Bisphenol-type polyarylate and method for preparing biomass-derived polyarylate material using the same

Abstract

The present invention belongs to the technical field of polyarylate materials, and in particular relates to bisphenol-type polyarylate and a method for preparing a biomass-derived polyarylate material using the same. The bisphenol-type polyarylate of the present invention has a general structural formula: #imgabs0#, wherein R is #imgabs1#, and the method for preparing a biomass-derived polyarylate material comprises the following steps: adding 4,4'-methylenebis(5-isopropyl-2-methylphenol), sodium hydroxide, and benzyltriethylammonium chloride to water; adding an aromatic diformyl chloride compound to dichloromethane; adding an organic phase solution to an inorganic phase solution to obtain a polymer solution; after acid washing, washing and purification, precipitation and filtration; crushing and washing the precipitate, vacuum drying, stirring and dissolving the bisphenol-type polyarylate with a solvent, suction filtering, volatilization, and drying to obtain a polyarylate material. The bisphenol-type polyarylate provided by the present invention is a bisphenol-type polyarylate material prepared using the bisphenol-type polyarylate, and is prepared using biomass as raw material, is environmentally sustainable, and is environmentally friendly.

Description

Technical Field

[0001] The invention belongs to the technical field of polyarylate materials, and particularly relates to bisphenol polyarylate and a method for preparing a biomass-derived polyarylate material using the same. Background Art

[0002] Polyarylates (PAR) are a class of thermoplastic polymers whose main molecular chain is primarily composed of benzene rings linked by ester bonds. Their molecular structure is similar to that of polycarbonate (PC), but they have a higher benzene ring density. Due to their rigid molecular structure, these materials possess excellent heat resistance, mechanical properties, weather resistance, and light transmittance. Operating temperatures can exceed 150°C, making them a second-tier specialty engineering plastic, after polyimide, in the plastics pyramid. They can be used in films, fibers, and composite materials for a wide range of applications in aerospace, automotive, electronics, and other fields, attracting considerable research interest. The most popular product currently on the market is model U-100.

[0003] Traditional polyarylate materials offer excellent overall performance, but their commonly used monomer, bisphenol A, is industrially produced from phenol and acetone. BPA has been found to be released from plastics (through incomplete polymerization, biochemical degradation, and thermomechanical stress), polluting the environment and has been detected in bodily fluids (such as blood and urine) and tissues of children and adults. BPA also has multiple adverse effects on human health, including cancer and reproductive problems.

[0004] In addition, the raw materials isophthaloyl chloride and terephthaloyl chloride used in the preparation of traditional polyarylate materials are also petroleum-based monomers, and their upstream monomers are terephthalic acid and isophthalic acid.

[0005] CN114573801A proposes a method for preparing a phenol red-based polyarylate material. Using phenol red, bisphenol A, isophthaloyl chloride, and terephthaloyl chloride as raw materials, a novel polyarylate is prepared. This material exhibits excellent heat resistance, mechanical properties, and processing fluidity. CN110408021A proposes a high-strength, hydrolysis-resistant, and highly fluid polyarylate and its preparation method. A series of bisphenol monomers and aromatic dicarboxyl chloride monomers are used to prepare a polyarylate material with even better performance. However, the synthetic monomers used in these methods are all petroleum-based, not biomass-derived.

[0006] In summary, while traditional polyarylate materials offer excellent performance, their commonly used monomers are all petroleum-based, which is detrimental to sustainable energy development. Therefore, developing biomass-derived monomers to replace petroleum-based monomers in the synthesis of polyarylates and preparing bio-based polyarylates is of great significance. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a bisphenol-type polyarylate. A method for preparing a biomass-derived polyarylate material using the bisphenol-type polyarylate is provided. The polyarylate is prepared using biomass as raw material, which is environmentally friendly, sustainable and environmentally friendly.

[0008] The bisphenol polyarylate of the present invention has the general structural formula:

[0009] ,

[0010] Where R is 、 or , n is an integer, and its value is 30-150.

[0011] The method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0012] (1) Add 4,4'-methylenebis(5-isopropyl-2-methylphenol), sodium hydroxide, and benzyltriethylammonium chloride into water and stir to dissolve to obtain an inorganic phase solution;

[0013] (2) adding an aromatic diformyl chloride compound to dichloromethane and stirring to obtain an organic phase solution;

[0014] (3) adding the organic phase solution dropwise to the inorganic phase solution to carry out polymerization reaction, and obtaining a polymer solution after the reaction is completed;

[0015] (4) After acid washing, the polymer solution was purified by washing with water, poured into ethanol for precipitation and filtration;

[0016] (5) crushing the precipitate, washing it, and vacuum drying it to obtain bisphenol-type polyarylate;

[0017] (6) Dissolve the bisphenol-type polyarylate in a solvent by stirring, filter, evaporate the filtrate, and vacuum dry to obtain the polyarylate material.

