KR101973671B1 - Method for preparing polysulfone copolymer and polysulfone copolymer for 3d printing prepared by the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a polysulfone copolymer and the polysulfone copolymer for 3D printing manufactured by the same. More specifically, the present invention relates to the method for manufacturing the polysulfone copolymer which contains a sulfone-based compound as a repeating unit and an anhydrosugar alcohol as a biogenic material, thereby being eco-friendly, and has a low viscosity-average molecular weight than that of an existing polysulfone copolymer, thereby being able to manufacture the polysulfone copolymer suitable for processing characteristics required for 3D printing filaments at an improved yield, and the polysulfone copolymer for 3D printing manufactured by the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for producing a polysulfone copolymer, and a polysulfone copolymer for 3D printing produced by the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a process for producing a polysulfone copolymer and a polysulfone copolymer for 3D printing produced thereby. More particularly, the present invention relates to a process for producing a polysulfone copolymer which is eco- A polysulfone copolymer having a low viscosity average molecular weight as compared with conventional polysulfone copolymers and suitable for the processing characteristics required for 3D printing filaments can be produced at an improved yield and a polysulfone copolymer for 3D printing produced thereby .

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrosugar alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared by utilizing hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid- -2012-0066904). Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, alcohol-free alcohol has attracted a great deal of attention due to its versatility and its use in real industry is increasing.

Polysulfone is generally manufactured by using raw materials derived from petroleum resources. Due to the exhaustion of finite petroleum resources, it is required to provide polysulfone using raw materials obtained from biomass resources such as plants. In addition, there is concern that global warming due to increase and accumulation of carbon dioxide emissions may cause climate change, etc., and carbon dioxide-neutral plant-derived monomers are used to prevent carbon dioxide from being emitted even after disposal. Development of polysulfone as a raw material is required.

Korean Patent Laid-Open No. 10-2016-0025439 discloses polysulfone copolymers which include anhydrosugar alcohol as repeating units to improve environmental friendliness and are excellent in heat resistance and chemical resistance, and are suitable for use in membrane production, and a method for producing the same . However, the polysulfone copolymer disclosed in this document has a high viscosity average molecular weight and is therefore unsuitable as a filament for 3D printing, and the yield thereof is unsatisfactory.

Accordingly, there is a need for a polysulfone copolymer suitable as a filament for 3D printing that can solve the problem of resource depletion, is eco-friendly, and has a low viscosity average molecular weight at the same time, and a method capable of producing the polysulfone copolymer at an improved yield.

SUMMARY OF THE INVENTION The present invention has been made to overcome the problems of the prior art as described above, and it is an object of the present invention to provide a polysulfone aerofoil suitable for 3D printing filaments because it can solve the problem of resource depletion, It is another object of the present invention to provide a method for producing a polysulfone copolymer for 3D printing by an improved yield.

In order to solve the above-mentioned technical problems, the present invention provides a process for producing a diol compound comprising the steps of: (1) polymerizing a diol component containing anhydrosugar alcohol and a dihalogenated sulfone compound in the presence of an alkali metal salt catalyst for 3 to 9.5 hours; (2) diluting the polymerization reaction product with an organic solvent, passing the diluted reaction product through a decanter operating at a decanter speed of 15 to 55 Hz, and removing the alkali metal halide from the reaction product; And (3) precipitating the result of the diluted polymerization reaction, followed by washing the resultant. The present invention also provides a process for producing a polysulfone copolymer.

According to another aspect of the present invention there is provided a process for the production of a polymer comprising repeating units derived from a diol component prepared according to the process and comprising anhydrosugar alcohol; And a dihalogenated sulfone compound, and having a viscosity-average molecular weight of from 0.35 to 0.60 based on IV, is provided.

According to another aspect of the present invention, there is provided a filament for 3D printing comprising the polysulfone copolymer.

According to the present invention, a polysulfone copolymer suitable as a filament for 3D printing can be produced at an improved yield because it can solve the problem of resource depletion, is eco-friendly, and at the same time has a lower viscosity average molecular weight than conventional polysulfone copolymers.

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

The process for producing a polysulfone copolymer of the present invention comprises the steps of: (1) polymerizing a diol component containing anhydrosugar alcohol and a dihalogenated sulfone compound in the presence of an alkali metal salt catalyst for 3 to 9.5 hours; (2) diluting the polymerization reaction product with an organic solvent, passing the diluted reaction product through a decanter operating at a decanter speed of 15 to 55 Hz, and removing the alkali metal halide from the reaction product; And (3) precipitating the result of the diluted polymerization reaction, followed by washing.

