CN115888825A - A kind of bisphenol A synthetic composite resin catalyst and preparation method thereof - Google Patents

Abstract

The invention relates to a bisphenol A synthetic composite resin catalyst and a preparation method thereof, which mainly solves the problems that the existing resin catalysts have poor shrinkage resistance in the industrial application of bisphenol A, which may easily cause catalyst pores to shrink, impurities to accumulate, and catalytic performance to decline . Using styrene or substituted styrene as a monomer, divinylbenzene as a crosslinking agent, adding a certain amount of nano-materials to synthesize a spherical particle copolymer, the copolymer is sulfonated as a base resin, and mercaptoalkyl quaternary ammonium salt As a mercaptolation agent, the base resin is modified by an ion exchange method to obtain a bisphenol A synthetic composite resin catalyst. The structure of the composite resin catalyst synthesized by this scheme is stable, the anti-shrinkage ability of the resin is improved, and at the same time, it has high catalytic activity and selectivity.

Description

A kind of bisphenol A synthetic composite resin catalyst and preparation method thereof

Technical field

The invention relates to a compound and a synthesis method thereof, in particular to a bisphenol A synthetic composite resin catalyst and a preparation method.

Background technique

The synthesis of bisphenol A by ion exchange resin has simple process, less equipment corrosion and less waste. The raw material of insulating grade epoxy resin - the advanced production process of bisphenol A.

Currently used ion exchange resin catalysts, the base resin is a gel or macroporous cation exchange resin with an exchange capacity of 2.0-5.5 mmol/g dry resin. Such as sulfonated styrene-divinylbenzene copolymer, sulfonated phenolic resin, etc., applicable brand names such as: Amberlite-118, -200, -IR, -XE307; Amberlyst-15, -31, -121, -131, -232; Dowex-50WX2, 50WX4, -M31, -DR2030; Diaion SK104, SK1B, PK208, PK212, PK216; Purolite CT124, CT122, CT151; Suqing 002CR, etc.

The aforementioned basic resin is modified into a resin catalyst for the synthesis of bisphenol A. The method usually adopted is to introduce a catalytic group, such as a mercapto group, into the ion exchange resin matrix, thereby improving its reaction rate and selectivity. The research work in this area has never stopped since the advent of the synthesis of bisphenol A by the ion exchange resin method. As far as the introduction of sulfhydryl groups is concerned, there are many methods reported in the literature.

One is to introduce mercapto groups in the form of covalent bonding: such as partial reduction method US3172916), partial esterification method (US3153001; BP937072), and the method of re-reduction by sulfonamide (US4294995; US4346247; US4396728).

One is to introduce mercapto groups in the form of ionic bonds. Because the catalysts obtained by this method have better catalytic performance, this method has attracted people's attention, and a variety of compounds containing mercapto groups have been developed for partial neutralization and ion exchange.

Partially neutralized mercapto compounds include: thiazolidine (US3634341; US3760006), aryl mercaptoamine or its salt (JP10211434; US4045379), pyridyl alkyl mercaptan (CN101130519; CN103483154; US4478956), N-(2-mercaptoalkane base) amides (US4595704; CN8510611), polymercaptoalkylamines (EP268318; US4820740), alkylmercaptoamines (US3394089; BP1183564), N-alkylmercaptoamines (EP144735), N, N-dialkylmercaptoamines ( CN1119129).

The mercapto compounds for ion exchange include: the quaternary ammonium salt with mercapto groups is exchanged with part of the hydrogen ions on the base resin, so that the catalytic group is introduced into the ion exchange resin matrix. A quaternary ammonium salt with a mercapto group of a suitable structure can be selected to obtain a resin catalyst (CN1544152A; JP8089819) for the synthesis of bisphenol A with good catalytic activity and high selectivity.

Various cation exchange resins developed by the above-mentioned technologies have high activity and selectivity of the catalyst itself. However, these resin catalysts have the problem of poor shrinkage resistance. In the fixed bed reaction system, the shrinkage of the resin volume makes the pore size smaller, which affects the diffusion of the reaction substance, and is easy to cause the accumulation of impurities, the blockage of the catalyst pores, and the catalyst activity and use. The lifespan decreases, which ultimately leads to a decrease in the economic benefit per unit mass of the catalyst. The invention adds nanometer material in the cationic exchange resin structure to improve the anti-shrinkage performance of the resin catalyst.