[0018] All raw materials of the inorganic phase solution of step (1) and the organic phase solution of step (2) are mixed according to the following weight proportions: 150-160 parts of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 45-50 parts of sodium hydroxide, 15-25 parts of benzyltriethylammonium chloride, 4000-6000 parts of water, 100-115 parts of aromatic diformyl chloride compound, and 2000-3000 parts of dichloromethane.

[0019] The aromatic dicarboxylic acid chloride is one or more of terephthaloyl chloride, isophthaloyl chloride, and 2,5-furandicarboxylic acid chloride.

[0020] The polymerization reaction temperature of step (3) is 20-30°C, the reaction time is 10-15h, and the stirring speed is 300-600r / min.

[0021] The organic phase solution in step (3) is added dropwise to the inorganic phase solution at a rate of 2 mL / min to 3 mL / min.

[0022] The washing and purification in step (4) is carried out until the pH of the aqueous phase solution separated by washing is neutral.

[0023] The vacuum drying temperature of step (5) is 120-150°C, and the drying time is 10-15h.

[0024] The solvent of step (6) is one or both of dichloromethane and chloroform, the drying temperature is 100-130° C., and the drying time is 10-15 h.

[0025] The structural formula of 4,4'-methylenebis(5-isopropyl-2-methylphenol) is: .

[0026] Specifically, the method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0027] (1) Add 4,4'-methylenebis(5-isopropyl-2-methylphenol), sodium hydroxide, and benzyltriethylammonium chloride into a three-necked flask with deionized water and mechanical stirring, stir and dissolve to obtain an inorganic phase solution.

[0028] (2) Add the aromatic dicarboxylic acid chloride compound into a single-necked flask containing dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0029] (3) Pour the organic phase solution into a constant pressure dropping funnel and slowly add it dropwise to the inorganic phase solution in the three-necked flask at 2 mL / min-3 mL / min under the condition of 300-600 r / min to carry out polymerization reaction. The reaction temperature is 20-30 ° C and the reaction time is 10-15 h. After the reaction is completed, the upper inorganic phase solution is separated to obtain the organic phase, i.e., the polymer solution.

[0030] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0031] (5) The precipitate is crushed, washed, and vacuum-dried at 120-150°C for 10-15 hours to obtain bisphenol-type polyarylate.

[0032] (6) Dissolve the bisphenol-type polyarylate in a solvent by stirring, filter with a sand core funnel, pour the filtrate into a watch glass, evaporate naturally, and dry in a vacuum oven at 100°C for 10 hours to obtain the polyarylate material.

[0033] The 4,4'-methylenebis(5-isopropyl-2-methylphenol) used in the present invention is obtained by synthesizing the bio-based monomer carvacrol extracted from turpentine through a simple one-step method. It has a strong rigid structure and a simple synthesis route. It is obtained from biomass resources, reducing the consumption of petroleum resources. It has great value in replacing bisphenol A in the synthesis of polyarylates.

[0034] The 2,5-furandicarboxylic acid (FDCA) used in this invention is currently considered the most ideal bio-based alternative to PTA. It is a bio-based aromatic chemical and a biomass monomer. 2,5-Furandicarboxylic acid chloride is prepared from 2,5-furandicarboxylic acid and thionyl chloride, also a bio-based monomer.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The method of preparing biomass-derived polyarylate material of the present invention is simple to operate, has low energy consumption, does not require protective gas protection, and the solvent can be recycled and reused in the later stage, thereby reducing costs and improving efficiency.

[0037] (2) The method for preparing the polyarylate material from biomass of the present invention uses monomers from biomass as the source of synthesis, which is a renewable green resource and is very friendly to energy consumption and the ecological environment.

[0038] (3) The polyarylate material prepared by the method of the present invention has relatively excellent heat resistance and solubility, and can replace petroleum-based polyarylate materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The infrared spectra of the polyarylate materials prepared in Examples 1-4 are shown.

[0040] Figure 2 The DSC spectra of the polyarylates prepared in Examples 1-4 and Comparative Examples 1-3 are shown.

[0041] In the figure: 1, Example 1; 2, Example 2; 3, Example 3; 4, Example 4; 5, Comparative Example 1; 6, Comparative Example 2; 7, Comparative Example 3. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to specific examples. The raw materials used in the following examples are all from normal commercial products.

