KR20200053003A - Polysulfone copolymer having improved heat resistance and processability and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysulfone copolymer having improved heat resistance and processability, and a method for manufacturing the same. More particularly, the present invention relates to a polysulfone copolymer having excellent processability (especially injection processability) while significantly improving heat resistance, compared to a conventional polysulfone copolymer, by including a phenolphthalein-based sulfone oligomer as a repeating unit; and to a method for manufacturing the polysulfone copolymer.

Description

Polysulfone copolymer with improved heat resistance and processability and its manufacturing method {POLYSULFONE COPOLYMER HAVING IMPROVED HEAT RESISTANCE AND PROCESSABILITY AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polysulfone copolymer having improved heat resistance and processability and a method for manufacturing the same, and more specifically, by including a phenolphthalein-based sulfone oligomer as a repeating unit, the heat resistance is significantly improved compared to the conventional polysulfone copolymer, but the processability ( In particular, it relates to a polysulfone copolymer having excellent injection processability) and a method for manufacturing the same.

Polysulfone is one of the compounds that are useful as materials for various insulating materials or membranes that require heat-resistance, electrical insulating materials, dimensional stability, and chemical resistance.

The prior patent document discloses a microfiltration membrane comprising a polysulfone-based polymer and a method for manufacturing the same, and more specifically, when a polysulfone-based polymer is used in the production of a microfiltration membrane or an ultrafiltration membrane, the shape and size of the surface or inside of the filter membrane It has been disclosed that it is possible to obtain properly adjusted pores (eg, Korean Patent Publication No. 2014-0054765).

However, these conventional polysulfone copolymers do not satisfy both heat resistance and processability (especially injection processability) at an excellent level. When the method of increasing the molecular weight of the polysulfone copolymer is selected to increase the heat resistance, the effect of improving the heat resistance due to the increase in molecular weight is not only insignificant, but also the viscosity average molecular weight is high, making it unsuitable as a filament for 3D printing.

Accordingly, there is a need to develop a polysulfone copolymer having excellent heat resistance and improved workability (especially injection processability) compared to a conventional polysulfone copolymer.

The present invention is intended to solve the problems of the prior art as described above, and provides a polysulfone copolymer having excellent heat resistance and improved processability (especially injection processability) and a method for manufacturing the same, compared to the conventional polysulfone copolymer. Let's do it as an assignment.

In order to solve the above technical problem, the present invention, a repeating unit derived from a diol component containing a phenolphthalein-based sulfone oligomer represented by the following formula (1); And a repeating unit derived from a dihalogenated sulfone compound.

[Formula 1]

In Formula 1, n is 1 to 21.

According to another aspect of the invention, (1) in the presence of an alkali metal salt catalyst, polymerizing a diol component and a dihalogenated sulfone compound comprising a phenolphthalein-based sulfone oligomer represented by Formula 1; (2) diluting the result of the polymerization reaction, and then removing the alkali metal halide therefrom; And (3) after the precipitation of the result of the diluted polymerization reaction, washing it; is provided a method for producing a polysulfone copolymer comprising a.

According to another aspect of the present invention, a molded article comprising the polysulfone copolymer is provided.

Since the polysulfone copolymer according to the present invention exhibits significantly improved heat resistance and excellent processability (especially injection processability) at the same time as conventional polysulfone copolymers, electrical insulating materials or various molding materials requiring heat resistance, Filament for 3D printing Alternatively, it can be suitably used for the use of a processed resin product such as a membrane.

Hereinafter, the present invention will be described in more detail.

The polysulfone copolymer of the present invention includes a repeating unit derived from a diol component containing a phenolphthalein-based sulfone oligomer represented by the following formula (1); And repeating units derived from dihalogenated sulfone compounds;

[Formula 1]

In Chemical Formula 1, n is 1 to 21, preferably 1 to 20, more preferably 1 to 19, and even more preferably 1 to 18. In Formula 1, when n is less than 1 or exceeds 21, the injection processability of the polysulfone resin may be deteriorated.

N in the formula (1) is an average value for the result of oligomer production. When preparing the phenolphthalein-based sulfone oligomer represented by Chemical Formula 1, while o = 1 or more oligomers are generated, unreacted phenolphthalein may remain, and n is an average value of phenolphthalein and oligomers.

