TWI652254B - Method for preparing compound and method for preparing polymer employing the same - Google Patents

Abstract

The present disclosure provides a method of preparing a compound and a method of preparing a polymer comprising the same. The method for producing the compound comprises reacting a compound of the formula (I) with a compound of the formula (III) in the presence of a compound of the formula (II) to obtain a structure represented by the formula (IV). compound of R ³ -SSR ³ (III) Wherein Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ² is hydroxy, C _1-6 An alkyl group, a phenyl group, or a tolyl group; and, R ³ is independently a C _1-6 alkyl group, a C _5-8 cycloalkyl group, or a C _2-6 alkoxyalkyl group.

Description

Method for preparing compound and preparation method of polymer containing same

The present invention relates to a process for the preparation of a compound and a process for the preparation of a polymer comprising the same.

Polyether sulfone (PES) or polythioether sulfone (PTES) has excellent physical properties such as heat resistance, chemical resistance, fire resistance, non-toxicity, and electrical insulation properties, so it is widely used in computers. Components, automotive components, food containers, and industrial fibers with chemical resistance.

However, since the conventional polyether oxime, polythioxanthene, or a monomer thereof is mainly prepared by a halogen process, in addition to a low yield, a halogen-containing by-product which cannot be recovered is generated, causing environmental pollution.

According to an embodiment of the present disclosure, the present disclosure provides a method for producing a compound comprising: subjecting a compound of the formula (I) to a compound of the structure of the formula (III) in the presence of a compound of the structure represented by the formula (II) Reaction to obtain a compound of the structure represented by formula (IV) R3-SSR ³ (III) Wherein Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ² is hydroxy, C _{1- 6} alkyl, phenyl, or tolyl; and R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl, or C _2-6 alkoxyalkyl.

According to an embodiment of the present disclosure, the present disclosure also provides a method for preparing a polymer comprising a compound having the structure of the formula (I) in the presence of a compound of the structure represented by the formula (II) and a compound of the formula (III). The reaction is carried out to obtain a compound of the formula (IV); the compound of the structure of the formula (IV) is reacted with a compound A to obtain a compound of the formula (V) wherein the compound A is nitric acid, sulfuric acid, Acetic acid, hydrogen peroxide, or a mixture thereof; and reacting a compound of the formula (V) with a compound of the formula (VI) to obtain a polymer having a repeating unit of the formula (VII) R ³ -SSR ³ (III) Wherein Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ² is hydroxy, C _{1- 6} alkyl, phenyl, or tolyl; R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl, or C _2-6 alkoxyalkyl; R ⁵ is a hydroxyl group, a C _1-6 alkyl group, a phenyl group, or a tolyl group; and, Ar ² is a substituted or unsubstituted divalent aromatic group.

The present disclosure provides a method for preparing a compound. The reaction starting material or the catalyst used in the preparation method of the compound does not contain halogen, except that halogen-containing by-products can be avoided, and residual halogen-containing compounds can be avoided in the obtained compound. . Therefore, the method for preparing the compound of the present disclosure does not require an additional step to remove the halogen-containing by-product or the residual halogen compound, which can reduce the production cost and increase the process yield, and obtain a halogen-free monomer which can be used in the subsequent polymerization process.

In addition, the present disclosure also provides a method for preparing a polymer (for example, polyether sulfone (PES) or polythioether sulfone (PTES)), a method for preparing the monomer of the polymer, and the polymerization. The reaction starting materials used in the preparation method do not contain halogen, except that halogen-containing by-products can be avoided, and residues can be avoided. A halogen-containing compound is included in the obtained compound. Therefore, the method for preparing the polymer of the present disclosure does not require an additional step to remove the halogen-containing by-product or the residual halogen compound, which can reduce the production cost and increase the process yield, thereby obtaining a halogen-free polymer. In addition, the preparation method of the polymer disclosed in the present invention is an electrophilic polymerization reaction of a reactive monomer in an acidic environment, and combined with a post-polymerization oxidation technique, the molecular weight of the obtained polymer can be greatly improved, and the obtained polymer has a comparatively high molecular weight. Low molecular weight distribution (PDI).

According to an embodiment of the present disclosure, the present disclosure provides a method for preparing a compound which can be used as a subsequent polymerization process (for example, a polyether sulfone (PES) or a polythioether sulfone (PTES) polymerization process). Reaction monomer. The method for producing the compound comprises reacting a compound of the formula (I) with a compound of the formula (III) in the presence of a compound of the formula (II) to obtain a structure represented by the formula (IV). compound of R ³ -SSR ³ (III) Wherein Ar ¹ may be a substituted or unsubstituted aryl group; X may be -O-, -S-, or -NH-; R ¹ may independently be hydrogen or a C _1-6 alkyl group; R ² may be a hydroxyl group, C _{a 1-6} alkyl group, a phenyl group, or a tolyl group; and, R ³ may independently be a C _1-6 alkyl group, a C _5-8 cycloalkyl group, or a C _2-6 alkoxyalkyl group. . Herein, the substituted aromatic group means that the hydrogen on at least one of the aromatic groups is substituted by a C _1-6 alkyl group.

