CN101423603A - Polyaromatic ether copolymer containing carboxyl side group and preparation method thereof - Google Patents

Abstract

The invention provides a carboxyl side group-containing polyarylether copolymer and a preparation method thereof. The copolymer is based on phenolphthalein and its substituent-containing derivatives, phenolphthalein or its substituent-containing derivatives and other commercial bisphenol monomers, in a polar solvent, under alkali catalysis, and a dihalogen monomer such as 4, Homopolymerization or copolymerization of 4'-difluorobenzophenone, 4,4'-difluorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone, 1,4-bis-4-fluorobenzoylbenzene be made of. Its characteristic is that there are carboxyl side groups in the polymer structure, and the content of carboxyl groups is adjustable. By introducing substituents on the benzene ring of the main chain, the prepared polyarylether polymers containing carboxyl side groups have good solubility in common organic solvents, and are suitable as membrane separation materials, and can also be used as reinforcement and toughening of composite materials material or matrix resin material of bonded rare earth polymer.

Description

Carboxyl side group-containing polyarylether copolymer and preparation method thereof

technical field

The invention belongs to the field of polymer materials, and relates to a series of novel polyarylether high-performance copolymers containing carboxyl side groups and a preparation method thereof.

Background technique

Polyarylether (polyarylether ketone, polyarylether sulfone, polyarylether ketone ketone) is a kind of engineering plastic material with excellent comprehensive performance, which is widely used in aerospace, electronic appliances, nuclear energy industry and civil high-tech fields . However, as people have higher and higher requirements on the use and processing performance of materials, traditional polyarylether materials can no longer meet the needs of scientific and technological development. Traditional bisphenol A polyarylether sulfone and polyarylether ketone have a completely amorphous structure and are soluble in common organic solvents, but their glass transition temperatures are only 154°C and 189°C, and their use temperatures are relatively low. Polyether ether ketone (PEEK) is a semi-crystalline polymer successfully developed by the British ICI company in 1980. The use temperature has been increased to above 200 ° C, but it cannot be dissolved in organic solvents. The difficulties come; Chinese invention patents CN85108751 and CN85101721 disclose the preparation method of phenolphthalein polyarylether ketone and polyarylether sulfone. Due to the large phthalein side group restricting the internal rotation of the molecular chain, the glass transition temperatures of phenolphthalein-type polyarylether ketone and polyarylether sulfone are 228 ° C and 261 ° C, respectively, and the polymers in chloroform, dimethyl formaldehyde It has good solubility in commonly used solvents such as amide and N-methylpyrrolidone, and has been used in the field of epoxy resin toughening and strengthening to prepare composite materials.

Soluble polyarylether materials provide convenience in the preparation of composite materials by the solution method, but their solvent resistance is poor, and the compatibility of polyarylether materials with epoxy resin or cyanate ester systems has yet to be resolved. If an active carboxyl group that can react with epoxy resin or cyanate ester can be introduced on the molecular chain of the polymer, after compounding, the carboxyl group on the molecular chain of polyarylether can participate in the reaction of epoxy resin and cyanate ester. The curing reaction forms a three-dimensional cross-linked interpenetrating network structure, which can simultaneously improve the toughening performance and solvent resistance of the material. In 2004, Chinese invention patent CN1583827 reported a class of polyarylether materials containing carboxyl side groups, using 4,4'-bis(p-hydroxyphenyl)-2-pentanoic acid as a bisphenol monomer, and different bisfluoro It is prepared by condensation polymerization of monomers. Since the molecular chain of the polymer carries carboxyl side groups of aliphatic structure, the glass transition temperature of the polymer is lower than 200°C.