In the step (1) of the process for producing a polysulfone copolymer of the present invention, the polymerization reaction with the diol component containing anhydrosugar alcohol and the dihalogenated sulfone compound is carried out for 3 to 9.5 hours, preferably for 4 to 9 hours , The reaction time becomes longer as the content of anhydrosugar alcohol in the diol component is larger. When the polymerization reaction time is shorter than 3 hours, there is a problem that the viscosity average molecular weight does not sufficiently increase. When the polymerization reaction time exceeds 9.5 hours, the viscosity average molecular weight becomes too large, which is not suitable as a filament for 3D printing.

In one embodiment, the polymerization reaction in the step (1) may be carried out at a temperature of, for example, 160 to 200 ° C and an atmospheric pressure.

In one embodiment, the polymerization in step (1) is carried out in the presence of a base such as N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), dimethyl acetamidate (DMAc), dimethylformamide ), Sulfolane, diphenylsulfone (DPS), dimethylsulfone (DMS), or a mixture thereof, but is not limited thereto. The reaction solvent may further include, but is not limited to, a co-solvent selected from the group consisting of chlorobenzene, tetrahydrofuran (THF), and mixtures thereof.

In one embodiment, the alkali metal salt catalyst used in step (1) may be selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or mixtures thereof. There is no particular limitation on the amount of the catalyst to be used, but if the amount of the catalyst is too small, the reaction rate becomes slow. On the other hand, if the amount is too large, the residual catalyst may deteriorate the physical properties of the product. According to one embodiment of the present invention, for example, based on 100 mole of the diol component, 80 to 300 moles of catalyst, more preferably 100 to 130 moles, may be used.

The anhydrous alcohol used in the step (1) is generally selected from a compound obtained by adding hydrogen to a reducing end group of a saccharide, which is generally called hydrogenated sugar or sugar alcohol, and removing one or more water molecules ≪ / RTI > As the anhydrosugar alcohol, dianhydrohexitol, which is a dehydrate of hexitol, can be preferably used. More preferably, the anhydrosugar alcohol is isosorbide (1,6-dianhydroisorbitol), isomannide (1, 6-dianhydro mannitol), isodide (1,6-dianhydroiditol), or a mixture thereof.

In one embodiment, the diol component used in the step (1) may further include a diol compound other than the anhydrosugar alcohol such as an aromatic diol, an alicyclic diol, an aliphatic diol, or a combination thereof, May further include an aromatic diol. Examples of the aromatic diol include bisphenol A, 4,4'-dihydroxy-diphenylsulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy- -Hydroxyphenoxy) phenol, bis (4-hydroxyphenyl) sulfide, or a combination thereof; The alicyclic diol includes 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecane di Methanol, or a combination thereof; Examples of the aliphatic diol include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 6-hexanediol, 1,4-cyclohexanedimethanol, or a combination thereof can be preferably used.

In one embodiment, examples of the alicyclic diol compound having a 5-atomic ring structure or a 6-atomic ring structure usable in the present invention include an alicyclic diol compound represented by the following formula (1) or .

[Chemical Formula 1]

(2)

In the general formulas (1) and (2), R ¹ and R ² each independently represent a cycloalkyl 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 step (1) may include 0.1 to 99 mol% of an alcohol without anhydride, based on 100 mol% of the total diol component, and a diol compound other than anhydrosugyl alcohol , Alicyclic diol and / or aliphatic diol), more preferably from 1 to 90 mol% of an alcohol without anhydride and from 10 to 99 mol% of a diol compound other than an alcohol without anhydride, Still more preferably from 5 to 80 mol% of an alcohol without anhydride and from 20 to 95 mol% of a diol compound other than an alcohol without anhydride.

In one embodiment, as the dihalogenated sulfone compound in the above step (1), dihalogenated diaryl sulfone is preferably used, and more specifically, 4,4'-dichlorodiphenyl sulfone, 4,4'-di Fluorodiphenyl sulfone, or a combination thereof, can be preferably used.

In the present invention, there is no particular limitation on the ratio of the diol component to the dihalogenated sulfone compound used in the production of the polysulfone copolymer. However, the amount of the dihalogenated sulfone compound is preferably 50 moles or more, 300 moles, and more preferably 80 moles to 150 moles. If the amount of the dihalogenated sulfone is excessively small or excessively larger than the total diol component used in the production of the polysulfone copolymer, the diol component and the dihalogen sulfone reaction may not be appropriately performed, which may make it difficult to obtain a desired molecular weight.