According to an embodiment of the present disclosure, wherein Ar ¹ may be a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a thienyl group, an indolyl group. ), phenanthrenyl, indenyl, anthracenyl, or fluorenylene. Wherein, substituted phenyl group, biphenyl group, naphthyl group, thienyl group, indolyl, phenanthrenyl, indenyl , anthracenyl, or fluorenylene means that the hydrogen on at least one of the aromatic groups is replaced by a C _1-6 alkyl group.

According to an embodiment of the present disclosure, the C _1-6 alkyl group may be a linear or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl. (isopropyl), n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, or hexyl.

According to an embodiment of the present disclosure, R ¹ may independently be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl. (t-butyl), sec-butyl, isobutyl, pentyl, or hexyl.

According to an embodiment of the present disclosure, R ² may be a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group ( T-butyl), sec-butyl, isobutyl, pentyl, hexyl, phenyl, or tolyl.

According to an embodiment of the present disclosure, R ³ may independently be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl (t -butyl), sec-butyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or , where 1≦n≦5, 0≦m≦4, and 1≦n+m≦5.

According to an embodiment of the present disclosure, the compound of the structure represented by the formula (I) may be , ,or Wherein R ^{1 is} as defined above; and R ⁴ is independently hydrogen or C _1-6 alkyl.

According to an embodiment of the present disclosure, R ⁴ may independently be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl. (t-butyl), sec-butyl, isobutyl, pentyl, or hexyl.

According to an embodiment of the present disclosure, the compound of the structure represented by the formula (II) may be sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid. Or a combination of the above.

According to an embodiment of the present disclosure, the compound of the structure represented by the formula (III) may be

According to an embodiment of the present disclosure, the present disclosure provides a method for preparing a compound of the formula (IV), wherein the compound of the structure represented by the formula (IV) can be Wherein R ¹ , R ³ , and R ⁴ have the same definitions as described above.

According to an embodiment of the present disclosure, a method for preparing a compound of the structure represented by the formula (IV) may comprise dissolving a compound of the structure represented by the formula (I) and a compound of the formula (II) in a solvent. , get a mixture. Next, a compound of the structure represented by the formula (III) is added to the mixture, and after the reaction, a compound of the structure represented by the formula (IV) is obtained. The preparation method of the above compound can be represented by the following chemical reaction formula: Wherein the definitions of Ar ¹ , X, R ¹ , R ² , and R ³ are the same as described above. Here, the solvent to be used may be any solvent (for example, a halogen-free organic solvent) which can be used to dissolve a compound of the structure represented by the formula (I) and a compound of the structure represented by the formula (II). Further, a halogen-containing organic solvent which is easy to remove after the completion of the reaction and does not participate in the reaction can also be considered. According to an embodiment of the present disclosure, the solvent may be an aprotic solvent, including: acetonitrile, a linear or cyclic alkane (such as propane, butane, cyclohexane), a halogenated alkane (dichloromethane, chloroform, Dichloroethane), or no added solvent.

According to an embodiment of the present disclosure, in the preparation method of the compound of the present disclosure, the molar ratio of the compound of the structure represented by the formula (II) to the compound of the structure of the formula (I) may be about 0.5 to 5; In the preparation method of the compound of the present disclosure, the molar ratio of the compound of the formula (I) to the compound of the structure of the formula (III) may be about 1 to 20, for example, about 1 to 3, Or it can be about 1 to 10.

According to some embodiments of the present disclosure, the preparation method of the compound, after preparing the compound of the structure represented by the formula (IV), further comprises reacting the compound of the structure represented by the formula (IV) with a compound A to obtain the formula (V). Compound of the structure shown Wherein the compound A may be nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or a mixture thereof; and, the definitions of Ar ¹ , X, and R ³ are the same as described above.

According to an embodiment of the present disclosure, the present disclosure provides a method for preparing a compound of the formula (V), wherein the compound of the structure represented by the formula (V) may be ,or Wherein R ¹ , R ³ and R ^{4 are} as defined above.

