkoxy group having 1 to 20 carbon atoms. a cycloalkyl group having 5 to 20 carbon atoms; the phenyl group having 6 to 18 carbon atoms; and the phenoxy group having 6 to 18 carbon atoms; The alkyl group has 1 to 17 carbon atoms.
The method according to claim 9, wherein the fluidity improving agent selects an aromatic polyhydric phenol represented by the formula (VII) or a derivative or structural analog thereof, and the structural formula (VII) is:

Wherein R 1 is an alkyl group of 1 to 28 carbon atoms or an aromatic hydrocarbon group of 6 to 26 carbon atoms; R 2 and R 3 are hydrogen, a hydroxyl group, an alkyl group of 1 to 28 carbon atoms, and 5 to 25 carbons. An alicyclic group of an atom, an alkoxy group of 1 to 28 carbon atoms, an aryl group of 6 to 25 carbon atoms or an alicyclic group of 6 to 26 carbon atoms.
The process according to claim 10, wherein the transparency improving agent selects an alkane-substituted phenol represented by the formula (VIII) or a derivative or structural analog thereof, and the structural formula (VIII) is:

Wherein R 1 is an alkyl group of 1 to 28 carbon atoms, an alicyclic group of 5 to 26 carbon atoms, an alkoxy group of 1 to 28 carbon atoms, an aryl group of 6 to 26 carbon atoms, 6 to 26 Any one of an aryloxy group of a carbon atom or an alicyclic oxy group of 5 to 26 carbon atoms; R 2 and R 3 are hydrogen, an alkyl group of 1 to 28 carbon atoms, and 5 to 25 carbon atoms. An alicyclic group, an alkoxy group having 1 to 28 carbon atoms, an aryl group having 6 to 25 carbon atoms, an alicyclic group having 6 to 26 carbon atoms or a substituent having a phenol group.
A method for preparing a polyaryl ether sulfone-etherimide copolymer, comprising the steps of:

1) Synthetic sulfone segment prepolymer

1A) Dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt and a water-carrying agent, heating under reflux under an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt At the same time, the water and the water-carrying agent are discharged to obtain a bisphenol monomer salt system for the sulfone segment prepolymerization reaction;

1B) the sulfone segment prepolymerization step prepared in step 1A) is carried out by adding a chloro monomer to the bisphenol monomer salt system to carry out sulfone pre-segment polymerization to obtain a sulfone segment prepolymer solution;

2) Synthetic phthalimide segment prepolymer

2A) Dissolving the bisphenol monomer in an organic solvent mixture, adding an alkali metal salt and a water-carrying agent, heating under reflux under an inert gas, performing a salt reaction of the bisphenol monomer, and reacting the bisphenol monomer to form a salt At the same time, water and a water-carrying agent are discharged to obtain a bisphenol monomer salt system for prepolymerization of the etherimide segment;

2B) adding the diimide monomer to the bisphenol monomer salt system for the etherimide segment prepolymerization reaction prepared in the step 2A), and performing ether phthalimide prepolymerization to obtain the etherimide Segment prepolymer solution;

3) mixing the sulfone segment prepolymer solution prepared in step 1) and the etherimide segment prepolymer solution prepared in step 2), performing block copolymerization reaction to obtain a block copolymer solution;

4) The prepared block copolymer solution is subjected to a purification treatment.
The method according to claim 19, further comprising the step of: (3) adding a blocking agent to the block copolymer mixture, and performing end group blocking treatment to obtain a blocked mixture.
The process according to claim 4 or 19, wherein the alkali metal salt is selected from sodium carbonate, potassium carbonate, potassium hydrogencarbonate or sodium hydrogencarbonate.
The preparation method according to claim 4 or 19, wherein the organic solvent mixture is a mixed system of an aprotic polar solvent and a catalyst, wherein the mass ratio of the aprotic polar solvent to the catalyst is 90-100. : 0-10, preferably 90-99: 1-10.
The method according to claim 22, wherein the aprotic polar solvent is selected from the group consisting of sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, diphenyl sulfone, N,N-dimethylformamide, N,N-dimethylacetamide, o-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene, anisole, o-dimethoxybenzene or acetic acid; the catalyst selects polyether, chain The polyethylene glycol, cyclic crown ether or quaternary ammonium salt is preferably a chain polyethylene glycol.