CN116041668A - Method for preparing epoxy resin by using bisphenol F mother liquor - Google Patents
Method for preparing epoxy resin by using bisphenol F mother liquor Download PDFInfo
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- CN116041668A CN116041668A CN202211326359.9A CN202211326359A CN116041668A CN 116041668 A CN116041668 A CN 116041668A CN 202211326359 A CN202211326359 A CN 202211326359A CN 116041668 A CN116041668 A CN 116041668A
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- bisphenol
- mother liquor
- epoxy resin
- phenol
- ethanol
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000012452 mother liquor Substances 0.000 title claims abstract description 94
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 118
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000012074 organic phase Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 87
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 32
- 238000007259 addition reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229930185605 Bisphenol Natural products 0.000 claims description 18
- -1 bisphenol compound Chemical class 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004480 active ingredient Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000005028 tinplate Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 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
- 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention provides a method for preparing epoxy resin by using bisphenol F mother liquor, which is characterized in that filtrate obtained in the process of preparing finished bisphenol F is separated to obtain an organic phase, the organic phase is recovered and treated to separate phenol and ethanol, the content of active ingredients in the bisphenol F mother liquor is improved, the bisphenol F mother liquor is kept in a liquid flowing state by adding an organic solvent, a subsequent epoxy resin synthesis reaction system is kept homogeneous, and then bisphenol compounds are added, so that the active ingredients of the system are further improved, the reactant concentration is high during the epoxy resin synthesis, the quality of epoxy resin products is improved, and hydroxyl groups contained on the bisphenol compounds and epoxy groups of epoxy chloropropane are fully reacted to obtain the epoxy resin products. The method provided by the invention directly utilizes the bisphenol F mother liquor to prepare the epoxy resin, realizes the environment-friendly recovery treatment of the bisphenol F mother liquor and the recycling of resources, and fundamentally solves the problem that the bisphenol F mother liquor is difficult to treat.
Description
Technical Field
The invention relates to the technical field of epoxy resin materials, in particular to a method for preparing epoxy resin by using bisphenol F mother liquor.
Background
Bisphenol F is a novel chemical raw material developed in the 80 s of the 20 th century, and is mainly used as a raw material of low-viscosity epoxy resin and special polyester, an additive of information recording paper and the like. The bisphenol F takes part in the finished product manufactured, has obviously improved heat resistance, water resistance and insulativity, especially the processing performance and mechanical property, can meet the requirements of materials such as high solid content coating, electronic grade epoxy resin, flame retardant material and the like and special performances of casting, casting forming and other processes, and the bisphenol F epoxy resin has all excellent characteristics of bisphenol A epoxy resin and also has unique properties, especially the viscosity is far lower than that of bisphenol A epoxy resin, thereby greatly increasing the application range of bisphenol F. Therefore, bisphenol F products have better development and application prospects.
At present, bisphenol F is synthesized by taking phenol and formaldehyde as raw materials in a majority of bisphenol F synthesis process under an acid catalyst, separating to obtain bisphenol F, washing with various solvents and auxiliary agents, separating redundant acid in residual mixed liquid to obtain an organic phase, recovering phenol from the organic phase, and taking bisphenol F mother liquor as the residual material. Therefore, the bisphenol F mother liquor has complex components and high post-treatment difficulty, but no technology for recovering and treating the bisphenol F mother liquor has been reported at present. Therefore, how to realize the green and environment-friendly recovery treatment of bisphenol F mother liquor and realize the recycling of resources so as to solve the problem that the bisphenol F mother liquor is difficult to treat is a problem which needs to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a method for preparing epoxy resin by using bisphenol F mother liquor, which directly utilizes bisphenol F mother liquor to prepare epoxy resin, realizes green and environment-friendly recovery treatment of bisphenol F mother liquor and resource recycling, and solves the problem that bisphenol F mother liquor is difficult to treat.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing epoxy resin by using bisphenol F mother liquor, which comprises the following steps:
(1) Mixing phenol and phosphoric acid, then dropwise adding formaldehyde aqueous solution, and carrying out addition reaction after the dropwise adding is finished to obtain a mixture containing bisphenol F;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with ethanol, and filtering to obtain bisphenol F and filtrate;
(3) Separating the filtrate obtained in the step (2) to obtain an organic phase and recovered phosphoric acid respectively;
recovering the organic phase to obtain mother liquor of phenol, ethanol and bisphenol F
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with an organic solvent to obtain a mixed solution;
(5) And (3) mixing the mixed solution obtained in the step (4) with bisphenol compound, epichlorohydrin and sodium hydroxide aqueous solution, and performing polymerization reaction to obtain the epoxy resin.
Preferably, the ratio of the amounts of phenol, formaldehyde in the aqueous formaldehyde solution and phosphoric acid in step (1) is (2 to 3.5): 1: (0.3-1.5).
Preferably, the temperature of the dripping in the step (1) is 40-55 ℃, and the dripping time is 1-14 h.
Preferably, the temperature of the addition reaction in the step (1) is 40-55 ℃, and the time of the addition reaction is 0.5-4 h.
Preferably, the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is (0.4 to 0.9): 1.
preferably, the recovery treatment in the step (3) includes reduced pressure distillation, rectification or column chromatography.