According to an embodiment of the present disclosure, a method for preparing a compound of the structure represented by the formula (V) may include dissolving a compound of the structure represented by the formula (I) and a compound of the formula (II) in a first form. In the solvent, a mixture is obtained. Next, a compound of the structure represented by the formula (III) is added to the mixture, and after the reaction, a compound of the structure represented by the formula (IV) is obtained. Next, the compound of the structure represented by the formula (IV) is dissolved in a second solvent, and Compound A (compound A) is added to obtain a compound of the structure represented by the formula (V). The preparation method of the above compound can be represented by the following chemical reaction formula: Wherein the definitions of Ar ¹ , X, R ¹ , R ² , and R ³ are the same as described above. Here, when X is S, since S has a small steric hindrance to R ³ and has an oxidation potential which is more suitable for oxidation, it is selectively oxidized compared with X.

According to an embodiment of the present disclosure, the first solvent used may be any solvent which can be used to dissolve the compound of the structure represented by the formula (I) and the compound of the structure represented by the formula (II), and the second solvent used may be any useful To dissolve the compound of the structure shown in the formula (IV). According to an embodiment of the present disclosure, a halogen-free organic solvent may be used as the first solvent or the second solvent. Further, a halogen-containing organic solvent which is easy to remove after the completion of the reaction and does not participate in the reaction can also be considered. According to an embodiment of the present disclosure, the first solvent or the second solvent may be an aprotic solvent, including: acetonitrile, a linear or cyclic alkane (such as propane, butane, cyclohexane), a halogenated alkane (dichloro Methane, chloroform, dichloroethane), or no added solvent. According to an embodiment of the present disclosure, the molar ratio of the compound of the formula (IV) to the compound A may be about 0.8 to 30.

According to an embodiment of the present disclosure, the present disclosure provides a method of preparing a polymer. The method for preparing the polymer comprises reacting a compound of the formula (I) with a compound of the formula (III) in the presence of a compound of the formula (II) to obtain a compound of the formula (IV). a compound of the structure; reacting a compound of the structure of the formula (IV) with a compound A to obtain a compound of the formula (V) wherein the compound A is nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or a mixture thereof; A compound of the structure represented by the formula (V) is reacted with a compound of the formula (VI) to obtain a polymer having a repeating unit of the formula (VII). R ³ -SSR ³ (III) Wherein Ar ¹ , X, R ¹ , R ² , and R ^{3 have} the same meanings as defined above; R ⁵ is hydroxy, C _1-6 alkyl, phenyl, or tolyl; and Ar ² is substituted Or unsubstituted divalent aromatic groups. The method for preparing the polymer of the present disclosure can be used to prepare a polymer having a number average molecular weight of 1,000 or more. It should be noted that the preparation method of the polymer of the present disclosure is very suitable for preparing a larger number average molecular weight (for example, a number average molecular weight of 80,000 or more) and a narrower molecular weight distribution (PDI) (for example, less than or equal to 2) polymer. According to embodiments of the present disclosure, the method of preparing the polymer of the present disclosure is very suitable for preparing a polymer having a number average molecular weight of from 80,000 to 500,000 and having a molecular weight distribution value of from 1 to 2. According to certain embodiments of the present disclosure, the method of preparing the polymer of the present disclosure is very suitable for preparing a polymer having a number average molecular weight of from 80,000 to 200,000 and having a molecular weight distribution value of from 1.4 to 2.

According to an embodiment of the present disclosure, R ⁵ may be hydroxy, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl ( T-butyl), sec-butyl, isobutyl, pentyl, hexyl, phenyl, or tolyl.

According to an embodiment of the present disclosure, the substituted divalent aromatic group of the present disclosure means that the hydrogen on at least one of the divalent aromatic groups is substituted by a C _1-6 alkyl group.

According to an embodiment of the present disclosure, Ar ² may be a substituted or unsubstituted phenylene group, a biphenylene group, a naphthylene group, a thienylene group, and a stilbene group. Indolylene, phenanthrenylene, indenylene, anthracenylene, or fluorenylene, in which a substituted phenylene group or a biphenyl group ( Biphenylene group), naphthylene group, thienylene group, indolylene, phenanthrenylene, indenylene, anthracenylene, or Fluorylene means that hydrogen on at least one of the divalent aromatic groups is replaced by a C _1-6 alkyl group.

According to an embodiment of the present disclosure, in the preparation method of the polymer of the present disclosure, the molar ratio of the compound of the structure represented by the formula (II) to the compound of the structure of the formula (I) may be about 0.5 to 5; In the preparation method of the compound of the present disclosure, the molar ratio of the compound of the formula (I) to the compound of the structure of the formula (III) may be about 1 to 20, for example, about 1 to 3. Or it can be about 1 to 10. The molar ratio of the compound of the formula (IV) to the compound A (nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or the like) may be about 0.8 to 30; and the compound and formula of the structure represented by the formula (V) The molar ratio of the compound of the structure shown in (VI) It is about 0.8 to 20, for example, about 1.2 to 5. Further, in addition to the reaction with the compound of the structure represented by the formula (V), the compound of the structure represented by the above formula (VI) may be added in excess as a solvent.