[0043] The 4,4'-methylenebis(5-isopropyl-2-methylphenol) used in the following examples was prepared by the following steps:

[0044] Carvacrol (10 g, 66.6 mmol) and paraformaldehyde (2 g, 21.8 mmol) were dispersed in 60 mL of water, and then 15 mL of concentrated hydrochloric acid was added dropwise to the system. The reaction was maintained at 80 °C for 6 h. At the end of the reaction, the product solidified into a light yellow block-like substance. After cooling to room temperature, the supernatant was poured out, and the solid product was dissolved in CH2Cl2, gently heated, and then washed with water. The organic layer was dried over MgSO4, heated and concentrated under reduced pressure, and the obtained light yellow substance was recrystallized from ethanol / water (V1:V2=1:1), placed in a refrigerator at -20 °C for 12 h, and filtered to obtain a white crystalline solid.

[0045] The preparation steps of 2,5-furandicarbonyl chloride are:

[0046] Furandicarboxylic acid (70 g, 0.45 mol), thionyl chloride (140 mL) and 3 mL DMF were placed in a three-necked flask equipped with a mechanical stirrer and a condensation reflux device. The condenser was connected to a washing bottle filled with concentrated sodium hydroxide aqueous solution through a glass tube filled with activated silica gel. The mixture was refluxed at about 80°C, near the boiling point of thionyl chloride, for 5 hours. It was found that the system gradually became clear. The reflux device was then removed, and the excess thionyl chloride was removed by vacuum distillation until no fraction was distilled out. The precipitate precipitated by cooling was the crude furandicarboxylic acid chloride, which was further purified by sublimation and collection to obtain refined 2,5-furandicarboxylic acid chloride.

[0047] This invention uses carvacrol as a bio-based alternative to bisphenol A, making it a bio-based polyester. The difference between the introduction of 2,5-furandicarboxylic acid chloride and terephthaloyl chloride and isophthaloyl chloride lies in the distinction between fully bio-based and semi-bio-based, but all are bio-based polyesters.

[0048] Example 1

[0049] The method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0050] (1) Add 1.56 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.47 g of sodium hydroxide, and 0.15 g of benzyltriethylammonium chloride into a three-necked flask with 40 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0051] (2) Add 1.00 g of isophthaloyl chloride into a single-necked flask containing 25 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0052] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 2 mL / min at 400 r / min to carry out polymerization reaction. The reaction temperature was 25 °C and the reaction time was 12 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0053] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0054] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 10 h to obtain bisphenol-type polyarylate.

[0055] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0056] Example 2

[0057] The method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0058] (1) Add 1.56 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.45 g of sodium hydroxide, and 0.15 g of benzyltriethylammonium chloride into a three-necked flask with 50 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0059] (2) Add 0.50 g of terephthaloyl chloride and 0.50 g of isophthaloyl chloride into a single-necked flask with 25 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0060] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 2 mL / min at 600 r / min to carry out polymerization reaction. The reaction temperature was 20 °C and the reaction time was 15 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0061] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0062] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 10 h to obtain bisphenol-type polyarylate.

[0063] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0064] Example 3

[0065] The method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0066] (1) Add 1.60 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.47 g of sodium hydroxide, and 0.20 g of benzyltriethylammonium chloride into a three-necked flask with 50 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0067] (2) Add 1.00 g of terephthaloyl chloride into a single-necked flask with 30 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0068] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 3 mL / min at 400 r / min to carry out polymerization reaction. The reaction temperature was 25 °C and the reaction time was 12 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0069] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0070] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 15 h to obtain bisphenol-type polyarylate.

[0071] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0072] Example 4

[0073] The method for preparing a biomass-derived polyarylate material using bisphenol-type polyarylate comprises the following steps:

[0074] (1) Add 1.65 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.50 g of sodium hydroxide, and 0.30 g of benzyltriethylammonium chloride into a three-necked flask with 60 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0075] (2) Add 1.15 g of 2,5-furandicarbonyl chloride into a single-necked flask containing 20 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0076] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 3 mL / min at 300 r / min to carry out polymerization reaction. The reaction temperature was 30 °C and the reaction time was 10 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0077] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0078] (5) The precipitate was crushed, washed, and vacuum-dried at 150°C for 10 h to obtain bisphenol-type polyarylate.

[0079] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of chloroform. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 130 ° C for 15 h to obtain the polyarylate material.

