CN112079756B - Preparation method of diallyl bisphenol S ether - Google Patents
Preparation method of diallyl bisphenol S ether Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 106
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 47
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 20
- 239000012065 filter cake Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- -1 diethylene glycol ethers Chemical class 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 38
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 27
- 238000001914 filtration Methods 0.000 description 26
- 239000012452 mother liquor Substances 0.000 description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- FKZIDBGIZLBDDF-UHFFFAOYSA-N 4-(4-prop-2-enoxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(OCC=C)C=C1 FKZIDBGIZLBDDF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of diallyl bisphenol S ether, which comprises the steps of adding solid alkali, bisphenol S and chloropropene into an anhydrous aprotic strong polar solvent, and reacting in the presence of a catalyst at the temperature of 55-100 ℃ for 7-12 hours; solid-liquid separation, namely separating diallyl bisphenol S ether and inorganic salt from the obtained filter cake; directly recycling the filtrate containing the solvent and the catalyst to be applied to the next preparation of diallyl bisphenol S ether; wherein the catalyst is a non-ionic surfactant and is used in an amount of at least 5% by weight based on the bisphenol S. The invention belongs to anhydrous reaction, not only improves the one-time conversion rate of raw materials, but also directly applies the used solvent and catalyst without recovery and purification, thereby fundamentally solving the problem of industrial wastewater and realizing high quality and high yield of target products and byproducts.
Description
Technical Field
The invention relates to a preparation method of diallyl bisphenol S ether.
Background
Diallyl bisphenol S ether (bisphenol S diallyl ether) is widely used as a raw material for a heat-resistant polymer material, a developer for a thermal recording material, or a raw material for a flame retardant. With bisphenol S (4,4' -dihydroxydiphenyl sulfone, formula C12H10O4S,) are gradually replacing the product bisphenol a, with an increasing market demand for diallyl bisphenol S ether as a follow-up product to bisphenol S. The synthesis method of the product comprises the steps of taking alcohols as a solvent, heating to 70-90 ℃ under the caustic alkali condition, reacting for more than 24 hours, carrying out substitution reaction on bisphenol S and 3-chlorinated propylene to generate diallyl bisphenol S ether, wherein the yield is about 92%, the product purity is relatively low, and the content of sodium chloride in the product is relatively high.
Production route of diallyl bisphenol S ether:
the Chinese patent application CN101792408A discloses a preparation method of bisphenol S diallyl ether, which comprises the steps of reacting bisphenol S with chloropropene in a mixed solvent of ethanol and water in the presence of sodium hydroxide and a surfactant for 10-12 hours at the temperature of 45-80 ℃, and filtering to obtain the product. Although this method is advantageous for recovering the solvent, it has disadvantages of treatment of waste brine and high salt content of the product.
Chinese patent application CN10774952A discloses a method for synthesizing bisphenol S allyl ether, which comprises the steps of placing bisphenol S in a mixed solution of alcohol and water under normal pressure, adding a catalyst, keeping the temperature at 80-90 ℃ for dissolving for 0.2-1h, reducing the temperature to 50-60 ℃ after the dissolution is finished, slowly dripping chloropropene, and evaporating solvent and unreacted chloropropene after the reaction is finished. Although this method can obtain high purity diallyl bisphenol S ether, the problem of salt-containing wastewater treatment still occurs after the solvent is distilled off.
The Chinese patent application CN102050767A discloses a preparation method of 1, 1' -sulfonyl bis [4- (2-propylene) oxybenzene ], which does not use organic solvent, takes water as solvent, and adds a Phase Transfer Catalyst (PTC) and a potassium iodide catalyst under alkaline condition for preparation. The method does not use solvent recovery, but has the disadvantages of subsequent treatment processes of a large amount of waste water and high price of the catalyst.
According to the preparation process in the prior art, the production process of diallyl bisphenol S ether by reacting bisphenol S as a raw material with alkali to form salt is unavoidable to generate a large amount of sodium chloride and potassium inorganic salt wastewater, and water or liquid alkali is added in the reaction, so that the target product is inevitably contaminated with bisphenol S triallyl ether. With the development of science and technology and the progress of society, people not only have higher and higher requirements on the quality of chemical products, but also advocate cleaner production, the production of each chemical product must keep the concept of 'safety and environmental protection', and the avoidance of the generation of 'three wastes' in chemical industry and the recycling of 'three wastes' must be considered. Therefore, how to solve the problem of wastewater treatment in the prior art and ensure the product yield and purity is urgently needed to be solved.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a novel preparation method of bisphenol S diallyl ether, which can realize high conversion rate of bisphenol S at one time and avoid impurities of bisphenol S triallylether in a product, thereby solving the problem of industrial wastewater. Furthermore, the method can obviously improve the purity and yield of the product.