In one embodiment, other dihalogen compounds may be used in addition to the dihalogenated sulfone compound in the step (1). Preferably, in addition to the dihalogenated sulfone compound, 1 to 50 parts by weight of other dihalogen compounds may be used relative to 100 parts by weight of the dihalogenated sulfone compound. Examples of the other dihalogen compounds include 1,4-dichlorobenzene, 1,4-difluorobenzene, bis (4-chlorophenyl) sulfide, di (4-fluorophenyl) sulfide, have.

Although not particularly limited thereto, according to some embodiments of the present invention, the polysulfone copolymer of the present invention may include a structure represented by any one of the following formulas (3) to (6) in the copolymer And the marked part represents a repeating unit).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the step (2) of the method for producing a polysulfone copolymer of the present invention, the polymerization reaction product obtained in the above step (1) is diluted in an organic solvent, and the diluted reaction product is decanter operated at a decanter speed of 15 to 55 Hz And the alkali metal halide is removed from the reaction product.

In one embodiment, the diluent solvent used in step (2) is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide But are not limited to, DMF, sulfolane, diphenylsulfone (DPS), dimethylsulfone (DMS), or mixtures thereof. The diluent solvent may further include, but is not limited to, a co-solvent selected from the group consisting of chlorobenzene, tetrahydrofuran (THF), and mixtures thereof. In one embodiment, the diluting solvent may be the same as the polymerization reaction solvent used in the step (1).

In the step (2), the diluted reaction product is passed through a decanter operating at a decanter speed of 15 to 55 Hz to remove the alkali metal halide (alkali metal halide from the alkali metal salt catalyst and dihalogenated sulfone compound For example, KCl) is removed from the reaction product.

In the present invention, the " decanter vehicle speed " is a parameter corresponding to the rotational speed difference between the decanter inner drum and the outer drum, expressed by the following equation:

Vehicle speed (Hz) = [External speed (Hz) - Internal speed (Hz)] / 50

In the step (2) of the process for producing a polysulfone copolymer of the present invention, the decanter vehicle speed may be 15 to 55 Hz, more specifically 15 to 50 Hz, and more particularly 20 to 50 Hz. If the decanter vehicle speed is less than 15 Hz, the salt removal may not be performed well, and if it exceeds 55 Hz, the yield may be lowered.

In the step (3) of the method for producing a polysulfone copolymer of the present invention, after the result obtained in the step (2) is precipitated, it is washed.

In one embodiment, the precipitation in step (3) may be carried out in an alcohol solvent such as, for example, methanol. In another embodiment, the precipitation may be carried out in such a way that a small amount of water is added to the diluted reaction mixture obtained as a result of step (2) to precipitate back. The resultant precipitate may be washed using water (for example, distilled water) or the like.

The polysulfone copolymer produced according to the above-described method can solve the problem of depletion of petroleum resources, which is a finite resource, because the polysulfone copolymer contains a sulfonic compound as a repeating unit and an anhydrosugar alcohol as a biogenic material, And is environmentally friendly because it does not emit carbon dioxide. Also, it can be suitably used as a filament for 3D printing with a low viscosity average molecular weight (for example, IV-based viscosity average molecular weight of 0.35 to 0.60) compared with conventional polysulfone copolymers.

In the present invention, " IV reference viscosity average molecular weight " means a value obtained by determining the relative viscosity and the specific viscosity by measuring the elution time of the solvent in which the polymer is dissolved and the pure solvent, and calculating the H viscosity equation based on this value. The larger the value.

Accordingly, in accordance with another aspect of the present invention, there is provided a process for preparing a polymer comprising repeating units derived from a diol component prepared according to the process of the present invention as described above and comprising anhydrosugar alcohol; A polysulfone copolymer for 3D printing having a viscosity average molecular weight of from 0.35 to 0.60 on the basis of IV and a repeating unit derived from a dihalogenated sulfone compound and a filament for 3D printing comprising the polysulfone copolymer do.

The IV standard viscosity average molecular weight of the polysulfone copolymer for 3D printing may be 0.35 to 0.60, preferably 0.35 to 0.55, and more preferably 0.35 to 0.50.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  One

(ISB) (0.05 mole), 4,4'-dichlorodiphenyl sulfone (DCDPS) (1.0 mole), and bisphenol A were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. N-methyl-2-pyrrolidone (NMP) (10.1 moles), and chlorobenzene (1.11 moles) were added to a solution of bisphenol A (BPA) (0.95 mole), potassium carbonate . The reaction mixture was heated at a high rate to a reaction temperature (160 ° C) under nitrogen purge to confirm that the chlorobenzene added to the co-solvent was evacuated by azeotropic distillation of water (H ₂ O) I could. After reaction at 192 ° C for 4 hours, the final reaction mixture turned dark brown, and the viscosity of the reaction mixture was visually confirmed. The final reaction mixture was cooled at room temperature and then diluted with NMP solvent prepared in advance. The diluted polymer solution was passed through a decanter (decanter vehicle speed: 20 Hz) to separate the salt, and the diluted reaction mixture was reprecipitated with a small amount of water. The precipitated product was washed and filtered in distilled water and then dried to obtain a polysulfone copolymer containing isosorbide (ISB) (5 mole%).

