Bisphenol compound, synthesis method and polycarbonate prepared from bisphenol compound

Abstract

The invention relates to a bisphenol compound, a synthesis method and polycarbonate prepared from the bisphenol compound, the bisphenol compound is abbreviated as bisphenol acenaphthene, and the bisphenol compound is synthesized through chemical reaction by taking acenaphthone and phenol as raw materials, solid superacid SO4 < 2-> / Fe2O3 as a catalyst, 3-mercaptopropionic acid as a cocatalyst and toluene as a solvent and a water-carrying agent. Compared with common bisphenol A type polycarbonate, the bisphenol acenaphthene type polycarbonate prepared by taking bisphenol acenaphthene as a raw material has better heat resistance and mechanical properties, and keeps the same transparency.

Description

Technical Field

[0001] The invention relates to a bisphenol compound, a synthesis method and polycarbonate prepared therefrom, and belongs to the field of polymer materials. Background Art

[0002] Polycarbonate (PC), usually refers to bisphenol A polycarbonate, which has excellent impact resistance, high and low temperature resistance and other properties, and is the best in transparency among the currently used engineering plastics. Due to these excellent properties, it is widely used in the automotive, electronics, building materials, packaging and other industries. Although bisphenol A polycarbonate has certain heat resistance and its glass transition temperature is 150°C, it is still insufficient, which limits its application in lighting, aerospace and other fields.

[0003] 1,1-bis(4-hydroxyphenyl)acenaphthene, referred to as bisphenolacenaphthene, is a functional polymer monomer. The acenaphthene ring is connected to two phenols in bisphenolacenaphthene. Due to its unique structure, it can improve the heat resistance and mechanical properties of polycarbonate and has good optical properties. Therefore, it can replace bisphenol A as a raw material for synthesizing new heat-resistant polycarbonate and is widely used in the fields of aerospace, electronics, and automobile industries.

[0004] The structural formulas of bisphenol A and bisphenol acenaphthene are as follows: .

[0005] Increasing the rigidity of the molecular chain is the main structural factor to improve the heat resistance of polymers. Using bisphenol acenaphthene to replace bisphenol A, polycarbonate is prepared by interfacial polycondensation with phosgene or by melt ester exchange with diphenyl carbonate. The introduction of acenaphthene rings into the polycarbonate molecule increases the rigidity of the polycarbonate molecular chain and reduces the flexibility of the polycarbonate main chain. The large molecular bond force and the entanglement of the rigid molecular chain are not easy to be released, making it difficult for the molecules to slide relative to each other, so that the glass transition temperature of bisphenol acenaphthene-type polycarbonate is more than 100°C higher than that of bisphenol A, and the heat resistance is greatly improved. Due to the considerable rigidity and large molecular bond force, a certain steric hindrance is strengthened, and its mechanical properties are also improved. Bisphenol acenaphthene-type polycarbonate maintains almost the same transparency as bisphenol A-type polycarbonate.

[0006] The structural formulas of bisphenol A polycarbonate and bisphenol acenaphthene polycarbonate are as follows: .

[0007] The main methods for synthesizing bisphenol compounds include sulfuric acid method, hydrogen chloride method, mercaptosulfonic acid method, cation exchange resin method and heteropoly acid method (Gao Qingping, Research on the Synthesis Process of Bisphenol Fluorene, Master's Thesis of Harbin Engineering University, 2006; Liu Huarong, Research on Clean Synthesis Process of Bisphenol Fluorene, Master's Thesis of Harbin Engineering University, 2008). Among them, the sulfuric acid method and hydrogen chloride method have serious equipment corrosion and environmental pollution problems; the mercaptosulfonic acid method is an improved method proposed by Dow Chemical Company in the United States to address the serious corrosion problem of inorganic acid catalysts, but it has not been promoted due to the high price of mercaptosulfonic acid; the thermal stability and swelling of cation exchange resin are the main problems of resin catalysts; heteropoly acid is expensive and has high production cost, and there is no industrial report. At the same time, the above methods all use a large amount of phenol, which is both a raw material and a solvent, resulting in difficulty in product separation and a large amount of raw material waste. The wasted raw material phenol is prone to environmental problems.

[0008] The synthesis method of bisphenol acenaphthene of the present invention uses acenaphthene ketone and phenol as raw materials, solid super acid SO 4 2- / Fe 2 O 3 as catalyst, 3-mercaptopropionic acid as co-catalyst, and toluene as solvent and water carrier. Catalyst solid superacid SO 4 2- / Fe 2 O 3 It is easy to prepare, inexpensive, does not corrode equipment, does not pollute the environment, has good catalytic effect, and is easy to separate; using toluene as a solvent avoids the use of large amounts of phenol. At the same time, toluene also acts as a water-carrying agent, promoting the reaction and improving the reaction conversion rate. Toluene can also be recycled. Summary of the invention

[0009] The purpose of the present invention is to provide a bisphenol compound, a synthesis method and a polycarbonate prepared therefrom.

