CN115888825A - Bisphenol A synthetic composite resin catalyst and preparation method thereof - Google Patents
Bisphenol A synthetic composite resin catalyst and preparation method thereof Download PDFInfo
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000000805 composite resin Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 mercapto alkyl quaternary ammonium salt Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical group ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000007796 conventional method Methods 0.000 claims 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 150000003440 styrenes Chemical class 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- XDTRNDKYILNOAP-UHFFFAOYSA-N phenol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC=C1 XDTRNDKYILNOAP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- SZEBGAQWWSUOHT-UHFFFAOYSA-N 2-(4-bromophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Br)C=C1 SZEBGAQWWSUOHT-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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Abstract
The invention relates to a bisphenol A synthetic composite resin catalyst and a preparation method thereof, and mainly solves the problems that the prior resin catalyst has poor anti-shrinkage performance in industrial application of bisphenol A, and is easy to cause the reduction of catalyst pore channels, impurity accumulation and the reduction of catalytic performance. Styrene or substituted styrene is used as a monomer, divinyl benzene and the like are used as a crosslinking agent, a certain amount of nano materials are added to synthesize a spherical particle copolymer, the copolymer is sulfonated to be used as a base resin, mercapto alkyl quaternary ammonium salt is used as a sulfhydrylation agent, and the base resin is modified by an ion exchange method to obtain the bisphenol A synthetic composite resin catalyst. The composite resin catalyst synthesized by the scheme has a stable structure, improves the anti-shrinkage capacity of resin, and has high catalytic activity and selectivity.
Description
Technical Field
The invention relates to a compound and a synthetic method thereof, in particular to a composite resin catalyst synthesized by bisphenol A and a preparation method thereof.
Background
The bisphenol A synthesized by the ion exchange resin method has the advantages of simple process, little equipment corrosion and little three wastes, is greatly developed in recent years, and particularly becomes an advanced production process method of bisphenol A which is a raw material of high-quality engineering plastics and high-insulation-level epoxy resin along with the continuous improvement of the performance of an ion exchange resin catalyst.
The ion exchange resin catalyst used at present, the base resin is gel or macroporous cation exchange resin with exchange capacity of 2.0-5.5 mmol/g dry resin. Such as sulfonated styrene-divinylbenzene copolymers, sulfonated phenolic resins, and the like, and are available under trade designations 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 and the like.
The aforementioned base resin is modified into a resin catalyst for the synthesis of bisphenol A, usually by introducing a co-catalyst group such as mercapto group into the ion exchange resin matrix, thereby increasing the reaction rate and selectivity. The research work in this area has been uninterrupted since the synthesis of bisphenol A by the ion exchange resin method was known. With respect to the introduction of thiol groups, many methods have been reported in the literature.
One is to introduce a thiol group in a covalently bound form: such as partial reduction method US 3172916), partial esterification method (US 3153001; BP 937072), methods of sulfonamide re-reduction (US 4294995; US4346247; US 4396728).
One is to introduce a mercapto group in an ionically bonded form, which attracts attention because of better catalytic performance of the catalyst obtained by this method, and several mercapto group-containing compounds have been successively developed for partial neutralization and ion exchange.
Partially neutralized mercapto compounds are: thiazolidine (US 3634341; US 3760006), arylmercaptoamines or their salts (JP 10211434; US 4045379), pyridylalkylthiols (CN 101130519; CN103483154; US 4478956), N- (2-mercaptoalkyl) amides (US 4595704; CN 8510611), polymercaptylamines (EP 268318; US 4820740), alkylmercaptoamines (US 3394089; BP 1183564), N-alkylmercaptoamines (EP 144735), N-dialkylmercaptoamines (CN 9129).
Examples of ion-exchanged mercapto compounds are: quaternary ammonium salt with mercapto group is exchanged with partial hydrogen ion on the base resin to introduce co-catalyst group into the ion exchange resin matrix. The resin catalyst (CN 1544152A; JP 8089819) with good catalytic activity and high selectivity for synthesizing bisphenol A can be obtained by selecting quaternary ammonium salt with sulfhydryl group and proper structure.