According to an embodiment of the present disclosure, the compound of the structure represented by the formula (VI) may be sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid. , trifluoromethanesulfonic acid or a combination of the above. Further, according to the embodiments of the present disclosure, the compound of the structure represented by the formula (II) and the compound of the structure represented by the formula (VI) may be the same or different compounds.

According to an embodiment of the present disclosure, the polymer preparation method of the present disclosure can be used to prepare a polymer having a structural repeating unit represented by the formula (VII). For example, the structural repeat unit of formula (VII) can be , ,or Wherein R ¹ , R ³ , R ⁴ , and R ^{5 have} the same definitions as described above.

According to an embodiment of the present disclosure, a method for preparing a polymer having a structural repeating unit represented by the formula (VII) may include dissolving a compound having a structure represented by the formula (I) and a compound having a structure represented by the formula (II). In a first solvent, a mixture is obtained. Next, a compound of the structure represented by the formula (III) is added to the mixture, and after the reaction, a compound of the structure represented by the formula (IV) is obtained. Next, the compound of the structure shown by the formula (IV) is dissolved in a second solvent, and the compound A is added, and the compound of the structure represented by the formula (V) is obtained by the reaction. Next, a compound of the structure represented by the formula (V) is reacted with a compound of the structure represented by the formula (VI) to obtain a polymer having a repeating unit of the structure represented by the formula (VII). The preparation method of the above polymer can be expressed by the following chemical reaction formula: Wherein the definitions of Ar ¹ , Ar ² , X, R ¹ , R ² , R ³ , and R ⁵ are the same as described above.

According to an embodiment of the present disclosure, after preparing a polymer having a repeating unit of the structure represented by the formula (VII), the method for preparing the polymer further comprises polymerizing a nucleophilic reagent with the repeating unit having the structure represented by the formula (VII). Reacting to obtain a polymer having a repeating unit of the structure represented by formula (VIII)

Wherein the definitions of Ar ² , X, R ¹ , and R ³ are the same as described above.

The preparation method of the above polymer having the structural repeating unit represented by the formula (VIII) can be represented by the following chemical reaction formula: Wherein the definitions of Ar ¹ , Ar ² , X, R ¹ , R ² , R ³ , and R ⁵ are the same as described above.

According to an embodiment of the present disclosure, the nucleophile may be a substituted/unsubstituted pyridine or a derivative thereof (eg, pyridine, 4-methylpyridine), an amine (eg, triethylamine), halogenated. Salts (eg potassium chloride), alcohols (eg methanol, ethanol), guanamines (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone), or The combination. The nucleophile and the polymer having a repeating unit of the structure represented by the formula (VII) The equivalent ratio of the groups may be from 1 to 10. According to the embodiment of the present disclosure, the nucleophilic reagent and the polymer having the structural repeating unit represented by the formula (VII) may be dissolved in an organic solvent as needed, and then reacted.

According to an embodiment of the present disclosure, when the polymer of the polymer having the structural repeating unit represented by the formula (VIII) is -O- or -NH- (that is, the structural repeating unit represented by the formula (VIII) is or , wherein Ar ² and R ¹ have the same meanings as defined above), after preparing a polymer having a repeating unit of the structure represented by formula (VII), the method for preparing the polymer may further comprise: having the formula (VIII) The polymer of the structural repeating unit is reacted with hydrogen peroxide to obtain a polymer having a structural repeating unit represented by the formula (X). Alternatively, a polymer having a structural repeating unit represented by the formula (VIII) is reacted with hydrogen peroxide (H ₂ O ₂ ) in the presence of a compound represented by the formula (IX) to obtain a structural repeating unit having the formula (X). Polymer Wherein X is -O- or -NH-; R ⁶ is C _1-6 alkyl; and, Ar ² and R ¹ are as defined above. The preparation method of the above polymer having the structural repeating unit represented by the formula (X) can be represented by the following chemical reaction formula: Wherein X is -O- or -NH-; and the definitions of Ar ¹ , Ar ² , R ¹ , R ² , R ³ , R ⁵ and R ⁶ are the same as described above.

According to other embodiments of the present disclosure, there is disclosed a method for preparing a polymer having a repeating unit of the structure represented by the formula (X), which may have a polymer having a repeating unit of the formula (VIII) and a compound represented by the formula (IX). The reaction with hydrogen peroxide is first mixed with a solvent, and then the reaction is carried out. For example, the solvent may be, for example, a guanamine solvent or a guanidine solvent.

According to an embodiment of the present disclosure, R ⁶ may independently be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl. (t-butyl), sec-butyl, isobutyl, pentyl, or hexyl.