Contents of the invention

The purpose of the present invention is to provide carboxyl side group-containing polyarylether copolymers and preparation methods thereof. The series of aromatic polymers prepared by the present invention have active carboxyl groups connected to benzene ring side groups and have greater rigidity. The prepared The glass transition temperature of the polymer measured by DSC method is above 200°C. Moreover, after introducing different types of alkyl substituents on the benzene ring of the molecular chain, the polymer has excellent solubility, and some of the polymers are even in acetone. Also soluble in. This series of polymers can not only be applied to the reinforcement and toughening of epoxy resin and cyanate resin, but also has important practical applications in the preparation of membrane separation materials, coatings, insulating paint materials, and bonded rare earth coordination fluorescent materials. value and development value.

The technical solution of the present invention is that the chemical structure of polyarylether containing carboxyl side group is as follows:

为：

for:

为：

for:

In the formula: a+b+c+d=1; 0≤a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤1, and a and b cannot be 0 at the same time; n is greater than An integer equal to 1; R ₁ , R ₂ , R ₃ , R ₄ are hydrogen or C ₁ -C ₁₀ alkyl, alicyclic, or aromatic groups.

when

When R ₁ =H, R ₂ =H, R ₃ =H, c=0, d=0, the polymer structure is:

when

When R ₁ =H, R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =H, R ₆ =H, b=0, d=0, the polymer structure is:

when

When R ₁ =H, R ₂ =H, R ₃ =H, b=0, c=0, d=0, the polymer structure is:

when

When R ₁ =H, R ₂ =H, R ₃ =CH ₃ , b=0, c=0, d=0, the polymer structure is:

when

When R ₁ =H, R ₂ =H, R ₃ =CH ₃ , a=0, c=0, d=0, the polymer structure is:

when

When R ₁ =H, R ₂ =CH ₃ , R ₃ =CH(CH ₃ ) ₂ , R ₄ =H, R ₅ =H, R ₆ =H, b=0, d=0, the polymer structure for:

when

When R ₁ =H, R ₂ =CH ₃ , R ₃ =CH(CH ₃ ) ₂ , R ₄ =H, R ₅ =H, R ₆ =H, a=0, c=0, the polymer structure for:

when

When R ₁ =H, R ₂ =H, R ₃ =H, R ₄ =H, R ₅ =CH ₃ , R ₆ =CH(CH ₃ ) ₂ , b=0, d=0, the polymer structure for:

when

When R ₁ =H, R ₂ =CH ₃ , R ₃ =CH(CH ₃ ) ₂ , R ₄ =H, R ₅ =H, R ₆ =H, a=0, c=0, the polymer structure for:

The preparation method of the polyarylether containing carboxyl side group of the present invention, route is as follows:

In the above formula: X is F, Cl atom, a+b+c+d=1; 0≤a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤1, and a and b cannot 0 at the same time; n is an integer greater than or equal to 1; R ₁ , R ₂ , R ₃ , R ₄ are hydrogen or C ₁ -C ₁₀ alkyl, alicyclic, or aromatic groups.

为：

for:

for:

The preparation method of the carboxyl-containing side group polyarylether homopolymer of the present invention is specifically carried out according to the following steps: the phenolphthalein monomer and equimolar dihalogen monomer, alkali catalyst, solvent and dehydrating agent are added successively to the In the reaction kettle with water separator, agitator, thermometer and nitrogen inlet pipe, first raise the temperature to 120°C-150°C for dehydration for 1-7 hours, evaporate the dehydrating agent, and continue to heat up to 160°C-220°C for 1-30 hours. Add solvent to dilute, filter to remove inorganic salt after cooling, settle in precipitant, wash with water three times, and the product after drying has a molar yield of 90-95%.

The preparation method of another kind of carboxyl-containing side group polyarylene ether copolymer of the present invention specifically carries out according to the following steps: with the phenolphthalein monomer of p mole, one or more of other bisphenol monomers of q mole, ( p+q) moles of one or more of the dihalogen monomers, alkali catalyst, solvent and dehydrating agent are sequentially added to the reaction kettle with water separator, stirrer, thermometer and nitrogen inlet pipe, and the temperature is first raised to 120 ℃-150℃ dehydration for 1-7 hours, steam the dehydrating agent, continue to heat up to 160℃-180℃ and react for 1-30 hours. Add solvent to dilute, filter to remove inorganic salt after cooling, settle in precipitant, wash with water three times, and the product after drying has a molar yield of 90-95%.