The activity and selectivity of the catalyst of various cation exchange resins developed by the technology are high. However, these resin catalysts have a problem of poor anti-shrinkage performance, and in a fixed bed reaction system, the pore diameter is reduced due to the shrinkage of the resin volume, which affects the diffusion of reaction substances, and also easily causes the accumulation of impurities, the blockage of catalyst pore channels, and the reduction of catalyst activity and service life, and finally leads to the reduction of economic benefit per unit mass of catalyst. The invention adds nano material in the cation exchange resin structure to improve the anti-shrinkage performance of the resin catalyst.
Disclosure of Invention
The invention aims to overcome the defects and provide a composite resin catalyst with good anti-shrinkage performance, which can be used as a catalyst for synthesizing bisphenol A by condensing phenol and acetone.
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 purposes, the technical scheme adopted by the invention is as follows: a bisphenol A synthetic composite resin catalyst.
Styrene or substituted styrene is used as a monomer, divinyl benzene, divinyl phenyl methane or dipropenyl benzene is used as a crosslinking agent, graphene, carbon nano tubes and the like are used as nano composite material additives to synthesize a crosslinked copolymer, and the crosslinked copolymer is sulfonated and then used as a base resin for preparing a bisphenol A catalyst. The bisphenol A synthetic composite resin catalyst can be obtained by modifying base resin by an ion exchange method by taking mercapto alkyl quaternary ammonium salt as a sulfhydrylation agent.
The base resin component was as follows:
1) 30-90% of polymerized monomers;
2) 1-30% of a cross-linking agent;
3) 0.1-20% of nano material;
4) 8.0 to 25 percent of mercapto alkyl 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, and preferably, the polymerized monomer is 4-chlorostyrene.
The crosslinking agent can be at least one of divinylbenzene, divinylphenylmethane and dipropenylbenzene, and preferably, the crosslinking agent is divinylbenzene.
The nano material can be at least one of graphene and carbon nano tube.
The graphene is selected from at least one of single-layer graphene, multi-layer graphene, aminated graphene, oxidized graphene, hydroxylated graphene and carboxylated graphene, and preferably, the graphene is single-layer graphene.
The carbon nanotube is at least one of a single-walled carbon nanotube and a multi-walled carbon nanotube, and preferably, the carbon nanotube is a single-walled carbon nanotube.
The quaternary ammonium mercaptoalkyl salt can be at least one of quaternary ammonium N, N-dimethyl-N-ethyl-3-mercaptopropyl salt, quaternary ammonium N, N, N-trimethyl-3-mercaptopropyl salt and quaternary ammonium N, N-dimethyl-N-propyl-3-mercaptopropyl salt, and preferably the quaternary ammonium mercaptoalkyl salt is quaternary ammonium N, N-dimethyl-N-ethyl-3-mercaptopropyl salt.
In order to achieve the second purpose, the invention adopts the following technical scheme: a preparation method of a bisphenol A synthetic composite resin catalyst comprises the following steps:
(1) Uniformly mixing styrene or substituted styrene, divinyl benzene, divinyl phenyl methane or dipropenyl benzene, graphene and carbon nano tubes, and then carrying out suspension copolymerization to obtain composite copolymer pellets which can be gel type or macroporous type. Wherein, the divinyl benzene, divinyl phenyl methane or dipropenyl benzene accounts for 1 to 30 percent of the total mass of the monomer, and the best accounts for 2 to 6 percent of the total mass of the monomer. The graphene and the carbon nano tube account for 0.1 to 20 percent of the total mass of the monomer, preferably 0.5 to 5 percent.
(2) And sulfonating the obtained composite copolymer pellets according to a preparation method of conventional sulfonic acid type cation exchange resin to obtain the base resin for preparing the bisphenol A catalyst.
(3) According to the disclosed technology, mercapto alkyl quaternary ammonium salt is used as a sulfhydrylation agent, the base resin is modified by an ion exchange method, and a sulfonic acid group and mercapto alkyl quaternary ammonium are combined in an ionic bond mode to obtain the composite ion exchange resin catalyst. Wherein, the quaternary ammonium mercaptoalkyl salt accounts for 8.0 to 25 percent of the total mass of the base resin, preferably 18 to 22 percent.