In the prior art, water exists in the reaction, and impurities of bisphenol S triallyl ether can appear. The reaction of the present invention is carried out in an anhydrous solvent, such as a single solvent of diethylene glycol monomethyl ether. The applicant found through research and experiments that in the case of anhydrous reaction, the reaction solution after the completion of the reaction contains only a small amount of bisphenol S, bisphenol S monoallyl ether and diallyl bisphenol S ether, and no other impurities. This significant discovery allows for multiple or even unlimited uses of the solvent without purification.
The invention provides a preparation method of diallyl bisphenol S ether, which comprises the following steps: adding solid alkali, bisphenol S and chloropropene into an anhydrous aprotic strong polar solvent, reacting in the presence of a catalyst at the temperature of 55-100 ℃ for 7-12 hours, and carrying out solid-liquid separation; wherein the catalyst is a non-ionic surfactant and is used in an amount of at least 5% by weight based on the weight of bisphenol S. After solid-liquid separation, directly recycling the filtrate containing the solvent and the catalyst to the next preparation of diallyl bisphenol S ether; and dissolving the filter cake by using a non-polar or weak-polar solvent, preferably toluene, ethyl acetate or dichloromethane, and separating to obtain the inorganic salt and the diallyl bisphenol S ether.
In the invention, one of diethylene glycol ether and propylene glycol ether is preferably used as a solvent, and the solvent belongs to an aprotic polar solvent, so that the solvent has very high solubility for the sodium phenolate of the raw material bisphenol S, and a reaction system is in a homogeneous phase state; but also is beneficial to the alkylation reaction of benzene ring phenolic hydroxyl, thereby accelerating the reaction and simultaneously well avoiding the generation of other impurities.
The solid alkali used in the invention is preferably one or a mixture of sodium hydroxide and potassium hydroxide.
The catalyst used in the invention is a non-ionic surfactant, is low in price and has the best effect when being matched with a solvent. The amount of the catalyst added is very important, at least 5% by weight of the amount of bisphenol S added, so that the conversion rate of bisphenol S at one time is more than 99%, and the catalyst used is liquid and can be recycled together with the solvent, thus not involving a cost problem. Preferably, the catalyst is one or more than two of alkyl polyoxyethylene ether series, such as fatty alcohol polyoxyethylene ether RO (CH)2CH2O) nH, when the carbon chain R is C12-18, and n is 15-20, the generated fatty alcohol polyoxyethyleneThe ethers are known in the industry as peregal O (Peregal O), preferably one or more of peregal O-20 to O-100.
In the second preparation of diallyl bisphenol S ether after the first preparation, the filtrate obtained in the first preparation is preferably directly used, a proper amount of a supplementary solvent and a catalyst are added, the filtrate obtained in the second preparation is added in the third preparation of diallyl bisphenol S ether, a proper amount of the supplementary solvent and the catalyst are added, and the like, the yield of diallyl bisphenol S ether is gradually improved along with the increase of the reuse times of the filtrate, and bisphenol S triallyl ether is not generated in the reaction process. Preferably, the solvent is supplemented in an amount of 0.1% to 0.2% and the catalyst is supplemented in an amount of 0.2 to 0.4%.
The amount of the reaction raw materials added is, preferably, by weight, bisphenol S: solid base: chloropropene: solvent 1: 2.35: 2.4-2.6: 3-4.