The alkali catalyst described in the above preparation steps is one or more mixtures in sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood, and its consumption is bisphenol monomer and alkali catalyst by 1 :2—1:4 molar ratio.

The solvent described in the above preparation steps is dimethylsulfoxide, sulfolane, N,N-dimethylformamide, N-methylpyrrolidone or diphenylsulfone, and its consumption is 0.5-5.0 milliliters of solvent/gram of bisphenol and bisphenol Halogen monomer mixture.

The dehydrating agent described in the above preparation steps is one or more mixtures of benzene, toluene, xylene, and chlorobenzene, and its consumption is 0.2-2.0 ml of solvent/ml of dehydrating agent.

The precipitating agent described in the above preparation steps can be one or a mixture of ethanol, methanol, and water.

The chemical structure of the carboxyl side group-containing polyarylether of the present invention has been confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance analysis (NMR) methods. The number average molecular weight measured by gel permeation chromatography (GPC) is more than 60,000.

The beneficial effect of the present invention is that the content of carboxyl side groups in the carboxyl side group-containing polyarylether of the present invention can be adjusted by controlling the ratio of carboxyl group-containing bisphenol monomers to other bisphenol monomers. The crosslinking density of ethers with epoxy resins or cyanate esters provides a convenient technical condition. The glass transition temperature determined by DSC method is above 200°C (Table 1). By adjusting the type and number of alkyl substituents introduced on the main chain benzene ring, the solubility of the obtained polymer can be changed (Table 2). After the polymer is cast into a film, it is made into a 0.2mm film, which can be folded repeatedly at 180° for 5 times without cracks, and has good toughness.

Table 1 Polymer glass transition temperature determined by DSC method

Example 1 2 3 4 5 Glass transition temperature (°C 216 237 231 221 254

Table 2 Solubility of polymers in organic solvents

+: can be dissolved; —: not dissolved

Detailed ways

The examples provided below are only to further illustrate the present invention, but not to limit the scope of the present invention.

Example 1

Add 10.3915 grams (0.03mol) of 2', 2"-dimethylphenolphthalein, 6.5460 grams (0.03mol) of 4 , 4'-difluorobenzophenone, 7.6009 grams (0.055mol) of anhydrous potassium carbonate, 25 milliliters of dimethyl sulfoxide and 30 milliliters of toluene.Heating up to 140°C, azeotropic dehydration, after about 2 hours, all the toluene Evaporate, and continue to heat up to 175 ° C for 10 hours. Stop the reaction, dilute with N, N-dimethylformamide, precipitate in ethanol, repeatedly boil and wash with distilled water to remove inorganic salts, and obtain flocculent products after drying. Rate 94.8%.Reaction molecular formula is as follows:

Example 2

12.8138 grams (0.04mol) of phenolphthalein, 3.4912 grams (0.016mol) of 4,4'-difluorobenzophenone, 6.1021 grams (0.024mol) of 4,4'-difluorodiphenylsulfone, 11.0559 grams (0.08mol) Anhydrous potassium carbonate, 36 milliliters of dimethyl sulfoxide and 40 milliliters of toluene were successively placed in a 250-ml three-necked flask equipped with a nitrogen conduit, a condenser, a water separator, a thermometer and a mechanical stirrer. Raise the temperature to 140°C for azeotropic dehydration. After about 2 hours, distill off all the toluene, and continue to raise the temperature to 175°C for 10 hours. The reaction was stopped, diluted with N,N-dimethylformamide, precipitated in ethanol, washed repeatedly with distilled water to remove inorganic salts, and dried to obtain a flocculent product with a molar yield of 96.2%. The molecular formula of the reaction is as follows (wherein m:n=0.4:0.6):