In one embodiment, the number average molecular weight (Mn) range of the phenolphthalein-based sulfone oligomer represented by Formula 1 is preferably 800 to 11,600, more preferably 800 to 11,000, and even more preferably 800 to 10,000. If the number average molecular weight (Mn) of the phenolphthalein-based sulfone oligomer represented by Chemical Formula 1 is less than 800, the manufacturing reaction of the polysulfone copolymer occurs slowly, and injection processability at the time of injection molding using the polysulfone copolymer will be relatively low. If it exceeds 11,600, the molecules in the polysulfone copolymer are not uniformly distributed, and thus the partial thermal properties are different, so that the injection processability may be very poor during injection molding.

Although not particularly limited thereto, according to some embodiments of the present invention, the phenolphthalein-based sulfone oligomer may be represented by any one of the following Chemical Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the present invention, the diol component used in the production of the polysulfone copolymer may further include diol compounds other than the phenolphthalein-based sulfone oligomer represented by Formula 1, for example, aromatic diols, alicyclic diols, aliphatics Diols or combinations thereof may be further included, preferably aromatic diols may be further included.

Examples of the aromatic diol include bisphenol A, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy-diphenyl ether, and 3- (4 -Hydroxyphenoxy) phenol, bis (4-hydroxyphenyl) sulfide, or a combination thereof can be preferably used.

As the alicyclic diol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane dimethanol, adamantanediol, pentacyclopentadecanedi What is selected from the group consisting of methanol or a combination thereof can be preferably used.

As the aliphatic diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1, The one selected from the group consisting of 6-hexanediol, 1,4-cyclohexanedimethanol or a combination thereof can be preferably used.

As an alicyclic diol compound containing a 5-atom ring structure or a 6-atom ring structure usable in the present invention, specifically, an alicyclic diol compound represented by the following Chemical Formula 2 or 3 is mentioned.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ¹ and R ² each independently represent a cycloalkylene group having 4 to 20 carbon atoms or a cycloalkoxy group having 6 to 20 carbon atoms.

In one embodiment, the diol component used in the production of the polysulfone copolymer, preferably from 0.1 to 49.9 mol% of the phenolphthalein-based sulfone oligomer of Formula 1 based on 100 mol% of the total diol component and other diol compounds ( For example, aromatic diols, alicyclic diols and / or aliphatic diols) 50.1 to 99.9 mol% may be included, more preferably 0.2 to 49 mol% of phenolphthalein-based sulfone oligomers of Formula 1 and 51 to 99.9 mol of other diol compounds % May be included, more preferably 0.5 to 45 mol% of the phenolphthalein-based sulfone oligomer of Formula 1 and 55 to 99.5 mol% of other diol compounds. When the phenolphthalein-based sulfone oligomer of Chemical Formula 1 among all diol components is within the above-described range, the effect of simultaneously improving the heat resistance and injection processability of the polysulfone copolymer may be more excellent.

In the present invention, a dihalogenated diaryl sulfone can be preferably used as a dihalogenated sulfone compound used in the production of a polysulfone copolymer, and more specifically, 4,4'-dichlorodiphenylsulfone, 4,4 The one selected from the group consisting of '-difluorodiphenylsulfone or combinations thereof can be preferably used.

In the present invention, the amount of the diol component and the dihalogenated sulfone compound used in the production of the polysulfone copolymer is not particularly limited, but the amount of the dihalogenated sulfone compound is preferably 50 mol to 100 mol based on 100 mol of the total diol component. It may be 300 mol, more preferably 80 to 150 mol. If the amount of the dihalogenated sulfone is too small or too large compared to the total diol component used in the preparation of the polysulfone copolymer, the reaction between the diol component and the dihalogen sulfone reaction is not properly performed, which may cause difficulty in obtaining a desired molecular weight.

Additionally, other dihalogen compounds can be used in addition to the dihalogenated sulfone compounds. Preferably, 1 to 50 parts by weight of other dihalogen compounds may be used in addition to the dihalogenated sulfone compound with respect to 100 parts by weight of the dihalogenated sulfone compound. As the other dihalogen compound, 1,4-chlorobenzene, 1,4-diflurobenzene, bis (4-chlorophenyl) sulfide, di, (4-fluorophenyl) sulfide, or a combination thereof can be used. Can be.