In a preferred embodiment, the anhydrous reaction is achieved using diethylene glycol monomethyl ether as a solvent, without the addition of a liquid base, but rather a solid base such as, but not limited to, sodium hydroxide, potassium hydroxide, and the like. By weight, bisphenol S: solid base: chloropropene: diethylene glycol monomethyl ether: catalyst 1: 2.35: 2.4-2.6: 3-4: 0.05, adding solid alkali into diethylene glycol monomethyl ether, adding bisphenol S and a catalyst under the stirring condition, adding chloropropene, replacing the environment in the reaction kettle with nitrogen, sealing the reactor, setting the initial temperature to be 60 ℃, continuously increasing the reaction temperature along with the reaction, and finally maintaining the temperature at 100 ℃ for reaction for 5 hours; cooling to room temperature; filtering, recycling the filtrate, dissolving the filter cake with a weak polar solvent, and separating to obtain inorganic salt and diallyl bisphenol S ether. Wherein, the filter cake is dissolved by weak polar solvent, and then inorganic salt is removed by filtration, and the finished product of diallyl bisphenol S ether is obtained after mother liquor concentration, crystallization and filtration.
After the materials are mixed, nitrogen replacement and sealing are needed to be carried out to form a micro-positive pressure reaction, so that the color of the reaction solution is well ensured, and the recycling of the reaction solvent is facilitated.
The invention uses the surface active agent of non-ionic alkyl polyoxyethylene ether as the catalyst, and increases the usage amount of the catalyst, thereby realizing that the one-time conversion rate reaches more than 99 percent, the content of diallyl bisphenol S ether reaches more than 99.6 percent, solving the problem of low single-time conversion rate, carrying out solid-liquid separation after the reaction is finished and the temperature is reduced, realizing that the solvent and the catalyst can be directly used repeatedly without recovery and purification, and the application frequency can be more than 10 times or even more at least. Particularly, the method is favored to adopt a reuse mode, because the used catalyst is liquid and can be remained in the reaction liquid along with the solvent, only a small amount of catalyst needs to be added after the reaction liquid is reused, so that the catalyst is recycled, and the product cost is obviously reduced. The experimental result shows that the yield of the target product can reach 96% after the reaction solution containing the solvent and the catalyst is reused for 8 times.
In the post-treatment process, the non-polar solvent or the weak-polar solvent is adopted to dissolve the filter cake, the salt is removed by hot filtration, and the salt is separated out in a solid form, so that the byproducts with very high purity, such as sodium chloride and potassium chloride, are obtained. The characteristic that the low-polarity solvent is insoluble to inorganic salt is utilized, so that the problem of high salt content in the product can be effectively solved. Preferably, the characteristic that toluene has no solubility to inorganic salts can be utilized to realize no metal ions or extremely low metal ions in the product, so that the problem of high metal ions in the product is solved, the solid salt with the purity of 99 percent can be obtained, and waste utilization is well realized.
In general, the preparation method of the invention not only improves the one-time conversion rate of the raw materials, but also directly applies the used solvent and catalyst without recovery and purification, thus fundamentally solving the problem of industrial wastewater and realizing high quality and high yield of the target product and by-products.
Detailed Description
The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples.
The solvent used in examples 1-4 was diethylene glycol monomethyl ether and the catalyst was fatty alcohol polyoxyethylene ether (peregal O-25).
Example 1：
192 g of diethylene glycol monomethyl ether and 24 g of sodium hydroxide are added into a three-mouth bottle with stirring, the stirring is carried out for about 10 minutes, 64 g of bisphenol S is added under the stirring condition, 3.2 g of catalyst is added, 50 g of chloropropene is added after the stirring is carried out for 10 minutes, the environment in the kettle is replaced by nitrogen, the reactor is sealed, the reaction temperature is adjusted to 60 ℃, then the reaction temperature is gradually adjusted to 100 ℃, the reaction temperature is maintained for 5 hours, the temperature is reduced to room temperature, and the reaction mother liquor is filtered and left for application.
After filtration, 250 g of toluene is added into the obtained filter cake, the product is heated and dissolved, then the filter cake is filtered by heating, the filter cake is washed by the toluene to obtain sodium chloride with the purity of 99 percent, and then the mother liquor is concentrated, crystallized, filtered by throwing and dried to obtain 69 g of diallyl bisphenol S ether with the content of 99.6 percent and the yield of 82 percent.