Example 3

12.9767 grams (0.03mol) of 2', 2"-diisopropyl-5', 5"-dimethylphenolphthalein, 6.5460 grams (0.03mol) of 4,4'-difluorobenzophenone, 9.1081 grams ( 0.066mol) of anhydrous potassium carbonate, 19 milliliters of dimethyl sulfoxide and 25 milliliters of toluene were successively placed in a 250-ml three-neck flask equipped with a nitrogen conduit, a condenser, a water separator, a thermometer and a mechanical stirrer. Raise the temperature to 140°C for azeotropic dehydration. After about 2 hours, distill off all the toluene, and continue to raise the temperature to 175°C for 10 hours. The reaction was stopped, diluted with N,N-dimethylformamide, precipitated in ethanol, washed repeatedly with distilled water to remove inorganic salts, and dried to obtain a flocculent product with a molar yield of 95.7%. The molecular formula of the reaction is as follows:

Example 4

9.0837 grams (0.021mol) of 2',, 2"-diisopropyl-5', 5"-dimethylphenolphthalein, 2.8650 grams (0.009mol) of phenolphthalein, 6.5461 grams (0.03mol) of 4,4'- Difluorobenzophenone, 8.2801 grams (0.06mol) of anhydrous potassium carbonate, 18 milliliters of dimethyl sulfoxide and 22 milliliters of toluene were placed successively in a 250ml vessel equipped with a nitrogen conduit, a condenser, a water separator, a thermometer and a mechanical stirrer. in a three-neck flask. Raise the temperature to 140°C for azeotropic dehydration. After about 2 hours, distill off all the toluene, and continue to raise the temperature to 175°C for 10 hours. The reaction was stopped, diluted with N,N-dimethylformamide, precipitated in ethanol, washed repeatedly with distilled water to remove inorganic salts, and dried to obtain a flocculent product with a molar yield of 96.2%. The molecular formula of the reaction is as follows (wherein m:n=0.7:0.3):

Example 5

5.1255 grams (0.016mol) of phenolphthalein, 10.3330 grams (0.024mol) of 2',, 2"-diisopropyl-5', 5"-dimethylphenolphthalein, 10.1703 grams (0.04mol) of 4,4'- Difluorodiphenyl sulfone, 11.0400 grams (0.08mol) of anhydrous potassium carbonate, 20 milliliters of dimethyl sulfoxide and 28 milliliters of toluene are placed successively in a 250ml vessel equipped with nitrogen conduit, condenser, water separator, thermometer and mechanical stirrer. in a three-neck flask. Raise the temperature to 140°C for azeotropic dehydration. After about 2 hours, distill off all the toluene, and continue to raise the temperature to 175°C for 10 hours. The reaction was stopped, diluted with N,N-dimethylformamide, precipitated in ethanol, washed repeatedly with distilled water to remove inorganic salts, and dried to obtain a flocculent product with a molar yield of 95.9%. The molecular formula of the reaction is as follows (wherein m:n=0.4:0.6):

Claims (10)

1, the polyarylether copolymer of oxatyl-containing lateral group is characterized in that, this polyarylether copolymer has following structural formula:

Wherein:

For:

For:

B is:

In the formula: a+b+c+d=1; 0≤a≤1,0≤b≤1,0≤c≤1,0≤d≤1, and a and b can not be 0 simultaneously; N is the integer more than or equal to 1; R ₁, R ₂, R ₃, R ₄Be hydrogen or C ₁-C ₁₀Alkyl, alicyclic radical, aromatic group.

According to the polyarylether copolymer of the described oxatyl-containing lateral group of claim 1, it is characterized in that 2, the used carboxyl biphenol monomer that contains is a phenolphthalin, 2 '; 2 "-dimethyl phenolphthalein quinoline, 2 ', 5 ', 2 "; 5 "-tetramethyl-phenolphthalin, 2 ', 2 "-di-isopropyl-5 ', 5 "-dimethyl phenolphthalein quinoline.