Contents of the invention

The purpose of the present invention is to overcome above-mentioned defect, provide a kind of composite resin catalyst with good anti-shrinkage property, it can be used as the catalyst of phenol and acetone condensation synthesis bisphenol-A.

Another object of the present invention is to provide a method for preparing the composite resin catalyst.

In order to achieve one of the above objects, the technical scheme adopted by the present invention is as follows: a catalyst for synthesizing bisphenol A composite resin.

Using styrene or substituted styrene as a monomer, divinylbenzene, divinylphenylmethane or dipenylbenzene as a crosslinking agent, and graphene, carbon nanotubes, etc. as nanocomposite additives to synthesize crosslinked copolymers The interpolymer is used as the base resin for the preparation of bisphenol A catalyst after sulfonation. Using mercaptoalkyl quaternary ammonium salt as mercaptolation agent, the base resin is modified by ion exchange method to obtain bisphenol A synthetic composite resin catalyst.

The base resin components are as follows:

1) 30-90% polymerized monomer;

2) 1-30% cross-linking agent;

3) 0.1-20% nanomaterials;

4) 8.0-25% mercaptoalkyl quaternary ammonium salt.

Wherein, the polymerized monomer has the following general structural formula:

X can be hydrogen, halogen (including fluorine, chlorine, bromine), nitro, carboxyl and other electron-withdrawing groups. Preferably, the polymerizable monomer is 4-chlorostyrene.

The crosslinking agent may be at least one of divinylbenzene, divinylphenylmethane, and dialnylbenzene. Preferably, the crosslinking agent is divinylbenzene.

The nanomaterial may be at least one of graphene and carbon nanotubes.

The graphene is selected from at least one of single-layer graphene, multi-layer graphene, aminated graphene, graphene oxide, hydroxylated graphene, carboxylated graphene, preferably, the graphene is a single layer Graphene.

The carbon nanotubes are at least one of single-wall carbon nanotubes and multi-wall carbon nanotubes. Preferably, the carbon nanotubes are single-wall carbon nanotubes.

The mercaptoalkyl quaternary ammonium salt can be N,N-dimethyl-N-ethyl-3-mercaptopropyl quaternary ammonium salt, N,N,N-trimethyl-3-mercaptopropyl quaternary ammonium salt , N,N-dimethyl-N-propyl-3-mercaptopropyl quaternary ammonium salt, preferably, the mercaptoalkyl quaternary ammonium salt is N,N-dimethyl-N-ethyl -3-Mercaptopropyl quaternary ammonium salt.

For realizing the above-mentioned object two, the technical scheme that the present invention adopts is as follows: a kind of preparation method of bisphenol A synthetic composite resin catalyst comprises the following steps:

(1) After mixing styrene or substituted styrene with divinylbenzene, divinylphenylmethane or dipenylbenzene, and graphene and carbon nanotubes, carry out suspension copolymerization to obtain composite copolymer beads, It can be of gel type or macroporous type. Among them, divinylbenzene, divinylphenylmethane or dialenylbenzene accounts for 1-30% of the total mass of the monomers, preferably 2-6%. Graphene and carbon nanotubes account for 0.1-20% of the total mass of the monomer, preferably 0.5-5%.

(2) Sulfonate the obtained composite copolymer pellets according to the preparation method of conventional sulfonic acid type cation exchange resins to obtain the base resin for preparing bisphenol A catalyst.

(3) According to the disclosed technology, the mercaptoalkyl quaternary ammonium salt is used as the mercaptolation agent, and the above-mentioned base resin is modified by the ion exchange method, and the sulfonic acid group and the mercaptoalkyl quaternary ammonium are ionically bonded to obtain a composite Ion exchange resin catalyst. Among them, the mercapto alkyl quaternary ammonium salt accounts for 8.0-25% of the total mass of the base resin, preferably 18-22%.

Description of drawings

Fig. 1 is a fixed-bed continuous reaction evaluation diagram of composite resin catalyst A.