According to an embodiment of the present disclosure, when the polymer of the polymer having the structural repeating unit represented by the formula (VII) is -S- (that is, the structural repeating unit represented by the formula (VII) is , wherein Ar ² , R ¹ , and R ³ have the same meanings as defined above), after preparing the polymer having the structural repeating unit of the formula (VII), the method for preparing the polymer may further comprise: having the formula (VII) The polymer of the structural repeat unit shown is reacted with hydrogen peroxide to obtain a polymer having a repeating unit of the structure represented by the formula (XI). Alternatively, a polymer having a structural repeating unit represented by the formula (VII) is reacted with hydrogen peroxide in the presence of a compound represented by the formula (IX) to obtain a polymer having a structural repeating unit represented by the formula (XI).

Wherein X is -S-; and, the definitions of Ar ² , R ¹ , R ³ , R ⁵ , and R ⁶ are the same as described above. The preparation method of the above polymer having the structural repeating unit represented by the formula (XI) can be represented by the following chemical reaction formula: Wherein X is -S-; and the definitions of Ar ¹ , Ar ² , R ¹ , R ² , R ³ , R ⁵ , and R ⁶ are the same as described above.

According to other embodiments of the present disclosure, the present invention discloses a method for preparing a polymer having a repeating unit of the structure represented by the formula (XI), which can react a polymer having a repeating unit of the formula (VII) with hydrogen peroxide with a solvent. Mix and react again. For example, the solvent can be, for example, a nitrile, a guanamine or an anthraquinone solvent. Further, the polymer having a repeating unit of the structure represented by the formula (VII) can be reacted with a solvent by reacting a compound represented by the formula (IX) with hydrogen peroxide.

According to an embodiment of the present disclosure, after preparing the polymer having the structural repeating unit represented by the formula (XI), the method for preparing the polymer may further comprise: repeating a nucleophilic reagent and the structural unit having the structure represented by the formula (XI) Polymer reaction to obtain a polymer having a repeating unit of the formula represented by formula (XII) Wherein the definitions of Ar ² , R ¹ , R ³ , and R ⁵ are the same as described above. The preparation method of the above polymer having the structural repeating unit represented by the formula (XII) can be represented by the following chemical reaction formula: Wherein X is -S-; and the definitions of Ar ¹ , Ar ² , R ¹ , R ² , R ³ , R ⁵ , and R ⁶ are the same as described above.

According to an embodiment of the present disclosure, the nucleophile may be a substituted/unsubstituted pyridine or a derivative thereof (eg, pyridine, 4-methylpyridine), an amine (eg, triethylamine), halogenated. Salts (eg potassium chloride), alcohols (eg methanol, ethanol), guanamines (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone), or The combination. The nucleophile and the polymer having the repeating unit of the structure represented by the formula (XI) The equivalent ratio of the groups may be from 1 to 10. According to the embodiment of the present disclosure, the nucleophilic reagent and the polymer having the structural repeating unit represented by the formula (VII) may be dissolved in an organic solvent as needed, and then reacted.

The above and other objects, features and advantages of the present invention will become more apparent and understood.

Example 1:

Five grams of diphenyl ether, 11.7 grams of benzenesulfonic acid and 50 milliliters of dichloromethane were added to a reaction flask under nitrogen and cooled to 15 °C. Next, 5.54 grams of dimethyl disulfide (1,2-dimethyldisulfane) was slowly added to the reaction flask. After reacting at 15 ° C for 20 hours, the product was poured into 50 ml of an aqueous sodium hydroxide solution (weight ratio of sodium hydroxide to water: 1:10). After stirring for 0.5 hours, extraction was carried out three times with dichloromethane and deionized water. After the organic layer was drained and dehydrated, the compound (1) was obtained. The reaction formula of the above reaction is as follows:

The compound (1) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (400 MHz, ppm, CDCl ₃ ): 2.50 (-CH ₃ , 3H, s), 7.00 (phenyl, 4H, m), 7.14 ( Phenyl, 1H, t), 7.32-7.41 (phenyl, 4H, m).

Example 2:

0.73 g of the compound (1), 12 ml of an aqueous solution of nitric acid (concentration of 20%), and 4 ml of acetonitrile were placed in a reaction flask. After stirring at room temperature for 4 hours, 10 ml of an aqueous sodium hydroxide solution (concentration: 3%) was added to the reaction flask. Next, after the reaction was completed, the resultant was drained and dehydrated to obtain a compound (2) (orange powder). The reaction formula of the above reaction is as follows:

The compound (2) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (400 MHz, ppm, CD ₃ CO): 2.71 (-CH ₃ , 3H, s), 7.10-7.25 (phenyl, 5H, m) , 7.44 - 7.48 (phenyl, 2H, t), 7.70 - 7.72 (phenyl, 2H, d).