Drawings
FIG. 1 is a view showing the fixed bed continuous reaction evaluation of a composite resin catalyst A.
FIG. 2 is a view showing the fixed bed continuous reaction evaluation of the resin catalyst E.
Detailed Description
The following specific examples further illustrate the invention but are not to be construed as limiting the invention.
The shrinkage rate measuring method of the composite grease catalyst comprises the following steps: measuring a certain volume of composite resin catalyst, and recording the volume as V 1 Washing the composite resin catalyst with anhydrous phenol until the water content of the effluent phenol is less than 0.1%, soaking the catalyst in the anhydrous phenol for 2 hours, and recording the volume as V 2 . Shrinkage rate meterCalculating the formula: phi = (V) 2 -V 1 )/V 1 …………………(1)
The yield and selectivity of bisphenol A produced by the reaction of phenol and acetone are calculated as follows
Yield Y (%) = C BPA (94.11×R m + 58.08)/228.28X 100 \8230inthe formula (2) C BPA Is the content of bisphenol A in the reaction solution; 94.11 is the molecular weight of phenol; r is m Is the molar ratio of the raw material phenol to the acetone; 58.08 is the molecular weight of acetone; 228.28 is the molecular weight of bisphenol A.
Bisphenol A selectivity S (%) = (8230) \ 8230; (3)
In the formula C BPA 、C Color saturation 、C 2,4-BPA、 、C Trisphenol 、C Others The contents of bisphenol A, chroman, 2, 4-bisphenol A, triphenol and other impurities in the reaction solution are shown respectively.
Example 1
In a 250 ml four-neck flask, 150 ml of distilled water and 1.5 g of gelatin and 0.15 g of dispersion aid were added, and after stirring to dissolve the dispersion aid, stirring was stopped. 30.0 g of 4-chlorostyrene, 2.6 g of divinylbenzene (50 mass percent), 0.32 g of benzoyl peroxide and 0.32 g of single-layer graphene are weighed into a 100 ml beaker, and after uniform mixing, the solution is poured into a flask. Starting stirring, adjusting the stirring speed, heating to 80 ℃, keeping the temperature for 2 hours, heating to 85 ℃, keeping the temperature for 2 hours, heating to 95 ℃, and keeping the temperature for 2 hours. Taking out the materials, washing with water, and drying to obtain the composite copolymer pellets.
And (2) adding 20 g of the composite copolymer pellets prepared by the method into a 250 ml four-neck flask, adding 20 ml of dichloroethane, swelling for 20 minutes, adding 100 ml of concentrated sulfuric acid, heating to 78 ℃, keeping the temperature for 5 hours, heating to evaporate the dichloroethane, keeping the temperature at 100 ℃ for 5 hours, cooling, filtering, diluting with dilute sulfuric acid, washing with water to be neutral, and draining to obtain the sulfonic acid composite resin a.
Adding 60 ml of deionized water, 20 g of the sulfonic acid composite resin a and 4.6 g of N, N-dimethyl-N-ethyl-3-mercaptopropyl quaternary ammonium salt into a 150 ml four-neck flask, reacting for 5 hours, taking out the resin, and washing the resin to be neutral by using the deionized water to obtain the bisphenol A synthetic composite resin catalyst A.
Example 2
As in example 1, a sulfonic acid composite resin B and a bisphenol a synthetic composite resin catalyst B were prepared by changing single-layer graphene to 1.3 g of multi-walled carbon nanotubes.
Example 3
As in example 1, the sulfonic acid composite resin C and bisphenol a synthetic composite resin catalyst C were prepared by changing single-layer graphene to 0.65 g single-walled carbon nanotubes.
Example 4
As in example 1, the amount of single-layer graphene used was changed to 0.16 g of graphene oxide, and sulfonic acid composite resin D and bisphenol a synthetic composite resin catalyst D were prepared.
Comparative example 1
Bisphenol a synthetic resin catalyst E was obtained as in example 1 except that no single-layer graphene was added.
Example 5
Respectively measuring 10mL of each of the resin catalysts A, B, C, D and E, filling the resin catalysts into a resin washing column, washing the resin catalysts with phenol until the water content of the outflow phenol is less than 0.1%, soaking the resin catalysts with phenol for 2 hours, recording the volume of each resin catalyst, and calculating the shrinkage rate of the resin catalysts according to the formula (1), wherein the results are shown in Table 1.