[0080] Comparative Example 1

[0081] A method for preparing a polyarylate material comprises the following steps:

[0082] (1) Add 1.18 g of bisphenol A, 0.47 g of sodium hydroxide, and 0.15 g of benzyltriethylammonium chloride into a three-necked flask with 40 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0083] (2) Add 1.00 g of isophthaloyl chloride into a single-necked flask containing 25 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0084] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 2 mL / min and a flow rate of 400 r / min to carry out polymerization reaction. The reaction temperature was 25 °C and the reaction time was 12 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0085] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0086] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 10 h to obtain bisphenol-type polyarylate.

[0087] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0088] Comparative Example 2

[0089] A method for preparing a polyarylate material comprises the following steps:

[0090] (1) Add 1.56 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.47 g of sodium hydroxide, and 0.15 g of benzyltriethylammonium chloride into a three-necked flask with 40 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0091] (2) Add 1.00 g of isophthaloyl chloride into a single-necked flask containing 25 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0092] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 2 mL / min and a flow rate of 400 r / min to carry out polymerization reaction. The reaction temperature was 60 °C and the reaction time was 12 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0093] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was washed and purified with deionized water until the pH of the aqueous phase solution separated by washing was neutral. It was then poured into 400 mL of ethanol for precipitation and filtration.

[0094] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 10 h to obtain bisphenol-type polyarylate.

[0095] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0096] Comparative Example 3

[0097] A method for preparing a polyarylate material comprises the following steps:

[0098] (1) Add 1.56 g of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 0.47 g of sodium hydroxide, and 0.15 g of benzyltriethylammonium chloride into a three-necked flask with 40 mL of deionized water and stir to dissolve to obtain an inorganic phase solution.

[0099] (2) Add 1.00 g of isophthaloyl chloride into a single-necked flask containing 25 mL of dichloromethane and stir with a magnetic stirrer to obtain an organic phase solution.

[0100] (3) The organic phase solution was poured into a constant pressure dropping funnel and added dropwise to the inorganic phase solution in the three-necked flask at a rate of 2 mL / min and a flow rate of 400 r / min to carry out polymerization reaction. The reaction temperature was 60 °C and the reaction time was 12 h. After the reaction was completed, the upper inorganic phase solution was separated to obtain the organic phase, i.e., the polymer solution.

[0101] (4) After adding 4 mL of dilute hydrochloric acid to the polymer solution for pickling, it was purified by washing with deionized water until the pH of the aqueous phase solution separated by washing was neutral. 400 mL of ethanol was poured into the polymer solution and the precipitate was filtered.

[0102] (5) The precipitate was crushed, washed, and vacuum-dried at 120°C for 10 h to obtain bisphenol-type polyarylate.

[0103] (6) 0.4 g of bisphenol-type polyarylate was stirred and dissolved in 6 mL of dichloromethane. After filtering with a sand core funnel, the filtrate was poured into a watch glass. After natural evaporation, it was placed in a vacuum oven and dried at 100 °C for 10 h to obtain the polyarylate material.

[0104] The polyarylate materials prepared in the examples and comparative examples were tested as follows.

[0105] Test 1: Infrared spectroscopy

[0106] The sample and potassium bromide were ground evenly in agate at a mass ratio of 1:150 and then pressed into tablets using a tablet press. Infrared spectrum test was performed using a Nicolet 20DXB infrared spectrometer, as shown in Figure 2. Figure 1 shown.

[0107] Test 2: Differential Scanning Calorimetry

[0108] The glass transition temperature of the samples was tested using a TA-Q25 thermal analyzer. -1 ) and the heating rate was 10 °C min -1 .like Figure 2 shown.

[0109] Test 3: Solubility test

[0110] 5 mg of the polyarylate samples prepared in the above examples and comparative examples were dissolved in 1 mL of the selected solvent, and the solubility test of the polymer samples was performed. The test results are shown in Table 1.

[0111] Test result analysis

[0112] Depend on Figure 1It can be seen that 2974cm -1 The absorption vibration peak of the side methyl group of 4,4'-methylenebis(5-isopropyl-2-methylphenol) is near 1740 cm -1 The absorption vibration peak of the ester bond on the main chain is 1500cm -1 and 1600cm -1 The two strong absorption peaks are the stretching absorption vibration peaks of the CC skeleton of the benzene ring on the main chain of the four polymers. The wave number is 950cm -1 The COC absorption peak on the furan ring in Example 4 appeared at 100 nm, demonstrating the successful introduction of the furandicarboxylic acid structure. Furthermore, no significant -OH absorption peaks appeared at high wavenumbers, indicating that all four reactions were relatively complete. IR spectroscopic results indicate the successful preparation of four bio-based polyarylate materials.