Example 3:

0.65 g of the compound (2) was placed in a reaction flask. Next, 3 ml of methanesulfonic acid (CH ₃ SO ₃ H) was added to the reaction flask under ice bath. After reacting for 1 hour, the reaction flask was warmed to room temperature, and the reaction was continued at room temperature for 20 hours to obtain a solution containing the polymer (1). Next, the solution containing the polymer (1) was dropped into 100 ml of ethyl ether and stirred for 30 minutes. Next, 6 ml of 4-methylpyridine was added under a nitrogen atmosphere and stirred at 100 ° C for 4-6 hours. After completion of the reaction, the product was dropped into 100 ml of an aqueous hydrochloric acid solution (concentration: 10%), and stirred for 10 minutes. After filtration and drying, the polymer (2) was obtained. The reaction formula of the above reaction is as follows:

The polymer (2) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (400 MHz, ppm, (CD ₃ ) SO): 7.04 (phenyl, d), 7.36 (phenyl, d).

Example 4:

0.2 g of polymer (2), 10 ml of acetic acid, 0.9 g of aqueous hydrogen peroxide solution (concentration of 30%) and 2 ml of dimethylacetamide (DMAc) were added to a reaction flask at 80 ° C. Stir for 6 hours. Next, the product was filtered and dried to give a polymer (3). The reaction formula of the above reaction is as follows:

The polymer (3) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1H NMR (400 MHz, ppm, (CD3)SO): 7.28 (phenyl, d), 7.99 (phenyl, d). Subsequently, the infrared spectroscopy (FT-IR) measurement of the polymer (3), the following results: ^1483-1 (vibration signal benzene ring), 1575 ^cm-1 (vibration signal benzene ring), 1295cm ^-1 (S = O asymmetric Vibration), 1318 cm ^-1 (S = O asymmetric vibration), 1145 cm ^-1 (S = O symmetric vibration signal). The obtained polymer (3) was measured by differential scanning calorimetry (DSC), and its glass transition temperature (Tg) was found to be 210 °C. The polymer (3) has a weight average molecular weight (Mw) of about 128,287, a number average molecular weight (Mn) of about 85,435, and a molecular weight distribution value (PDI) of, by gel permeation chromatography (GPC) analysis. 1.50.

Example 5: 5.58 g of diphenyl sulfide and 5.64 g of dimethyl disulfide were placed in a reaction flask, 50 ml of dichloromethane was added as a solvent, and 11.7 g of benzenesulfonic acid was slowly added dropwise thereto, and the reaction was carried out at 15 ° C. After 44 hr, extraction with 150 ml of n-hexane and deionized water for 3 times, and purification by column chromatography to obtain a product of 0.76 g, yield: 10.9%; the product was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H _{NMR (400MHz, ppm, CDCl 3} ): 2.50 (-CH 3, 3H, s), 7.21-7.34 (phenyl, 9H, m).

Example 6: 5.07 g of methylthio (p-diphenyl sulfide) was placed in a reaction flask, 20 ml of acetonitrile was added as a solvent, and 60 ml of 20% nitric acid was slowly added dropwise thereto, and reacted at room temperature for 4 hr, and the reaction was completed. The reaction solution was neutralized with 12 g of sodium hydroxide, and then the product solution was subjected to extraction three times with 150 ml of dichloromethane to obtain a product of 5.15 g, yield: 95%; the product was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H _{NMR (400MHz, ppm, CDCl 3} ): 2.73 (-CH 3, 3H, s), 7.34-7.49 (phenyl, 9H, m).

Example 7: 3 g of methyl (p-diphenyl sulfide) hydrazine was taken, placed in a reaction flask, and 10 ml of methanesulfonic acid was slowly added at 15 ° C for 20 hr. After the reaction, 50 ml of deionized water was used. Reprecipitation was carried out to obtain a white solid; this solid was dissolved in 46 ml of chloroform and 46 ml of trifluoroacetic acid. The mixture was slowly added dropwise to 4.14 g of 30% hydrogen peroxide, and the reaction was continued at 60 ° C for 5 hr. After the reaction was over, the product was poured into 5%. Reprecipitation in brine or deionized water gave 2.91 g of the product as a white solid, yield: 97%. The product was analyzed by NMR spectroscopy. The obtained spectral information is as follows: ¹ H NMR (400 MHz, ppm, d ⁶ -DMSO): 7.56 (Phenyl, 4H, s), 7.93 (phenyl, 4H, s); the obtained product was measured by differential scanning calorimetry (DSC), and its glass transition temperature (Tg) was found to be 222 °C.

