TWI646129B - Polymer - Google Patents

Abstract

The present disclosure provides a polymer. The polymer having a repeating unit of the structure represented by formula (I) or formula (II) Wherein Ar ¹ and Ar ² may independently be a substituted or unsubstituted divalent aromatic group; Y ^- may be R ² SO ₃ ^- or ClO ₄ ^- ; R ¹ may be a C _1-6 alkyl group; Ar ¹ and Ar ^{2 are} not The same; and, R ² may be a C _1-6 alkyl group, a substituted or unsubstituted aromatic ring, or a C _1-6 haloalkyl group.

Description

polymer

The present disclosure relates to a polymer, particularly a polyarylene sulfide or a salt thereof.

Polyarylene sulfides are excellent in physical properties such as heat resistance, chemical resistance, fire resistance, and electrical insulation properties, and are therefore widely used in computer accessories, automotive accessories, coatings for parts in contact with corrosive chemicals, and Chemically resistant industrial fibers.

However, since the preparation method of the conventional polyarylene sulfide is mainly based on a halogen process, in addition to the low polyarylene sulfide resin yield, a halogen-containing by-product which cannot be recovered is generated, which causes environmental pollution. In addition, polyarylene sulfides having conventionally having at least two repeating units have a repeating unit generally arranged in a random fashion, so that heat resistance, chemical resistance, fire resistance, and electrical insulating properties of the polyarylene sulfide are obtained. Can't further improve the decline.

According to an embodiment of the present disclosure, the present disclosure provides a polymer which may have a repeating unit of the structure shown in formula (I) or formula (II):

Wherein Ar ¹ and Ar ² are independently substituted or unsubstituted divalent aromatic groups; Y ^- may be R ² SO ₃ ^- or ClO ₄ ^- ; R ¹ may be C _1-6 alkyl; Ar ¹ and Ar ^{2 are} not The same; and, R ² may be a C _1-6 alkyl group, a substituted or unsubstituted aromatic ring, or a C _1-6 haloalkyl group.

The disclosed embodiments provide a polymer, such as a polyarylene sulfide or a salt thereof. According to an embodiment of the present disclosure, the polymer of the present disclosure has a main chain structure composed of different aromatic groups in an alternating arrangement, and thus has a higher crystallinity such that the polymer has a higher melting point (for example, greater than or equal to 330 ° C), and further improve heat resistance, chemical resistance, fire resistance, and electrical insulation properties.

According to an embodiment of the present disclosure, the polymer of the present disclosure may have a repeating unit of the structure shown in formula (I) or formula (II):

Wherein Ar ¹ and Ar ² are independently substituted or unsubstituted divalent aromatic groups; Y ^- may be R ² SO ₃ ^- or ClO ₄ ^- ; R ¹ may be C _1-6 alkyl; Ar ¹ and Ar ^{2 are} not The same; and, R ² may be a C _1-6 alkyl group, a substituted or unsubstituted aromatic ring, or a C _1-6 haloalkyl group. Herein, 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, the substituted aromatic ring means that the hydrogen on at least one of the aromatic rings is replaced by a C _1-6 alkyl group.

According to an embodiment of the present disclosure, Ar ¹ and Ar ² are independently a substituted or unsubstituted phenylene group, a biphenylene group, a naphthylene group, a thienylene group. , indolylene, phenanthrenylene, indenylene, anthracenylene, or fluorenylene, in which phenylene group, phenylene group Biphenylene group, naphthylene group, thienylene group, indolylene, phenanthrenylene, indenylene, exfoliation Anthracenylene) or fluorenylene 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, the C _1-6 alkyl group may be a linear or branched chain alkyl group. For example, for example, R ¹ may be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl. ), sec-butyl, isobutyl, pentyl, or hexyl.