According to another aspect of the invention, (1) in the presence of an alkali metal salt catalyst, polymerizing a diol component and a dihalogenated sulfone compound comprising a phenolphthalein-based sulfone oligomer represented by Formula 1; (2) diluting the result of the polymerization reaction, and then removing the alkali metal halide therefrom; And (3) after the precipitation of the result of the diluted polymerization reaction, washing it; is provided a method for producing a polysulfone copolymer comprising a.

As the alkali metal salt catalyst, one selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or mixtures thereof can be preferably used. There is no particular limitation on the amount of the catalyst used, but if the amount of the catalyst is too small, the reaction rate is slowed down. On the contrary, if the amount of the catalyst is too large, the residual catalyst may discolor the product or degrade the physical properties. According to one embodiment of the present invention, for example, based on 100 moles of diol component, 80 to 300 moles of catalyst, more preferably 100 to 200 moles may be used.

The polymerization reaction is, for example, at a temperature of 160 to 200 ° C. and atmospheric pressure for 5 to 10 hours, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc) , In reaction solvents such as dimethylformamide (DMF), sulfolane, diphenyl sulfone (DPS), dimethylsulfone (DMS), cosolvents such as chlorobenzene, tetrahydrofuran (THF) or mixed solvents thereof It may be performed in, but is not limited to. After the polymerization is completed, the polymerization reaction product is diluted (the same solvent as the polymerization solvent can be used as a dilution solvent), and from the diluted reaction product, an alkali metal halide (alkali metal from the alkali metal salt catalyst) generated during the reaction The salt of halogen from the dihalogenated sulfone compound, such as KCl), is removed by a method such as a decanter centrifuge centrifuge using a celite filter or specific gravity difference. Thereafter, the diluted and filtered reaction product is precipitated in a solvent (for example, alcohol or water such as methanol), and then washed with water or the like to prepare the polysulfone copolymer of the present invention.

Since the polysulfone copolymer of the present invention as described above has significantly better heat resistance and processability (especially injection processability) than the conventional polysulfone copolymer, various molding materials and filaments for 3D printing Alternatively, it can be suitably used for resin processing products such as membranes.

Accordingly, according to another aspect of the present invention, a molded article comprising the polysulfone copolymer of the present invention, preferably a filament or membrane for 3D printing may be provided.

The process for manufacturing the molded article may include solution spinning, casting (coating), extrusion or injection, but is not limited thereto, and the application field of the membrane provided according to the present invention is a water treatment R / O membrane, a fuel cell Electrolyte membranes, medical dialysis membranes, electrical and electronic connectors, automotive parts, and the like, and 3D printing filaments can be used for 3D printing, but are not limited thereto.

The method for producing a molded product such as a membrane using the polysulfone copolymer of the present invention is not particularly limited, and a method generally used for manufacturing a resin molded article can be used as it is or by appropriately modifying it.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[ Example ]

<Preparation of phenolphthalein-based sulfone oligomer>

Manufacturing example  One

1L 3-neck flask equipped with a stirrer, thermometer and condenser, phenolphthalein (2.0 mol), 4,4'-dichlorodiphenyl sulfone (DCDPS) (1.0 mol), potassium carbonate ( Potassium Carbonate (1.1 mol), N-Methyl-2-pyrrolidone (NMP) (10.1 mol) and Chlorobenzene (1.11 mol) were supplied. Under nitrogen purging, the temperature of the reaction mixture was rapidly raised to a reaction temperature of 160 ° C., and it was confirmed that chlorobenzene put as a co-solvent was discharged by azeotroping the reaction by-product H ₂ O over time. there was. After reacting at 192 ° C. for 4 hours, the final reaction mixture turned dark brown, and the viscosity of the reaction mixture was visually confirmed. After the final reaction mixture was cooled to room temperature, it was diluted in NMP, a dilution solvent prepared in advance. The diluted reaction mixture was passed through a decanter to separate the salt, which was then backprecipitated with a small amount of water. The precipitated product was washed and filtered in distilled water, and then dried to obtain a phenolphthalein-based sulfone oligomer compound represented by Chemical Formula 1-1.

[Formula 1-1]

Manufacturing example  2

A phenolphthalein-based sulfone oligomer compound represented by the following Chemical Formula 1-2 was obtained by performing the same method as in Production Example 1, except that the mole number of phenolphthalein was changed from 2.0 moles to 1.2 moles.

[Formula 1-2]

Manufacturing example  3

The phenolphthalein-based sulfone oligomer compound of Chemical Formula 1-3 was obtained by performing the same method as in Production Example 1, except that the mole number of phenolphthalein was changed from 2.0 moles to 1.1 moles.