[0010] The chemical name of the bisphenol compound is 1,1-bis(4-hydroxyphenyl)acenaphthene, referred to as bisphenolacenaphthene, and the structural formula is as follows: .

[0011] The synthesis method of bisphenol acenaphthene comprises the following steps: Step 1: Use acenaphthene and phenol as raw materials and solid superacid SO 4 2- / Fe 2 O 3 as a catalyst, 3-mercaptopropionic acid as a co-catalyst, toluene as a solvent and a water-carrying agent, and the above substances are prepared in a mass ratio of acenaphthene ketone: phenol: solid superacid SO 4 2- / Fe 2 O 3:3-Mercaptopropionic acid:toluene = 1:1.3:0.2:0.1:5 are added to a reaction vessel with a condenser, stirred and heated to 90℃~100℃, toluene continuously takes out the water generated by the reaction, and after standing and stratification, toluene is returned to the reaction vessel. After 10h~12h, the reaction is completed, and the catalyst solid superacid SO is recovered after hot filtration. 4 2- / Fe 2 O 3 ; Step 2: Cool the filtrate obtained in step 1 to 5°C to 10°C, precipitate crystals, filter and dry, add twice the mass of toluene for recrystallization, heat the recrystallization to 90°C, cool to 5°C to 10°C, filter to obtain white crystals, dry to obtain bisphenol acenaphthene, and the mass fraction is greater than 99.5% as determined by liquid chromatography; Step 3: The catalyst solid superacid SO recovered in step 1 4 2- / Fe 2 O 3 Can be reused; Step 4: The filtrate after cooling, crystallization and filtration in step 2 is a toluene solution containing unreacted raw material phenol and product bisphenol acenaphthene, which can be directly recycled as a solvent without separation.

[0012] Bisphenol acenaphthene is used as the raw material and polymerized with phosgene or diphenyl carbonate to produce bisphenol acenaphthene type polycarbonate, the structural formula of which is as follows: .

[0013] The acenaphthene ring is connected to the two phenols in bisphenol acenaphthene, which is a large cyclic side group, which is significantly different from the two methyl groups of bisphenol A. Using bisphenol acenaphthene to synthesize polycarbonate can effectively improve the rigidity of the polycarbonate molecular chain, increase the intermolecular sliding steric hindrance, and thus improve the heat resistance and mechanical properties of polycarbonate. Bisphenol acenaphthene and bisphenol A are both bisphenol compounds, so it can replace bisphenol A as a raw material for synthesizing new heat-resistant polycarbonate and maintain its original transparency.

[0014] The reaction equation for the synthesis of bisphenol acenaphthene is: .

[0015] From the reaction equation, it can be seen that the theoretical molar ratio of acenaphthene to phenol is 1:2. In order to ensure the generation of bisphenols and avoid the generation of monophenol by-products, an appropriate excess of phenol is required. The current process directly uses a large amount of phenol as both a raw material and a solvent. A large amount of phenol is easy to cause waste and bring environmental problems, and is not conducive to separation from the product bisphenol acenaphthene. Using toluene as a solvent and an appropriate excess of raw material phenol can ensure the generation of bisphenol products and keep the raw materials in a reasonable ratio, saving raw material phenol. At the same time, cooling and crystallization make it easy to separate the product bisphenol acenaphthene. The filtrate after filtration is a toluene solution containing a small amount of phenol and bisphenol acenaphthene, so it does not need to be separated and can be directly used as a solvent for the next reaction, achieving zero emission of substances. In addition, toluene is also a water-carrying agent. During the reaction, the generated water can be continuously taken away, prompting the reaction to proceed to the right and improving the conversion rate of the reaction. Solid superacid SO 4 2- / Fe 2 O 3 Strong acidity and good catalytic effect; directly with (NH 4 ) 2 SO 4 ·Fe 2 (SO 4 ) 3 ·24H 2 O is used as raw material and calcined at high temperature (Li Jianwei et al., Solid Superacid SO 4 2- / Fe 2 O 3 Preparation and catalytic performance of bisphenol acenaphthene, Applied Chemical Industry, 2005.5), simple preparation, low cost; solid superacid is easy to separate after reaction, does not corrode equipment, and does not pollute the environment. The synthesized bisphenol acenaphthene has a purity of more than 99.5% and a yield of more than 84%. DETAILED DESCRIPTION

[0016] The present invention is further described below by examples: Example 1

[0017] 1. Preparation of bisphenol acenaphthene In a 250 ml three-necked flask equipped with a stirrer, a thermometer and a condenser, 10 g of acenaphthene, 13 g of phenol, and a catalyst solid superacid SO were added. 4 2- / Fe 2 O 3 2g, co-catalyst 3-mercaptopropionic acid 1g, toluene 50g.