Example 2：
Adding the reaction mother liquor obtained by filtering in example 1 into a three-neck flask with stirring, adding 10 g of solvent and 24 g of sodium hydroxide, stirring for about 10 minutes, adding 64 g of bisphenol S under the stirring condition, then adding 0.2 g of catalyst, stirring for 10 minutes, then adding 50 g of chloropropene, replacing the environment in the kettle with nitrogen, sealing the reactor, adjusting the reaction temperature to 60 ℃, then gradually adjusting the reaction temperature, after the temperature reaches 100 ℃, maintaining the reaction temperature for 5 hours, cooling to room temperature, filtering, and keeping the reaction mother liquor for use.
Sodium chloride and bisphenol S diallyl ether were isolated from the filter cake according to the procedure used in example 1. And (3) detection results: 77.7 g of diallyl bisphenol S ether, 99.7 percent of content and 92 percent of yield.
Example 3：
Adding the reaction mother liquor obtained by filtering in the example 2 into a three-neck flask with stirring, adding 10 g of solvent and 24 g of sodium hydroxide, stirring for about 10 minutes, adding 64 g of bisphenol S under the stirring condition, then adding 0.1 g of catalyst, stirring for 10 minutes, then adding 50 g of chloropropene, replacing the environment in the kettle with nitrogen, sealing the reactor, adjusting the reaction temperature to 60 ℃, then gradually adjusting the reaction temperature, maintaining the temperature for 5 hours after the temperature is 100 ℃, cooling to room temperature, and filtering.
Sodium chloride and bisphenol S diallyl ether were isolated from the filter cake according to the procedure used in example 1. And (3) detection results: 78.6 g of diallyl bisphenol S ether, 99.6 percent of content and 93 percent of yield.
Example 4：
Using the reaction mother liquor which is used for 8 times, supplementing 10 g of solvent and 24 g of sodium hydroxide, stirring for about 10 minutes, adding 64 g of bisphenol S under the stirring condition, then adding 0.1 g of catalyst, stirring for 10 minutes, then adding 50 g of chloropropene, replacing the environment in the kettle with nitrogen, sealing the reactor, adjusting the reaction temperature to 60 ℃, then gradually adjusting the reaction temperature, maintaining the temperature to react for 5 hours after the temperature reaches 100 ℃, cooling to room temperature, filtering, and keeping the reaction mother liquor for use.
Sodium chloride and bisphenol S diallyl ether were isolated from the filter cake according to the procedure used in example 1. And (3) detection results: the content of diallyl bisphenol S ether was 99.6%, and the yield was 96%.
The monitoring of the reaction and the product content were measured, analyzed, and calculated under the following conditions.
An analytical instrument: shimadzu LC-10A system, Japan.
A chromatographic column: c18150 mm × 4.6mm × 5 um.
Mobile phase: methanol: 70 parts of water: 30, adjusting the pH value to 3.5 by using phosphoric acid.
Flow rate: 0.8 ml/min.
A detector: UV 254 nm.
Under these conditions the peak time of bisphenol S was: about 2.8 minutes.
The peak time of monoallyl bisphenol S ether was: about 5.0 minutes.
The peak time of diallyl bisphenol S ether was: about 11.0 minutes.
The amounts of the above-mentioned materials and the results of the tests of examples 1 to 4 are shown in tables 1.1 and 1.2. Ethylene glycol monomethyl ether is used as a solvent, and a solid alkali is added for an anhydrous reaction, wherein the input amount of the catalyst is 5 percent of the weight of the bisphenol S. The reaction mother liquor obtained in each preparation is indiscriminately used, and a proper amount of solvent and catalyst needs to be supplemented in the indiscriminate use process so as to ensure that the addition amount of the solvent and the catalyst is sufficient. The detection result shows that the yield is gradually improved after the reaction mother liquor is reused for many times, bisphenol S triallyl ether and other impurities do not appear in the product, the purity of the product is over 99.6 percent, and meanwhile, the salt content in the product is very low and is 100 PPM.