Example 2

(ISB) (0.1 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.9 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 moles), N-methyl-2-pyrrolidone (NMP) (10.1 moles) and chlorobenzene (1.11 moles) were fed and the reaction time was changed from 4 hours to 6 hours. Was carried out in the same manner as in Example 1, except that the amount of isosorbide (ISB) (10 mole%) was changed as shown in Table 1, to obtain a polysulfone copolymer containing 10 mole% of isosorbide (ISB).

Example 3

(ISB) (0.15 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.85 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 moles), N-methyl-2-pyrrolidone (NMP) (10.1 moles) and chlorobenzene (1.11 moles), the reaction time was changed from 4 hours to 7 hours, (ISB) (15 mole%) was obtained in the same manner as in Example 1, except that the amount of isosorbide (ISB) was changed as shown in Table 1.

Example 4

(ISB) (0.2 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.8 mole) were placed in a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 moles), N-methyl-2-pyrrolidone (NMP) (10.1 moles) and chlorobenzene (1.11 moles) were fed into the reactor, the reaction time was changed from 4 hours to 8 hours, (ISB) (20 mole%) was obtained in the same manner as in Example 1, except that the amount of isosorbide (ISB) was changed as shown in Table 1.

Example 5

(ISB) (0.25 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.75 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 moles), N-methyl-2-pyrrolidone (NMP) (10.1 moles) and chlorobenzene (1.11 moles) were fed and the reaction time was changed from 4 hours to 8 hours and 30 minutes. Was carried out in the same manner as in Example 1, except that the vehicle speed was changed as shown in Table 1 to obtain a polysulfone copolymer containing isosorbide (ISB) (25 mole%).

Example 6

(ISB) (0.3 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.7 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 moles), N-methyl-2-pyrrolidone (NMP) (10.1 moles) and chlorobenzene (1.11 moles) were fed, the reaction time was changed from 4 hours to 9 hours, (ISB) (30 mole%) was obtained in the same manner as in Example 1, except that the amount of isosorbide (ISB) was changed as shown in Table 1.

Example 7

(ISB) (0.05 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.95 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. , Potassium carbonate (1.1 mole), N-methyl-2-pyrrolidone (NMP) (10.1 mole) and chlorobenzene (1.11 mole) and the reaction time was varied from 4 hours to 5 hours. (ISB) (5 mole%) was obtained in the same manner as in Example 1, except that the amount of isosorbide (ISB) was changed as shown in Table 1.

Example 8

(ISB) (0.3 mole), 4,4'-dichlorodiphenylsulfone (DCDPS) (1.0 mole), and bisphenol A (BPA) (0.7 mole) were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a condenser. Except that potassium carbonate (1.1 mole), N-methyl-2-pyrrolidone (NMP) (10.1 mole) and chlorobenzene (1.11 mole) were supplied and the reaction time was changed from 4 hours to 9 hours Was carried out in the same manner as in Example 1 to obtain a polysulfone copolymer containing isosorbide (ISB) (30 mole%).

[Table 1]

Comparative Example 1

(ISB) (5 mole%) was prepared by changing the reaction time from 4 hours to 2 hours and varying the vehicle speed of the decanter as shown in Table 2, in the same manner as in Example 1, Copolymer was obtained.

Comparative Example 2

Except that the reaction time was changed from 7 hours to 10 hours and the vehicle speed of the decanter was changed as shown in Table 2 to obtain a polysulfone containing isosorbide (ISB) (15 mole%) Copolymer was obtained.

Comparative Example 3

A polysulfone copolymer containing isosorbide (ISB) (5 mole%) was obtained in the same manner as in Example 1 except that the decenter was changed in vehicle speed as shown in Table 2.

Comparative Example 4

The polysulfone copolymer containing isosorbide (ISB) (30 mole%) was obtained in the same manner as in Example 6 except that the vehicle speed of the decanter was changed as shown in Table 2.

Comparative Example 5

A polysulfone copolymer containing isosorbide (ISB) (5 mole%) was obtained in the same manner as in Example 1 except that the decenter was changed in vehicle speed as shown in Table 2.