[Formula 1-3]

Manufacturing example  4

A phenolphthalein-based sulfone oligomer compound of the following Chemical Formula 1-4 was obtained by performing the same method as in Production Example 1, except that the mole number of phenolphthalein was changed from 2.0 moles to 10 moles.

[Formula 1-4]

Manufacturing example  5

A phenolphthalein-based sulfone oligomer compound of the following Chemical Formula 1-5 was obtained by performing the same method as in Production Example 1, except that the mole number of phenolphthalein was changed from 2.0 moles to 1.05 moles.

[Formula 1-5]

In Preparation Examples 1 to 5, the number average molecular weights of the prepared compounds together with the contents of reactants, catalysts, and solvents used for preparing the phenolphthalein-based sulfone oligomer compounds are shown in Table 1 below.

<Preparation of polysulfone copolymer>

Example  One

Bisphenol A (0.8 mol) in a 1 L 3-neck flask equipped with a stirrer, thermometer, and condenser, and a phenolphthalein-based sulfone oligomer compound (0.2 mol) of Formula 1-1 prepared in Preparation Example 1, 4,4'-dichlorodiphenyl Sulfone (1.0 mole), potassium carbonate (1.1 mole), N-methyl-2-pyrrolidone (NMP) (10.1 mole) and chlorobenzene (1.11 mole) were fed. Under nitrogen purging, the reaction mixture was rapidly heated to a reaction temperature (160 ° C.), and it was confirmed that chlorobenzene, which was added as a co-solvent, was discharged by azeotroping the reaction by-product H ₂ O over time. After reacting at a temperature of 192 ° C., the final reaction mixture turned dark brown, and the viscosity of the reaction mixture could be visually confirmed After cooling at room temperature, the final reaction mixture was diluted in a solvent NMP prepared in advance. The diluted reaction mixture was passed through a decanter to separate the salt, followed by back-precipitation with a small amount of water.The precipitated product was washed and filtered in distilled water, and then dried to dry a polysulfone copolymer (yield: 83%). Was obtained.

Example  2

The content of bisphenol A was changed from 0.8 mol to 0.6 mol, the content of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1 was changed from 0.2 mol to 0.4 mol, and the content of potassium carbonate was changed from 1.1 mol to 1.3 mol. A polysulfone copolymer (yield: 87%) was obtained by performing the same method as in Example 1, except that it was changed.

Example  3

The content of bisphenol A was changed from 0.8 mol to 0.9 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.1 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-2 prepared in Preparation Example 2 A polysulfone copolymer (yield: 85%) was obtained in the same manner as in Example 1, except that was used.

Example  4

The content of bisphenol A was changed from 0.8 mol to 0.95 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.05 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-2 prepared in Preparation Example 2 Was used, and the polysulfone copolymer (yield: 92%) was obtained in the same manner as in Example 1, except that the content of potassium carbonate was changed from 1.1 mol to 1.2 mol.

Example  5

The content of bisphenol A was changed from 0.8 mol to 0.95 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.05 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-3 prepared in Preparation Example 3 Was used, and the polysulfone copolymer (yield: 85%) was obtained in the same manner as in Example 1, except that the content of potassium carbonate was changed from 1.1 mol to 1.7 mol.

Example  6

The content of bisphenol A was changed from 0.8 mol to 0.99 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.01 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-3 prepared in Preparation Example 3 Was used, and the polysulfone copolymer (yield: 91%) was obtained in the same manner as in Example 1, except that the content of potassium carbonate was changed from 1.1 mol to 1.3 mol.

Table 2 below shows the measured values of physical properties of each polysulfone copolymer, together with the contents of reactants, catalysts, and solvents used for the preparation of polysulfone copolymers in Examples 1 to 5 above.

Comparative example  One

Polysulfone was carried out in the same manner as in Example 1, except that the content of bisphenol A was changed from 0.8 mol to 1 mol, and the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1 was not used. The copolymer (yield: 80%) was obtained.

Comparative example  2

SOLVAY 3500: Polysulfone copolymer for membranes manufactured by Solvay

Comparative example  3

The content of bisphenol A was changed from 0.8 mol to 0.9 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.1 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-4 prepared in Preparation Example 4 A polysulfone copolymer (yield: 62%) was obtained in the same manner as in Example 1, except that was used.