TABLE 1 shrinkage of resin catalyst
Example 6
A four-necked flask equipped with a stirrer and a thermometer was charged with a dry resin catalyst A, or B, or C, or D, or E,10.0 g, 65.0 g of phenol dried at 105 ℃ for 12 hours, heated to 70 ℃ with stirring, kept at a constant temperature for 3 hours, charged with 5.0 g of acetone, reacted for 60 minutes, stopped, analyzed for the contents of the respective components by HPLC, and the yield and selectivity of bisphenol A were calculated according to the formulas (2), (3), and the results are shown in Table 2.
TABLE 2 comparison of catalytic Activity of resin catalysts
Example 7
20 ml of the composite resin catalyst A is placed in a stainless steel fixed bed reactor with the inner diameter of 16mm and the length of 200mm, and phenol acetone solution with the molar ratio of 10/1 is put in the reactor at 70 ℃ at the airspeed of 1h -1 The reaction was continued, and the yield and selectivity of bisphenol A were measured, and the results are shown in FIG. 1.
Comparative example 2
As in example 7, the composite resin catalyst A was changed to resin catalyst E, and a 10/1 molar ratio of phenol-acetone solution was introduced at 70 ℃ at a space velocity of 1 hour -1 The reaction was continued, and the yield and selectivity of bisphenol A were measured, and the results are shown in FIG. 2.
Example 8
The catalyst of example 7 and comparative example 2, which was run for 1100 hours, was taken out, washed with water, methanol, acetone, and methylene chloride, then washed with 5% sodium hydroxide, and finally adjusted to PH =2 with 5% aqueous hydrochloric acid to precipitate solid impurities, which were filtered, dried, and weighed. The impurities in example 7 accounted for 0.13% of composite resin catalyst a, and the impurities in comparative example 2 accounted for 0.21% of catalyst E.
Claims (5)
1. The bisphenol A synthetic composite resin catalyst is characterized by comprising the following components in percentage by mass:
1) 30-90% of monomer;
2) 1-30% of a cross-linking agent;
3) 0.1-20% of nano material;
4) 8.0 to 25 percent of mercapto alkyl quaternary ammonium salt;
wherein the monomer has the following structural general formula:
x includes, but is not limited to, hydrogen, halogen (including fluorine, chlorine, bromine), nitro, carboxyl electron withdrawing groups;
the crosslinking agent is at least one of divinylbenzene, divinyl phenyl methane and dipropenyl benzene;
the nano material is at least one of graphene, carbon nano tube and nano silicon oxide;
the mercaptoalkyl quaternary ammonium salts include, but are 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. The bisphenol-A synthetic composite resin catalyst as claimed in claim 1, wherein the monomer is selected from 4-chlorostyrene.
3. The bisphenol-a synthetic composite resin catalyst as claimed in claim 1, wherein the crosslinking agent is selected from divinylbenzene.
4. The bisphenol-A synthesis composite resin catalyst as claimed in claim 1, wherein the nanomaterial is selected from one or more nanomaterials selected from the group consisting of single-layer graphene, multi-layer graphene, aminated graphene, oxidized graphene, hydroxylated graphene, carboxylated graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes.
5. The preparation method of the bisphenol A synthetic composite resin catalyst is characterized by comprising the following steps:
1) Firstly, uniformly mixing a monomer, a cross-linking agent and a nano material, and then carrying out suspension copolymerization to obtain a composite copolymer pellet;
2) Sulfonating the composite copolymer pellets according to a conventional method to obtain sulfonic acid type composite cation exchange resin serving as base resin for preparing the bisphenol A catalyst;
3) According to the disclosed technology, mercapto alkyl quaternary ammonium salt is used as a sulfhydrylation agent, basic resin is modified by an ion exchange method, and a sulfonic acid group on the resin is combined with mercapto alkyl ammonium in an ionic bond mode; wherein, the mercapto alkyl quaternary ammonium salt accounts for 8.0 to 25 percent of the total mass of the base resin.
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