According to an embodiment of the present disclosure, Ar ¹ and Ar ² may be independently , x is 0, 1, or 2; R ³ may independently be hydrogen or a C _1-6 alkyl group. For example, R ³ 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 repeating unit having the structure shown in the formula (I) may be And the repeating unit having the structure represented by the formula (II) may be Wherein R ¹ , R ³ , and Y ^{- are} as defined above.

In accordance with embodiments of the present disclosure, the degree of polymerization of the polymers described herein may be adjusted as desired, for example, may have a number average molecular weight of from about 600 to 120,000 or a number average molecular weight of from about 10,000 to 30,000.

According to an embodiment of the present disclosure, a method for preparing a polymer according to the present disclosure comprises reacting a compound having a structure represented by the formula (III) with an acid to obtain a polymer having a structure represented by the formula (I):

Wherein Ar ¹ may be a substituted or unsubstituted divalent aromatic group, such as a substituted or unsubstituted phenylene group, a biphenylene group, a naphthylene group, a thienyl group ( Thienylene group), indolylene, phenanthrenylene, indenylene, anthracenylene, or fluorenylene; Ar ³ may be substituted or unsubstituted aromatic a group, for example, a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a thienyl group, an indolyl group, a phenanthrenyl group, Indenyl, anthracenyl, or fluorenylene, wherein the substituted aryl group means that at least one of the carbons of the aromatic group is replaced by a C _1-6 alkyl group. When Ar ¹ and Ar ³ are derived from different compounds, for example, when Ar ¹ is a phenylene group, Ar ³ is not a phenyl group. The above acid may be, for example, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid. In addition to the reaction of the above-mentioned acid with a compound having a structure represented by the formula (III), an excess may be added as a solvent.

Further, the obtained polymer having the structure represented by the formula (I) may further replace the anion (Y ^- ) group of the polymer having the structure represented by the formula (I) with another anion (for example, CH ₃ SO ₃ ^- ). To obtain other polymers with different anions.

Further, the polymer having the structure represented by the formula (I) can be subjected to a dealkylation reaction using a nucleophilic reagent to obtain a polymer having a structure represented by the formula (II). According to embodiments of the present disclosure, the nucleophile may be a metal halide, a metal hydroxide, an alcohol, an amine (eg, a secondary amine, or a tertiary amine), or a thiol. For example, the nucleophile can be sodium chloride, potassium chloride, aluminum chloride, or 4-methylpyridine.

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

Example 1:

0.7 g of methyl phenyl sulfoxide and 1 g of methyl biphenyl sulfide were added to a reaction flask under nitrogen and cooled to 0 °C. Next, 10 ml of methanesulfonic acid was slowly added to the reaction flask and stirred for about half an hour. Next, return to room temperature and continue stirring for about 20 hours. Next, the obtained product was poured into 40 ml of perchloric acid and stirred for about 1 hour, and extracted three times with 50 ml of dichloromethane and 100 ml of deionized water. After the organic layer was drained and water was removed, compound (1) was obtained in a yield of about 92%. 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 ): 2.48 (-CH ₃ , s), 3.67 (sulfonium-CH ₃ , s), 7.40-7.94 (aromatic H, 13H, m). The compound (1) was analyzed by liquid chromatography-mass spectrometry (LC-MS), and m/z = 323 (excluding CH ₃ SO ₃ ^- anion) was measured.

Next, 1.9 g of the compound (1) and 30 ml of glacial acetic acid were placed in a reaction flask under nitrogen. After stirring for a few minutes, 2.02 ml of hydrogen peroxide was slowly added. After about 90 minutes of reaction, the obtained product was extracted three times with 50 ml of dichloromethane and 100 ml of deionized water. After the organic layer was drained and dehydrated, compound (2) (orange) was obtained. Next, 10 ml of 4-methylpyridine and the compound (2) were placed in a next reaction flask under nitrogen, and stirred for 30 minutes. After heating and refluxing for about 20 minutes, the compound (3) was obtained. The reaction formula of the above reaction is as follows:

The compound (3) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: ¹ H NMR (400 MHz, ppm, CDCl ₃ ): 2.72 (-CH ₃ , s), 7.38 - 7.63 (aromatic H, 13H, m). The compound (3) was analyzed by liquid chromatography-mass spectrometry (LC-MS), and m/z = 325 (M+H ⁺ ), 347 (M+Na ⁺ ) and 671 (measured). 2*M+Na ⁺ ) three sets of signals (M is the molecular weight).