[0018] Start stirring and heat the electric heating mantle to 90°C. The water generated by the reaction is taken out of the reaction solution by toluene, and the toluene is circulated back to the three-necked flask. After reacting for 10 hours, filter while hot. The filter cake is the catalyst solid superacid SO 4 2- / Fe2 O 3 , rinse with toluene and dry naturally before reuse. The filtrate is cooled to 5°C with an ice-water mixture, at which time crystals appear. Filter after 1 hour, and the filter cake is a crude product, which weighs 18.56g after drying. The filtrate is a toluene solution containing a small amount of phenol and bisphenol acenaphthene, which can be directly used as the solvent for the next reaction.

[0019] Take 18.56g of the crude product and put it into a beaker, add 37.12g of toluene, raise the temperature to 90°C, keep it warm for 1h, then gradually cool it to 5°C for recrystallization, filter out white crystals, and dry them to obtain bisphenol acenaphthene, weighing 17.28g. The purity detected by liquid chromatography is 99.58% (mass fraction), and the yield based on acenaphthene is 85.52%.

[0020] The recrystallization solvent toluene can be recycled or directly used as the solvent for the next reaction.

[0021] 2. Properties of Bisphenol Acenaphthene Polycarbonate Bisphenol acenaphthene prepared above was used as raw material and phosgene was polymerized by interfacial polycondensation to prepare bisphenol acenaphthene type polycarbonate, and its performance indicators are shown in Table 1. Bisphenol A type polycarbonate was prepared under the same conditions for performance comparison. Glass transition temperature (Tg) is the upper limit of the use temperature of engineering materials, which is suitable for measuring the heat resistance of polymer materials; simply supported beam impact strength (notch) and tensile strength are the two most important indicators for characterizing the mechanical properties of plastics, which can be used to characterize the mechanical properties of polymer materials; light transmittance can characterize the transparency of polymer materials.

[0022] Table 1 Properties of bisphenol A polycarbonate and bisphenol acenaphthene polycarbonate type Tg / ℃ <![CDATA[Izod impact strength (notched, 23 °C) / KJ·m -2 > Tensile strength (23℃) / MPa Light transmittance Bisphenol A polycarbonate 150 52.46 63.67 89.8 Bisphenol acenaphthene type polycarbonate 284 54.14 65.43 89.6

[0023] As shown in Table 1, the glass transition temperature of bisphenol acenaphthene polycarbonate increased by 134°C, indicating that its heat resistance has been greatly improved. From the perspective of simply supported beam impact strength (notch) and tensile strength, the mechanical properties of bisphenol acenaphthene polycarbonate have been improved to a certain extent. From the perspective of light transmittance, bisphenol acenaphthene polycarbonate basically maintains its original transparency. Example 2

[0024] 1. Preparation of bisphenol acenaphthene In a 250 ml three-necked flask equipped with a stirrer, a thermometer and a condenser, 12 g of acenaphthene, 15.6 g of phenol, and a catalyst solid superacid SO 4 2- / Fe 2 O 3 The raw material is 2.4g, the co-catalyst is 1.2g of 3-mercaptopropionic acid, and the toluene is 60g.

[0025] Start stirring and heat the electric heating mantle to 90°C. The water generated by the reaction is carried out of the reaction liquid by toluene. After reacting for 11 hours, filter while hot. The filter cake is the catalyst solid superacid SO 4 2- / Fe 2 O 3 , rinsed with toluene and dried naturally before reuse. The filtrate was cooled to 8°C with an ice-water mixture, at which time crystals appeared. After 1 hour, the filter cake was the crude product, which weighed 22.23 g after drying. The filtrate was directly used as the solvent for the next reaction.

[0026] Take 22.23 g of the crude product and put it into a beaker, add 44.46 g of toluene, raise the temperature to 90 ° C, keep it warm for 1 hour, then gradually cool it to 8 ° C for recrystallization, filter out white crystals, and dry them to obtain bisphenol acenaphthene, weighing 20.53 g. The purity was 99.62% as determined by liquid chromatography, and the yield was 84.71%.

[0027] The recrystallization solvent toluene can be recycled or directly used as the solvent for the next reaction.

[0028] 2. Properties of Bisphenol Acenaphthene Polycarbonate Bisphenol acenaphthene-based polycarbonate was prepared by using the bisphenol acenaphthene prepared above as a raw material and phosgene through an interfacial polycondensation method. The performance indicators are shown in Table 2.