TABLE 1.1
TABLE 1.2
Referring to tables 2.1 and 2.2, in comparative examples 1 to 4, ethylene glycol monomethyl ether was used as a solvent to add solid alkali, and an anhydrous reaction was performed, the amount of the catalyst added was 3% of the weight of bisphenol S, and mother liquor was used twice for reaction, and the solvent and the catalyst were added in appropriate amounts during the use. The detection result shows that after the reaction mother liquor is reused for many times, although the product yield is gradually improved, the content of the product is reduced, and the high-purity product cannot be obtained. If a high-purity product is obtained, recrystallization is needed, the production efficiency is reduced, and the cost is increased. Also, as the monoallyl bisphenol S ether content increased, the yield decreased. It follows that the amount of catalyst added has an effect on both the purity and yield of the reaction product. In contrast, as in examples 1-4, when the catalyst loading amount reaches 5% of the bisphenol S weight, the purity and yield of the reaction product can be maintained at high levels even if 8 times of reaction mother liquor is used; from the reaction result, the content of diallyl bisphenol S ether can always reach more than 99.6 percent, and when the first addition of the catalyst is 5 to 6 percent, the yield of the diallyl bisphenol S ether which is a reaction product after the reaction mother solution is repeatedly used can reach 96 percent.
Comparative example 1：
192 g of diethylene glycol monomethyl ether and 24 g of sodium hydroxide are added into a stirred three-neck flask, the mixture is stirred for about 10 minutes, 64 g of bisphenol S is added under the stirring condition, 1.92 g of catalyst is added, 50 g of chloropropene is added after the mixture is stirred for 10 minutes, the reactor is sealed, the reaction temperature is adjusted to 60 ℃, the reaction temperature is gradually adjusted to 100 ℃, the reaction temperature is maintained for 5 hours, the temperature is reduced to room temperature, and the reaction mother liquor obtained by filtering is reserved for application.
And adding 250 g of toluene into the filter cake obtained by filtering, heating to dissolve the product, carrying out hot filtration, concentrating the mother liquor, crystallizing, carrying out swing filtration, and drying to obtain the product. And (3) detection results: the content of diallyl bisphenol S ether was 98.5%, and the yield was 82%.
Comparative example 2：
Adding the reaction mother liquor obtained by filtering in comparative example 1 into a three-neck flask with stirring, adding 10 g of solvent and 24 g of sodium hydroxide, stirring for about 10 minutes, adding 64 g of bisphenol S under the stirring condition, then adding 0.2 g of catalyst, stirring for 10 minutes, then adding 50 g of chloropropene, replacing the environment in the kettle with nitrogen, sealing the reactor, adjusting the reaction temperature to 60 ℃, then gradually adjusting the reaction temperature, maintaining the temperature for reaction for 5 hours after the temperature reaches 100 ℃, cooling to room temperature, filtering, and keeping the reaction mother liquor obtained by filtering for use.
Sodium chloride and bisphenol S diallyl ether were separated from the filter cake according to the procedure used in comparative example 1. And (3) detection results: the content of diallyl bisphenol S ether was 97.5%, and the yield was 92%.
Comparative example 3：
The reaction conditions were the same as in comparative example 2, and the reaction mother liquor in comparative example 2 was charged with: adding 10 g of solvent, 24 g of sodium hydroxide, 64 g of bisphenol S, 0.1 g of catalyst and 50 g of chloropropene.
Sodium chloride and bisphenol S diallyl ether were separated from the filter cake according to the procedure used in comparative example 1. And (3) detection results: the content of diallyl bisphenol S ether was 95.7%, and the yield was 92%.
Comparative example 4：
The reaction conditions were the same as in comparative example 2, and the reaction mother liquor was charged in 8 times: adding 10 g of solvent, 24 g of sodium hydroxide, 64 g of bisphenol S, 0.1 g of catalyst and 50 g of chloropropene.
Sodium chloride and bisphenol S diallyl ether were separated from the filter cake according to the procedure used in comparative example 1. And (3) detection results: the content of diallyl bisphenol S ether was 85.5%, and the yield was 88%.
TABLE 2.1
TABLE 2.2
Referring to tables 3.1 and 3.2, in comparative examples 5 to 7, ethylene glycol monomethyl ether was used as a solvent, water was added to perform a reaction, the amount of the catalyst added was 3% of the weight of bisphenol S, mother liquor was used twice for the reaction, the solvent and the catalyst were supplemented in the process of using, and in the process of using, the contents of bisphenol S and bisphenol monoallyl ether as raw materials and bisphenol S triallyl ether as impurities were increased more and more, so that the quality of the product was affected, and the salt content in the product was more than 1000 PPM. In the aspect of the three wastes, after the reaction mother liquor is stopped to be reused, a large amount of salt-containing wastewater is generated and needs to be treated, so that the pollution problem is caused, and the industrial production is not facilitated.