Next, 1 g of the compound (3) was placed in a reaction flask under nitrogen, and the temperature was lowered to 0 °C. Next, 15 ml of trifluoromethanesulfonic acid was slowly added and stirred for about 2 hours. Then, after returning to about 18 ° C, the product was poured into deionized water at 0 ° C, and a white precipitate was observed to precipitate. Next, a white precipitate was collected and the white precipitate was washed repeatedly with deionized water until the white precipitate appeared neutral. Next, the obtained white precipitate was vacuum dried for about 6 hours to obtain a polymer (1) in a yield of 100%. Next, 1 g of the polymer (1) was placed in a reaction flask under nitrogen, and 10 ml of 4-methylpyridine was slowly added. After reacting at room temperature for about 30 minutes, the reaction flask was heated to 150 ° C and refluxed. After continuously stirring for 5 hours, the reaction was cooled to room temperature, and the reaction solution was poured into a 200 ml methanol solution containing 10% hydrochloric acid (HCl), and a white precipitate was observed. Next, a white precipitate was collected to obtain a polymer (2) in a yield of 98%. The reaction formula of the above reaction is as follows:

It has been found by measurement that the polymer (1) and the polymer (2) have a number average molecular weight of about 17,000 to 19,000.

The obtained polymer (2) was measured by differential scanning calorimetry (DSC), and it was found that its melting temperature (Tm) reached about 330 ° C and its temperature-reducing recrystallization temperature (Tcc) reached about 251 ° C. Next, the polymer (2) was measured by an infrared spectrometer (FT-IR), and the results were as follows: IR (cm ^-1 ): 3023, 1593, 1472, 1388, 1090, 1006, 808.

The present disclosure is based on the above, since the polymer (for example, polyarylene sulfide or a salt thereof) of the present disclosure has a main chain structure composed of different aromatic groups in an alternating arrangement, and thus has crystallinity so that the polymer has Higher melting point (for example, greater than or equal to 330 ° C), and further improve heat resistance, chemical resistance, and fire resistance.

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 (6)

a polymer having a repeating unit having a structure represented by formula (I) or formula (II) Wherein Ar ¹ and Ar ² are independently unsubstituted divalent aromatic groups; Y ^- series R ² SO ₃ ^- or ClO ₄ ^- R ¹ is C _1-6 alkyl; Ar ^{1 is} different from Ar ² ; ² is a C _1-6 alkyl group, a substituted or unsubstituted aromatic ring, or a C _1-6 haloalkyl group. The polymer of claim 1, wherein R ¹ is methyl, ethyl, propyl, isopropyl, n-butyl , t-butyl, sec-butyl, isobutyl, pentyl, or hexyl. The polymer according to claim 1, wherein the Ar ¹ and Ar ² are independently an unsubstituted phenylene group, a biphenylene group, a naphthylene group, and an extension. Thienylene group, indolylene, phenanthrenylene, indenylene, anthracenylene, or fluorenylene. The polymer of claim 1, wherein the Ar ¹ and Ar ² are independently R ³ is hydrogen, and x is 0, 1, or 2. The polymer according to claim 1, wherein the repeating unit having the structure represented by the formula (I) Wherein R ¹ is C _1-6 alkyl; R ³ is hydrogen; and Y ^- is R ² SO ₃ ^- or ClO ₄ ^- . The polymer according to claim 1, wherein the repeating unit having the structure represented by formula (II) Wherein R ³ is hydrogen.