Based on the above, the present disclosure provides a method for preparing a compound. The reaction starting material or the catalyst used in the preparation method of the compound does not contain halogen, except that halogen-containing by-products are avoided, and residual halogen-containing compounds can be avoided. Among the obtained compounds. Therefore, the method for preparing the compound of the present disclosure does not require an additional step to remove the halogen-containing by-product or the residual halogen compound, which can reduce the production cost and increase the process yield, and obtain a halogen-free monomer which can be used in the subsequent polymerization process. In addition, the present disclosure also provides a method for preparing a polymer (for example, polyether sulfone (PES) or polythioether sulfone (PTES)), which is electrophilic to a reactive monomer in an acidic environment. Gather The combined reaction and the post-polymerization oxidation technique can greatly increase the molecular weight of the obtained polymer, and the obtained polymer has a lower molecular weight distribution value (PDI).

The present disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any one skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.

Claims (27)

A method for producing a compound comprising: reacting a compound of the formula (I) with a compound of the formula (III) in the presence of a compound of the formula (II) to obtain a compound of the formula (IV) Structural compound R ³ -SSR ³ (III) Wherein Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ² is hydroxy, C _1-6 An alkyl group, a phenyl group, or a tolyl group; and, R ³ is independently a C _1-6 alkyl group, a C _5-8 cycloalkyl group, or a C _2-6 alkoxyalkyl group. The method for preparing a compound according to claim 1, wherein Ar ¹ is a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a thienyl group. Group), indolyl, phenanthrenyl, indenyl, anthracenyl, or fluorenylene. The method for preparing a compound according to claim 1, wherein R ¹ is independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl N-butyl, t-butyl, sec-butyl, isobutyl, pentyl, or hexyl. The method for producing a compound according to claim 1, wherein the compound of the structure represented by the formula (I) is , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; and R ⁴ is independently hydrogen or C _1-6 alkyl. The method for preparing a compound according to claim 1, wherein the compound of the formula (II) is sulfuric acid, methanesulfonic acid, benzenesulfonic acid, or the like. Toluenesulfonic acid (p-toluenesulfonic Acid), or a combination of the above. The method for preparing a compound according to claim 1, wherein R ³ is independently methyl (methyl), ethyl (ethyl), propyl (propyl), isopropyl (isopropyl), n-butyl ( N-butyl), t-butyl, sec-butyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptane Base, cyclooctyl, or , where 1≦n≦5, 0≦m≦4, and 1≦n+m≦5. The method for preparing a compound according to claim 1, wherein the compound of the structure represented by the formula (IV) , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; R ⁴ is independently hydrogen or C _1-6 alkyl; and R ³ is independently C _1-6 alkyl, C _5-8 naphthenic Or a C _2-6 alkoxyalkyl group. The method for preparing a compound according to claim 1, further comprising: reacting a compound of the formula (IV) with a compound A to obtain a compound having the structure represented by the formula (V) Wherein the compound A is nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or a mixture thereof; Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen Or a C _1-6 alkyl group; and, R ³ is independently a C _1-6 alkyl group, a C _5-8 cycloalkyl group, or a C _2-6 alkoxyalkyl group. A method for producing a compound according to item 8 of the patent application, wherein the compound of the structure represented by the formula (V) is , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; R ⁴ is independently hydrogen or C _1-6 alkyl; and R ³ is independently C _1-6 alkyl, C _5-8 naphthenic Or a C _2-6 alkoxyalkyl group. A method for preparing a polymer comprising: reacting a compound of the formula (I) with a compound of the formula (III) in the presence of a compound of the formula (II) to obtain a compound of the formula (IV) a compound of the formula; reacting a compound of the formula (IV) with a compound A to obtain a compound of the formula (V) wherein the compound A is nitric acid, sulfuric acid, acetic acid, hydrogen peroxide, or a mixture thereof; And reacting a compound of the structure represented by the formula (V) with a compound of the structure represented by the formula (VI) to obtain a polymer having a repeating unit of the formula represented by the formula (VII) R ³ -SSR ³ (III) Wherein Ar ¹ is a substituted or unsubstituted aryl group; X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ² is hydroxy, C _{1- 6} alkyl, phenyl, or tolyl; R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl, or C _2-6 alkoxyalkyl; R ⁵ is a hydroxyl group, a C _1-6 alkyl group, a phenyl group, or a tolyl group; and, Ar ² is a substituted or unsubstituted divalent aromatic group. The method for producing a polymer according to claim 10, wherein Ar ¹ is a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a thienyl group ( Thienyl group), indolyl, phenanthrenyl, indenyl, anthracenyl, or fluorenylene. The method