Comparative example 5：
192 g of diethylene glycol monomethyl ether, 80 g of water and 24 g of sodium hydroxide are added into a stirred three-mouth bottle, the stirring is carried out for about 10 minutes, 64 g of bisphenol S is added under the stirring condition, 1.92 g of catalyst is added, 50 g of chloropropene is added after the stirring is carried out for 10 minutes, the environment in the kettle is replaced by nitrogen, the reactor is sealed, the reaction temperature is adjusted to 60 ℃, then the reaction temperature is gradually adjusted, the temperature is maintained for reaction for 5 hours after the reaction temperature is 100 ℃, the temperature is reduced to room temperature, the filtration is carried out, and the reaction mother liquor obtained by the filtration is reserved for application.
And adding 250 g of toluene into the filter cake obtained by filtering, heating to dissolve the product, carrying out hot filtration, concentrating the mother liquor, crystallizing, carrying out swing filtration, and drying to obtain 72.6 g of the product. And (3) detection results: the content of diallyl bisphenol S ether was 98.9% and the yield was 86%.
Comparative example 6：
Adding mother liquor of comparative example 4 into a stirred three-neck flask, adding 50 g of diethylene glycol monomethyl ether, 80 g of water and 24 g of sodium hydroxide, stirring for about 10 minutes, adding 64 g of bisphenol S under the stirring condition, then adding 0.2 g of catalyst, stirring for 10 minutes, then adding 50 g of chloropropene, sealing the reactor, adjusting the reaction temperature to 60 ℃, then gradually adjusting the reaction temperature, maintaining the temperature for 5 hours after the temperature is 100 ℃, cooling to room temperature and filtering.
And adding 250 g of toluene into a filter cake obtained by filtering, heating to dissolve a product, carrying out hot filtration, concentrating, crystallizing, carrying out filter spinning on a mother solution, and drying to obtain 76 g of a product, wherein the content of diallyl bisphenol S ether is 96.5%, and the yield is 90%.
Comparative example 7：
The reaction conditions were the same as in comparative example 6, and the reaction mother liquor was charged in 2 times: adding 50 g of diethylene glycol monomethyl ether, 80 g of water, 24 g of sodium hydroxide, 64 g of bisphenol S, 0.1 g of catalyst and 50 g of chloropropene. And (3) detection results: the content of diallyl bisphenol S ether was 93.53%, and the yield was 93%.
TABLE 3.1
TABLE 3.2
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the previous embodiments can be modified, or the preparation reaction conditions can be replaced, or part of technical features can be replaced equivalently; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A process for producing diallyl bisphenol S ether, characterized in that,
adding solid alkali, bisphenol S and chloropropene into an anhydrous aprotic polar solvent, reacting in the presence of a catalyst at the temperature of 55-100 ℃ for 7-12 hours, and carrying out solid-liquid separation; the weight ratio of the solvent to the bisphenol S is 3-4: 1;
separating diallyl bisphenol S ether and inorganic salt from a filter cake obtained by solid-liquid separation;
directly recycling the filtrate containing the solvent and the catalyst to be applied to the next preparation of diallyl bisphenol S ether; supplementing the solvent and the catalyst in the process of mechanically using the filtrate to ensure that the addition amount of the solvent and the catalyst is sufficient, gradually improving the yield of the diallyl bisphenol S ether along with the increase of the mechanically using times of the filtrate, and not generating the bisphenol S triallyl ether in the reaction;
wherein the catalyst is one or more than two of nonionic surfactant alkyl polyoxyethylene ether, and the dosage of the catalyst is at least 5% of the weight of bisphenol S.
2. The method for producing diallyl bisphenol S ether according to claim 1, wherein the reaction is a gradual temperature rise reaction process, and then the temperature is maintained for 5 to 6 hours.
3. The method for producing diallyl bisphenol S ether according to claim 1 or 2, wherein the solvent is one of diethylene glycol ethers and propylene glycol ethers.
4. The method for preparing diallyl bisphenol S ether according to claim 3, wherein the solid base is one or a mixture of sodium hydroxide and potassium hydroxide.
5. The method for producing diallyl bisphenol S ether according to claim 1, wherein the solvent used for separating diallyl bisphenol S ether and inorganic salt from the filter cake is toluene, ethyl acetate or dichloromethane.
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