Fig. 2 is an evaluation diagram of the fixed bed continuous reaction of the resin catalyst E.

Detailed ways

The following specific examples will further illustrate the present invention, but the present invention is not limited thereby.

The method for determining the shrinkage of the composite fat catalyst of the present invention is as follows: measure a certain volume of composite resin catalyst, record the volume as V ₁ , wash the composite resin catalyst with anhydrous phenol until the water content of the phenol is less than 0.1%, and then use Infiltrate with anhydrous phenol for 2 hours, record the volume as V ₂ . Calculation formula of shrinkage rate: Φ=(V ₂ -V ₁ )/V ₁ …………………(1)

The yield and selectivity calculation method of phenol and acetone reaction to generate bisphenol A is as follows

Yield Y (%)=C _BPA (94.11 × R _m +58.08)/228.28 × 100... (2) In the formula, C _BPA is the content of bisphenol A in the reaction solution; 94.11 is the molecular weight of phenol; R _m is the raw material phenol and The molar ratio of acetone; 58.08 is the molecular weight of acetone; 228.28 is the molecular weight of bisphenol A.

Bisphenol A selectivity S (%)=...(3)

In the formula, C _BPA , C _chroman , C _2,4-BPA, C _triphenol , C _other , are respectively bisphenol A, chroman, 2,4-bisphenol A, triphenol, and other impurities in the reaction solution content.

Example 1

In a 250 ml four-neck flask, add 150 ml of distilled water, 1.5 g of gelatin and 0.15 g of auxiliary dispersant, stir to dissolve the dispersant, then stop stirring. Take by weighing 30.0 grams of 4-chlorostyrene in a 100 milliliter beaker, 2.6 grams of divinylbenzene (mass content 50%), 0.32 grams of benzoyl peroxide, 0.32 grams of single-layer graphene, pour this solution after mixing into the flask. Start stirring, adjust the stirring speed, heat up to 80°C, keep warm for 2 hours, heat up to 85°C, keep warm for 2 hours, heat up to 95°C, keep warm for 2 hours. The materials are taken out, washed with water and dried to obtain composite copolymer pellets.

In a 250 ml four-neck flask, add 20 g of composite interpolymer pellets prepared by the above method, 20 ml of dichloroethane, and swell for 20 minutes, then add 100 ml of concentrated sulfuric acid, heat up to 78°C, and keep warm for 5 hours. Evaporate dichloroethane by heating up, keep warm at 100°C for 5 hours, cool, filter, dilute with dilute sulfuric acid, wash with water until neutral, and drain to obtain sulfonic acid composite resin a.

In a 150 ml four-necked flask, add 60 ml of deionized water, 20 g of the above-mentioned sulfonic acid composite resin a, 4.6 g of N,N-dimethyl-N-ethyl-3-mercaptopropyl quaternary ammonium salt, reaction 5 hour, take out the resin, wash it to neutral with deionized water, and obtain bisphenol A synthetic composite resin catalyst A.

Example 2

As in Example 1, 1.3 grams of multi-walled carbon nanotubes were changed from single-layer graphene to obtain sulfonic acid composite resin b and bisphenol A synthetic composite resin catalyst B.

Example 3

As in Example 1, the single-layer graphene was changed to 0.65 g of single-walled carbon nanotubes to prepare sulfonic acid composite resin c and bisphenol A composite resin catalyst C.

Example 4

As in Example 1, the amount of single-layer graphene was changed to 0.16 grams of graphene oxide to prepare sulfonic acid composite resin d and bisphenol A synthetic composite resin catalyst D.

Comparative Example 1

As in Example 1, only without adding single-layer graphene, bisphenol A synthetic resin catalyst E was obtained.

Example 5

Measure 10mL each of resin catalysts A, B, C, D, and E, put them into a resin washing column, wash with phenol until the water content of the effluent phenol is less than 0.1%, then infiltrate with phenol for 2 hours, and record the volume of each resin catalyst , according to the formula (1) to calculate the shrinkage of the resin catalyst, the results are shown in Table 1.