[0113] Depend on Figure 2 It can be seen that the glass transition temperature of the polymer materials obtained in the four examples is above 150°C, reaching the level of special engineering plastics, indicating that they have excellent heat resistance. A comparison of Examples 1, 2, and 3 shows that the addition of terephthaloyl chloride content affects the glass transition temperature of the polymer. This is because the addition of terephthaloyl chloride units enhances the regularity of the molecular chain, increases the rigidity of the polymer, and thus improves the heat resistance of the polymer. In addition, the introduction of furan ring structures can still maintain the rigid structure of a certain material, giving the polymer good heat resistance. The glass transition temperature of the petroleum-based polyarylate in Comparative Example 1 is 175°C, which is higher than that of the bio-based polyarylate prepared by the present invention. Examples 2 and 3 show that the heat resistance of the polymer can be further improved by adjusting the ratio of the two acyl chlorides. Comparative Examples 2 and 3 show that changes in reaction temperature and post-treatment methods both reduce the glass transition temperature. The heat resistance of the bio-based polyarylate prepared by the present invention meets the use standards of engineering plastics and has certain application value prospects.

[0114] Table 1 shows the solubility of the polymers. The test results show that Examples 1-4 are all soluble in common organic solvents at room temperature, demonstrating that the polyarylate materials with a carvacrol structure have excellent solubility. The petroleum-based polyarylate material with a bisphenol A structure in Comparative Example 1 is soluble in most organic solvents, but has poor solubility or even insolubility in some solvents. The bio-based polyarylate material with a carvacrol structure prepared by the present invention is soluble in all common organic solvents, demonstrating its excellent solution processing capability.

[0115] Table 1 Solubility test results of polymers

[0116]

[0117] In summary, the present invention uses bisphenol polyarylate to prepare biomass-derived bisphenol polyarylate material, and obtains the final polyarylate material through the fixed steps of interfacial polycondensation such as stirring and configuration, dropwise polymerization, acid washing, precipitation and filtration. Figure 1 Infrared spectrum analysis and Figure 2 The DSC spectrum analysis showed that this bio-based polyarylate material was successfully synthesized through the interfacial polymerization method, and the obtained material had excellent heat resistance and solubility.

Claims

1. A method for preparing bisphenol-type polyarylate, characterized in that: The following steps are involved: (1) Add 4,4'-methylenebis(5-isopropyl-2-methylphenol), sodium hydroxide, and benzyltriethylammonium chloride into water and stir to dissolve to obtain an inorganic phase solution; (2) adding an aromatic diformyl chloride compound to dichloromethane and stirring to obtain an organic phase solution; (3) Add the organic phase solution dropwise to the inorganic phase solution to carry out polymerization reaction, and obtain a polymer solution after the reaction is completed; the polymerization reaction temperature is 20-30°C, the reaction time is 10-15h, and the stirring speed is 300-600r / min; (4) After acid washing, the polymer solution was purified by washing with water, poured into ethanol for precipitation and filtration; (5) crushing the precipitate, washing it, and vacuum drying it to obtain bisphenol-type polyarylate; (6) Dissolving the bisphenol-type polyarylate with a solvent by stirring, filtering, volatilizing the filtrate, and vacuum drying to obtain a polyarylate material; The bisphenol polyarylate has the general structural formula: ， Where R is 、 or , n is an integer, and its value is 30-150; The structural formula of 4,4'-methylenebis(5-isopropyl-2-methylphenol) is: .

2. The method for preparing bisphenol-type polyarylate according to claim 1, wherein: All raw materials of the inorganic phase solution of step (1) and the organic phase solution of step (2) are mixed according to the following weight proportions: 150-160 parts of 4,4'-methylenebis(5-isopropyl-2-methylphenol), 45-50 parts of sodium hydroxide, 15-25 parts of benzyltriethylammonium chloride, 4000-6000 parts of water, 100-115 parts of aromatic diformyl chloride compound, and 2000-3000 parts of dichloromethane.

3. The method for preparing bisphenol-type polyarylate according to claim 1, wherein: The organic phase solution in step (3) is added dropwise to the inorganic phase solution at a rate of 2 mL / min to 3 mL / min.

4. The method for preparing bisphenol-type polyarylate according to claim 1, wherein: The washing and purification in step (4) is carried out until the pH of the aqueous phase solution separated by washing is neutral.

5. The method for preparing bisphenol-type polyarylate according to claim 1, wherein: The vacuum drying temperature of step (5) is 120-150°C, and the drying time is 10-15h.

6. The method for preparing bisphenol-type polyarylate according to claim 1, wherein: The solvent of step (6) is one or both of dichloromethane and chloroform, the drying temperature is 100-130° C., and the drying time is 10-15 h.

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