for preparing a polymer according to claim 10, wherein R ¹ is independently hydrogen, methyl, ethyl, propyl, isopropyl, or Butyl (n-butyl), t-butyl, sec-butyl, isobutyl, pentyl, or hexyl. The method for producing a polymer according to claim 10, wherein the compound of the structure represented by the formula (I) , , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; and R ⁴ is independently hydrogen or C _1-6 alkyl. The method for preparing a polymer according to claim 10, wherein the compound of the formula (II) is sulfuric acid, methanesulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid or a combination thereof. The method for preparing a polymer according to claim 10, wherein R ³ is independently methyl, ethyl, propyl, isopropyl or n-butyl. (n-butyl), tert-butyl (t-butyl), sec-butyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ring Heptyl, cyclooctyl, or , where 1≦n≦5, 0≦m≦4, and 1≦n+m≦5. The method for producing a polymer according to claim 10, wherein the compound of the structure represented by the formula (IV) , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; R ⁴ is independently hydrogen or C _1-6 alkyl; and R ³ is independently C _1-6 alkyl, C _5-8 naphthenic Or a C _2-6 alkoxyalkyl group. The method for preparing a polymer according to claim 10, wherein the compound of the structure represented by the formula (V) is , ,or Wherein R ¹ is independently hydrogen or C _1-6 alkyl; R ⁴ is independently hydrogen or C _1-6 alkyl; and R ³ is independently C _1-6 alkyl, C _5-8 naphthenic Or a C _2-6 alkoxyalkyl group. The method for preparing a polymer according to claim 10, wherein the compound of the structure represented by the formula (VI) is sulfuric acid, methanesulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid, or a combination thereof. The method for producing a polymer according to claim 10, wherein Ar ² is a substituted or unsubstituted phenylene group, a biphenylene group, a naphthylene group, Thienylene group, indolylene, phenanthrenylene, indenylene, anthracenylene, or fluorenylene. The method for preparing a polymer according to claim 10, further comprising: reacting a nucleophilic reagent with the polymer having the structural repeating unit of the formula (VII) to obtain a structure represented by the formula (VIII). Repeating unit polymer Wherein X is -O-, -S-, or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl Or a C _2-6 alkoxyalkyl; R ⁵ is a hydroxyl group, a C _1-6 alkyl group, a phenyl group, or a tolyl group; and, Ar ² is a substituted or unsubstituted divalent aromatic group. The method for preparing a polymer according to claim 20, wherein the nucleophilic reagent is pyridine, 4-methylpyridine, triethylamine, potassium chloride, methanol, ethanol, dimethylformamide, or the like. Methylacetamide, N-methylpyrrolidone, or a combination thereof. The method for preparing a polymer according to claim 20, wherein when the polymer having the structural repeating unit represented by the formula (VIII) has X as -O- or -NH-, it further comprises: having the formula (VIII) The polymer of the repeating unit of the structure shown is reacted with hydrogen peroxide to obtain a polymer having a repeating unit of the structure represented by the formula (X) Wherein X is -O- or -NH-; R ¹ is independently hydrogen or C _1-6 alkyl; and Ar ² is a substituted or unsubstituted divalent aromatic group. The method for producing a polymer according to claim 20, wherein a polymer having a structural repeating unit represented by the formula (VIII) is reacted with hydrogen peroxide in the presence of a compound represented by the formula (IX) Wherein R ⁶ is a C _1-6 alkyl group. The method for preparing a polymer according to claim 10, when the polymer having the structural repeating unit represented by the formula (VII), wherein X is -S-, further comprises: having the structure represented by the formula (VII) The polymer of the repeating unit is reacted with hydrogen peroxide to obtain a polymer having a repeating unit of the structure represented by the formula (XI) Wherein X is -S-; R ¹ is independently hydrogen or C _1-6 alkyl; R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl, or C _2-6 alkoxylated Alkoxyalkyl; R ⁵ is a hydroxyl group, a C _1-6 alkyl group, a phenyl group, or a tolyl group; and, Ar ² is a substituted or unsubstituted divalent aromatic group. The method for producing a polymer according to claim 24, wherein a polymer having a structural repeating unit represented by the formula (VII) is reacted with hydrogen peroxide in the presence of a compound represented by the formula (IX) Wherein R ⁶ is a C _1-6 alkyl group. The method for preparing a polymer according to claim 24, further comprising: reacting a nucleophilic reagent with the polymer having the structural repeating unit of the formula (XI) to obtain a structure represented by the formula (XII). Repeating unit polymer Wherein R ¹ is independently hydrogen or C _1-6 alkyl; R ³ is independently C _1-6 alkyl, C _5-8 cycloalkyl, or C _2-6 alkoxyalkyl; R ⁵ is a hydroxyl group, a C _1-6 alkyl group, a phenyl group, or a tolyl group; and, Ar ² is a substituted or unsubstituted divalent aromatic group. The method for preparing a polymer according to claim 26, wherein the nucleophilic reagent is pyridine, 4-methylpyridine, triethylamine, potassium chloride, methanol, ethanol, dimethylformamide, or the like. Methylacetamide, N-methylpyrrolidone, or a combination thereof.