Comparative Example 6

The polysulfone copolymer containing isosorbide (ISB) (30 mole%) was obtained in the same manner as in Example 6 except that the vehicle speed of the decanter was changed as shown in Table 2.

[Table 2]

The viscosity average molecular weight (IV standard), glass transition temperature (Tg), and filament processing characteristics for a 3D printer of the copolymers produced in the above Examples and Comparative Examples were measured or evaluated and are shown in Table 3 below.

Viscosity average molecular weight (IV basis)

The viscosity of the methylene chloride solution was measured at 20 DEG C using a Ubbelohde Viscometer.

The glass transition temperature (Tg)

The glass transition temperature was measured using Diamond DSC (Differential Scanning Calorimetry) of Perkin Elmer in order to confirm that the heat resistance property was improved as the free alcohol content was increased. Specifically, the temperature was raised from 30 ° C to 300 ° C at a rate of 10 ° C per minute, held for 1 minute, cooled to 30 ° C at a rate of 10 ° C per minute, held for 2 minutes, and then heated to 300 ° C at a rate of 10 ° C per minute The glass transition temperature of the polysulfone copolymer was measured.

Characteristics of filament processing for 3D printers

The following items were evaluated as filament processing characteristics during filament extrusion.

1. Evaluation of gas generation: When the filament was extruded, the gas was visually inspected in the filament passing through the die, and it was evaluated as No occurrence (5), Little occurrence (3), Most occurrence (1). When the byproducts of the synthesized polymer are large or decomposed, gas is generated.

2. Evaluation of uniform strand retention of filaments: Evaluation was made as to whether the strands having a uniform thickness were extruded when the filament extruded was rated as Excellent (5), Normal (3) or Bad (1). If the flowability is too good, the strand becomes thin, and if the flowability is poor, the strand is not stretched but broken.

[Table 3]

As shown in Table 3 above, the polysulfone copolymers according to Examples 1 to 8 were excellent in the production yield of 70% or more, and no gas was generated even when the filament for 3D printing using these copolymers was extruded , And was discharged as a uniform strand upon extrusion of the filament.

However, in the case of Comparative Examples 1, 2 and 4, no uniform strands were discharged when the filament for 3D printing using the polysulfone copolymer was extruded. In the case of Comparative Examples 2, 3 and 4, 3D printing using a polysulfone copolymer In the case of Comparative Examples 5 and 6, the filament processing characteristics were excellent, but the production yield of the polysulfone copolymer was inferior to less than 70%.

Claims (9)

(1) polymerizing, in the presence of an alkali metal salt catalyst, a diol component comprising anhydrosugar alcohol and a dihalogenated sulfone compound for 4 to 9 hours;
(2) diluting the polymerization reaction product with an organic solvent, passing the diluted reaction product through a decanter operating at a decanter speed of 20 to 50 Hz, and removing the alkali metal halide from the reaction product; And
(3) precipitating the diluted polymerization reaction product and then washing it.
And having a viscosity average molecular weight of from 0.35 to 0.5 based on IV. The process according to claim 1, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, or mixtures thereof. The process for producing a polysulfone copolymer according to claim 1, wherein the diol component further comprises a diol compound other than anhydrosugar alcohol. The process for producing a polysulfone copolymer according to claim 3, wherein the diol compound other than anhydrosugar alcohol is an aromatic diol, an alicyclic diol, an aliphatic diol or a combination thereof. 5. The method of claim 4,
Wherein the aromatic diol is selected from the group consisting of bisphenol A, 4,4'-dihydroxy-diphenylsulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy- Phenoxy) phenol, bis (4-hydroxyphenyl) sulfide, or a combination thereof,
It is preferable that the alicyclic diol is 1,4-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,2-cyclohexane dimethanol, tricyclodecane dimethanol, adamantanediol, pentacyclopentadecane dimethanol, ≪ / RTI >
It is preferred that the aliphatic diol is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5- Diol, 1,4-cyclohexane dimethanol, or a combination thereof. The preparation of polysulfone copolymer according to claim 1, wherein the diol component comprises from 0.1 to 99 mol% of anhydrosugar alcohol and from 1 to 99.9 mol% of a diol compound other than anhydrosugar alcohol, based on 100 mol% Way. The process for producing a 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 a combination thereof. 8. A process for the preparation of a copolymer comprising repeating units derived from a diol component prepared according to the process of any one of claims 1 to 7 and comprising anhydrosugar alcohol; And a dihalogenated sulfone compound, and having a viscosity average molecular weight of from 0.35 to 0.5 based on IV. A filament for 3D printing comprising the polysulfone copolymer of claim 8.