Comparative example  4

The content of bisphenol A was changed from 0.8 mol to 0.6 mol, and instead of the phenolphthalein-based sulfone oligomer compound of Formula 1-1 prepared in Preparation Example 1, 0.4 mol of the phenolphthalein-based sulfone oligomer compound of Formula 1-5 prepared in Preparation Example 5 A polysulfone copolymer (yield: 82%) was obtained by performing the same method as in Example 1, except that was used.

In Comparative Examples 1 to 4, the measurement values of the physical properties of each polysulfone copolymer are shown in Table 3, together with the contents of reactants, catalysts, and solvents used for the preparation of the polysulfone copolymer.

<Method for measuring physical properties>

(1) Glass transition temperature (Tg): Perkin Elmer's Diamond DSC (Differential Scanning Calorimetry) was used to measure the glass transition temperature of the polysulfone copolymer.

(2) Viscosity average molecular weight (IV): The viscosity of the methylene chloride solution was measured at 20 ° C using a Ubbelohde Viscometer.

(3) Injection processability: The defect rate during injection molding at a temperature of 320 ° C. was measured, and evaluated as follows according to the defect rate.

-Excellent: When the appearance of the molded product is clean and the defect rate is less than 0% to 3%

-Poor: When the defect rate is more than 3% and less than 30%

-Very poor: When the defective rate is more than 30%

As described in Table 2, in the case of the polysulfone copolymers of Examples 1 to 6 according to the present invention, the production yield was excellent at 70% or more, and the glass transition temperature was 200 ° C or more, which was excellent in heat resistance, and injection molding. The defect rate was less than 3%, so the injection processability was excellent.

On the other hand, as shown in Table 3, in Comparative Examples 1 and 2, the glass transition temperature was less than 200 ° C, and the heat resistance was low, and in Comparative Example 3, the injection processability was poor, and in Comparative Example 4, the injection processability was very poor. Did.

Claims (11)

A repeating unit derived from a diol component containing a phenolphthalein-based sulfone oligomer represented by Formula 1 below; And
A repeating unit derived from a dihalogenated sulfone compound; containing,
Polysulfone copolymer:
[Formula 1]

In Formula 1, n is 1 to 21. The polysulfone copolymer according to claim 1, wherein the number average molecular weight (Mn) range of the phenolphthalein-based sulfone oligomer represented by Chemical Formula 1 is 800 to 11,600. The polysulfone copolymer according to claim 1, wherein the diol component further comprises a diol compound other than the phenolphthalein-based sulfone oligomer represented by the formula (1). The polysulfone copolymer according to claim 3, wherein the diol compound other than the phenolphthalein-based sulfone oligomer represented by Formula 1 is selected from aromatic diols, alicyclic diols, aliphatic diols, or combinations thereof. 5. The method of claim 4, wherein the aromatic diol is bisphenol A, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy-diphenyl ether, 3 -(4-hydroxyphenoxy) phenol, bis (4hydroxyphenyl) sulfide, or combinations thereof; Alicyclic diols are 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol or these Is selected from the group consisting of; Aliphatic diol is ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexane A polysulfone copolymer selected from the group consisting of diols, 1,4-cyclohexanedimethanol or combinations thereof. According to claim 3, Diol component, based on 100 mol% of the total diol component, 0.1 to 49.9 mol% of phenolphthalein-based sulfone oligomers of Formula 1 and 50.1 to 99.9 mol of diol compounds other than the phenolphthalein-based sulfone oligomers represented by Formula 1 %, Comprising a polysulfone copolymer. The polysulfone copolymer according to claim 1, wherein the dihalogenated sulfone compound is selected from the group consisting of 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone or combinations thereof. (1) polymerizing a diol component and a dihalogenated sulfone compound comprising a phenolphthalein-based sulfone oligomer represented by the following Chemical Formula 1 in the presence of an alkali metal salt catalyst;
(2) after diluting the polymerization reaction product, removing alkali metal halide therefrom; And
(3) After precipitating the result of the diluted polymerization reaction, washing it;
Manufacturing method of polysulfone copolymer:
[Formula 1]

In Formula 1, n is 1 to 21. The method of claim 8, wherein the alkali metal salt catalyst is selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or mixtures thereof. A molded article comprising the polysulfone copolymer of claim 1. The molded article according to claim 10, which is a filament or membrane for 3D printing.