3, according to the polyarylether copolymer of the described oxatyl-containing lateral group of claim 1, it is characterized in that, the used carboxyl copolymerization biphenol monomer that do not contain is a phenolphthalein, 2 '; 2 "-dimethyl phenolphthalein, 2 ', 5 '; 2 "; 5 "-tetramethyl-phenolphthalein, 2 ', 2 "-di-isopropyl-5 ', 5 "-dimethyl phenolphthalein, Resorcinol, 2,2-two (4,4 '-dihydroxyl hexichol) propane, 2, two (4, the 4 '-dihydroxyl hexichol) HFC-236fa of 2-, 4-(4-hydroxyl-phenyl)-2H-naphthyridine-1-ketone, 4,4 '-dioxydiphenyl methane, 2,6-naphthalenediol, 4 ' 4 '-'-biphenyl diphenol.

According to the polyarylether copolymer of the described oxatyl-containing lateral group of claim 1, it is characterized in that 4, used two halogen monomers can be 4,4 '-difluoro benzophenone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl sulfone, 1,4-two-4-fluorobenzene acyl group benzene.

5, a kind of method for preparing the described oxatyl-containing lateral group polyarylether homopolymer of claim 1-4, it is characterized in that, the steps include: phenolphthalin class monomer and equimolar pair of halogen monomer, alkaline catalysts, solvent and dewatering agent join successively and have water trap, agitator, in the reactor of thermometer and nitrogen ingress pipe, be warmed up to 120 ℃-150 ℃ dehydrations 1-7 hours earlier, steam dewatering agent, continue to be warmed up to 160 ℃-220 ℃ reactions 1-30 hours, add solvent cut, cooled and filtered is removed inorganic salt, sedimentation in precipitation agent, wash dried product, molar yield 90-95% three times.

6, a kind of method for preparing the described polyaromatic ether copolymer containing carboxyl side group of claim 1-4, it is characterized in that, the steps include: phenolphthalin class monomer with the p mole, one or more of the biphenol monomer of q mole, (p+q) Mo Er two halogen monomeric one or more, alkaline catalysts, solvent and dewatering agent join successively and have water trap, agitator, in the reactor of thermometer and nitrogen ingress pipe, be warmed up to 120 ℃-150 ℃ dehydrations 1-7 hours earlier, steam dewatering agent, continue to be warmed up to 160 ℃-180 ℃ reactions 1-30 hours, add solvent cut, cooled and filtered is removed inorganic salt, and sedimentation in precipitation agent is washed three times, dried product, molar yield 90-95%.

7, according to claim 5 or 6 described a kind of methods that prepare polyaromatic ether copolymer containing carboxyl side group, it is characterized in that, described solvent is dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, dinethylformamide, N-Methyl pyrrolidone or sulfobenzide, its consumption are 0.5-5.0 milliliters of solvents/gram bis-phenol and two halogen monomer mixture.

8, according to claim 5 or 6 described a kind of methods that prepare polyaromatic ether copolymer containing carboxyl side group, it is characterized in that, described dewatering agent is one or more the mixture in benzene,toluene,xylene or the chlorobenzene, and its consumption is 0.2-2.0 milliliters of solvents/milliliter dewatering agent.

9, according to claim 5 or 6 described a kind of methods that prepare polyaromatic ether copolymer containing carboxyl side group, it is characterized in that, described alkaline catalysts is one or more the mixture in sodium hydride, potassium hydride KH, sodium hydroxide, potassium hydroxide, yellow soda ash or the salt of wormwood, and its consumption is that biphenol monomer and alkaline catalysts are by 1:2-1:4 mol ratio.

According to claim 5 or 6 described a kind of methods that prepare polyaromatic ether copolymer containing carboxyl side group, it is characterized in that 10, described precipitation agent can be one or more the mixture in ethanol, methyl alcohol or the water.