[0029] Table 2 Properties of bisphenol A polycarbonate and bisphenol acenaphthene polycarbonate type Tg / ℃ <![CDATA[Izod impact strength (notched, 23 °C) / KJ·m -2 > Tensile strength (23℃) / MPa Light transmittance Bisphenol A polycarbonate 150 52.46 63.67 89.8 Bisphenol acenaphthene type polycarbonate 286 54.32 65.51 89.7

[0030] As shown in Table 2, the glass transition temperature of bisphenol acenaphthene polycarbonate increased by 136°C. The simply supported beam impact strength (notched) and tensile strength were improved. The bisphenol acenaphthene polycarbonate maintained its original transparency. Example 3

[0031] 1. Preparation of bisphenol acenaphthene Add 15 g of acenaphthene, 19.5 g of phenol, and catalyst solid superacid SO into a three-necked flask. 4 2- / Fe 2 O 3 3g, co-catalyst 3-mercaptopropionic acid 1.5g, toluene 75g.

[0032] Start stirring and heat the electric heating mantle to 90°C. The water generated by the reaction is carried out of the reaction liquid by toluene. After reacting for 12 hours, filter while hot. The filter cake is the catalyst solid superacid SO 4 2- / Fe 2 O 3, rinsed with toluene and dried naturally before reuse. The filtrate was cooled to 10°C with an ice-water mixture, at which time crystals appeared. After 1 hour, the filter cake was the crude product, which weighed 27.48 g after drying. The filtrate was directly used as the solvent for the next reaction.

[0033] Take 27.48 g of the crude product and put it into a beaker, add 54.96 g of toluene, raise the temperature to 90 ° C, keep it warm for 1 hour, then gradually cool it to 10 ° C for recrystallization, filter out white crystals, and dry them to obtain bisphenol acenaphthene, weighing 25.61 g. The purity detected by liquid chromatography is 99.70%, and the yield is 84.60%.

[0034] 2. Properties of Bisphenol Acenaphthene Polycarbonate Bisphenol acenaphthene prepared above was used as a raw material and was polymerized with diphenyl carbonate by melt transesterification to prepare bisphenol acenaphthene type polycarbonate, and its performance indicators are shown in Table 3. Bisphenol A type polycarbonate was prepared under the same conditions for performance comparison.

[0035] Table 3 Properties of bisphenol A polycarbonate and bisphenol acenaphthene polycarbonate type Tg / ℃ <![CDATA[Izod impact strength (notched, 23 °C) / KJ·m -2 > Tensile strength (23℃) / MPa Light transmittance Bisphenol A polycarbonate 149 52.18 63.24 89.4 Bisphenol acenaphthene type polycarbonate 279 53.67 64.75 89.3

[0036] As shown in Table 3, the glass transition temperature of bisphenol acenaphthene polycarbonate increased by 130°C. The simply supported beam impact strength (notch) and tensile strength were improved. The bisphenol acenaphthene polycarbonate basically maintained its original transparency.

Claims

1. A bisphenol compound, characterized in that The chemical name of the compound is 1,1-bis(4-hydroxyphenyl)acenaphthene, referred to as bisphenolacenaphthene, and the structural formula of the compound is as follows: .

2. The method for synthesizing bisphenol acenaphthene as claimed in claim 1, characterized in that The following steps are involved: Step 1: Use acenaphthene and phenol as raw materials and solid superacid SO4 2- / Fe2O3 is the catalyst, 3-mercaptopropionic acid is the co-catalyst, toluene is the solvent and water-carrying agent, and the above substances are in the mass ratio of acenaphthene ketone: phenol: solid superacid SO4 2- / Fe2O3:3-mercaptopropionic acid:toluene = 1:1.3:0.2:0.1:5 are added to a reaction vessel with a condenser, stirred and heated to 90℃~100℃, toluene continuously takes out the water generated by the reaction, and after standing and stratification, toluene is returned to the reaction vessel. After 10h~12h, the reaction is completed, and it is filtered while hot to recover the catalyst solid super acid SO4 2- / Fe2O3; Step 2: Cool the filtrate obtained in step 1 to 5°C to 10°C, precipitate crystals, filter and dry, add twice the mass of toluene for recrystallization, heat the recrystallization to 90°C, cool to 5°C to 10°C, filter to obtain white crystals, dry to obtain bisphenol acenaphthene, and the mass fraction is greater than 99.5% as determined by liquid chromatography; Step 3: The catalyst solid superacid SO4 recovered in step 1 2- / Fe2O3 can be reused; Step 4: The filtrate after cooling, crystallization and filtration in step 2 is a toluene solution containing unreacted raw material phenol and product bisphenol acenaphthene, which can be directly recycled as a solvent without separation.

3. The bisphenol acenaphthene described in claim 1 is used as a raw material and polymerized with phosgene or diphenyl carbonate to produce a bisphenol acenaphthene type polycarbonate, characterized in that Its structural formula is as follows: .

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