Shrinkage of table 1 resin catalyst

Example 6

Add dry resin catalyst A, or B, or C, or D, or E, 10.0 g, 65.0 g phenol, dried at 105°C for 12 hours into a four-necked flask equipped with a stirrer and a thermometer, and heat to 70°C under stirring , constant temperature 3 hours, add 5.0 grams of acetone, react 60 minutes, stop reaction, high pressure liquid chromatography analyzes each component content, and calculates the yield and the selectivity of bisphenol A according to formula (2), (3), the results are shown in Table 2.

The catalytic activity comparison of table 2 resin catalyst

Example 7

Put 20 milliliters of the above-mentioned composite resin catalyst A into a stainless steel fixed-bed reactor with an inner diameter of 16 mm and a length of 200 mm, and continuously react the phenol-acetone solution with a molar ratio of 10/1 at 70 ° C at a space velocity of 1 h ^-1 to measure bisphenol A Yield and selectivity, the results are shown in Figure 1.

Comparative Example 2

As in Example 7, the composite resin catalyst A was changed to resin catalyst E, and the phenol-acetone solution with a molar ratio of 10/1 was continuously reacted at 70° C. with a space velocity of 1 h ⁻¹ to measure the yield and selectivity of bisphenol A. The result Figure 2.

Example 8

The catalyst of Example 7 and Comparative Example 2 was taken out for 1100 hours, washed with water, methanol, acetone, dichloromethane, washed with 5% sodium hydroxide, and finally adjusted to PH=2 with 5% aqueous hydrochloric acid, Precipitate solid impurities, filter, dry, and weigh. The impurities in Example 7 accounted for 0.13% of the composite resin catalyst A, and the impurities in Comparative Example 2 accounted for 0.21% of the catalyst E.

Claims (5)

1. a kind of bisphenol A synthetic composite resin catalyst is characterized in that, composition is as follows by mass ratio: 1) 30-90% monomer; 2) 1-30% cross-linking agent; 3) 0.1-20% nanomaterials; 4) 8.0-25% mercaptoalkyl quaternary ammonium salt; Wherein, the monomer has the following general structural formula:

X includes but not limited to hydrogen, halogen (including fluorine, chlorine, bromine), nitro, carboxyl electron-withdrawing groups; The crosslinking agent is at least one of divinylbenzene, divinylphenylmethane, and dialnylbenzene; The nanomaterial is at least one of graphene, carbon nanotubes, and nano-silicon oxide; The mercaptoalkyl quaternary ammonium salts include but not limited to N,N-dimethyl-N-ethyl-3-mercaptopropyl quaternary ammonium salt, N,N,N-trimethyl-3-mercaptopropyl quaternary Ammonium salt, N,N-dimethyl-N-propyl-3-mercaptopropyl quaternary ammonium salt. 2. a kind of bisphenol A synthetic composite resin catalyst according to claim 1 is characterized in that, described monomer is selected from 4-chlorostyrene. 3. a kind of bisphenol A synthetic composite resin catalyst according to claim 1 is characterized in that, described linking agent is selected from divinylbenzene. 4. a kind of bisphenol A synthetic composite resin catalyst according to claim 1, is characterized in that, described nanometer material is selected from monolayer graphene, multilayer graphene, aminated graphene, graphene oxide, hydroxylated One or more nanomaterials in graphene, carboxylated graphene, single-walled carbon nanotubes, and multi-walled carbon nanotubes. 5. a preparation method for bisphenol A synthetic composite resin catalyst, is characterized in that, comprises the following steps: 1) Mix monomers, crosslinking agents and nanomaterials evenly, and then carry out suspension copolymerization to obtain composite copolymer beads; 2) sulfonating the composite copolymer pellets according to a conventional method to obtain a sulfonic acid type composite cation exchange resin, as the base resin for preparing bisphenol A catalyst; 3) According to the disclosed technology, the mercaptoalkyl quaternary ammonium salt is used as the mercaptolation agent, and the base resin is modified by the ion exchange method, and the sulfonic acid group on the resin is combined with the mercaptoalkylammonium in the form of an ion bond; wherein , The mercapto alkyl quaternary ammonium salt accounts for 8.0-25% of the total mass of the base resin.

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