Preferably, the mass ratio of the organic solvent to the bisphenol F mother liquor in the step (4) is (0.2 to 0.5): 1.
preferably, the mass ratio of bisphenol compound in the step (5) to bisphenol F mother liquor in the step (4) is (0.1 to 0.4): 1.
preferably, the mass ratio of epichlorohydrin in the step (5) and bisphenol F mother liquor in the step (4) is (0.5-3): 1.
preferably, the temperature of the polymerization reaction in the step (5) is 55-80 ℃, and the time of the polymerization reaction is 2-8 h.
The invention provides a method for preparing epoxy resin by using bisphenol F mother liquor, which comprises the steps of firstly using phenol, phosphoric acid and formaldehyde aqueous solution as raw materials, carrying out addition reaction to obtain a mixture containing bisphenol F, adding ethanol for mixing, then filtering to obtain finished bisphenol F and filtrate, separating the filtrate to obtain organic phases and recovered phosphoric acid, carrying out recovery treatment on the organic phases to obtain phenol, ethanol and bisphenol F mother liquor, separating phenol and ethanol contained in the organic phases through liquid separation and recovery treatment, greatly improving the content of active ingredients (comprising 2, 2-bisphenol F, 2, 4-bisphenol F, 4-bisphenol F, triphenol, tetraphenol compounds and the like) in the bisphenol F mother liquor, and further improving the quality of epoxy resin by adding an epoxy compound to ensure that the epoxy resin is synthesized in a high-quality epoxy resin system and further has the advantages of fully producing epoxy resin due to the fact that the active ingredients are large molecules and are not beneficial to material use, and the bisphenol F mother liquor is kept in a liquid flowing state through adding an organic solvent. According to the method provided by the invention, the bisphenol F mother liquor is directly utilized to prepare the epoxy resin, so that the environment-friendly recovery treatment of the bisphenol F mother liquor and the resource recycling are realized, the problem that the bisphenol F mother liquor is difficult to treat is fundamentally solved, the preparation of the epoxy resin is fully utilized in a recycling way, the quality of the final product of the epoxy resin can be flexibly regulated by adding different bisphenol compounds, the epoxy resin product is customized according to the requirements of customers, and the conversion of functionalization is realized. The results of the examples show that the epoxy resins prepared in examples 1-4 are used as raw materials, the surface drying time of the prepared coating films-1-4 is as low as 2-3 h, the real drying time is as low as 8-19 h, and the epoxy value concentration in the epoxy resins prepared in examples 1-4 is 0.20-0.51 mol/100g; the cross-cut test of coating films-1 to-4 is grade 0 or 1, which shows that the adhesion between the epoxy resins prepared in examples 1 to 4 and the base material tinplate is better; the pencil hardness of the coating films-1 to-4 was HB, H or 2H, which means that the epoxy resins prepared in examples 1 to 4 were sufficiently reacted with the curing agent polyetheramine D230 to form a three-dimensional network structure, thereby improving the mechanical strength of the coating films.
Drawings
Fig. 1 is a flow chart of a method for preparing epoxy resin by using bisphenol F mother liquor.
Detailed Description
The invention provides a method for preparing epoxy resin by using bisphenol F mother liquor, which comprises the following steps:
(1) Mixing phenol and phosphoric acid, then dropwise adding formaldehyde aqueous solution, and carrying out addition reaction after the dropwise adding is finished to obtain a mixture containing bisphenol F;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with ethanol, and filtering to obtain bisphenol F and filtrate;
(3) Separating the filtrate obtained in the step (2) to obtain an organic phase and recovered phosphoric acid respectively;
recovering the organic phase to obtain mother liquor of phenol, ethanol and bisphenol F
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with an organic solvent to obtain a mixed solution;
(5) And (3) mixing the mixed solution obtained in the step (4) with bisphenol compound, epichlorohydrin and sodium hydroxide aqueous solution, and performing () reaction to obtain the epoxy resin.
The invention mixes phenol and phosphoric acid, then adds formaldehyde water solution, and carries out addition reaction after the addition is completed, thus obtaining the mixture containing bisphenol F.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
In the present invention, the phosphoric acid is preferably added in the form of an aqueous phosphoric acid solution; the mass percentage concentration of the phosphoric acid aqueous solution is preferably 85%.
The mixing mode of the phenol and the phosphoric acid is not particularly limited, and the components can be uniformly mixed.
In the present invention, the ratio of the amounts of substances of phenol, formaldehyde and phosphoric acid in the aqueous formaldehyde solution is preferably (2 to 3.5): 1: (0.3 to 1.5), more preferably (2.2 to 3): 1: (0.5-1). The invention controls the ratio of the substances of phenol, formaldehyde and phosphoric acid in the above range so that the phosphoric acid fully plays a catalytic role, promotes the addition reaction of phenol and formaldehyde to generate bisphenol F, improves the yield of bisphenol F and reduces the occurrence of side reactions.
In the present invention, the temperature of the dropping is preferably 40 to 55 ℃, more preferably 42 to 50 ℃. The invention controls the dropping temperature in the above range to ensure the slow reaction of phenol and formaldehyde, improve the conversion rate of bisphenol F and avoid side reaction. In the present invention, the time for the dropping is preferably 1 to 14 hours, more preferably 2 to 12 hours. In the invention, the addition reaction is a highly exothermic reaction, the dropping time is controlled in the range so as to control the dropping speed of formaldehyde, thereby controlling the system temperature of the addition reaction, promoting the smooth progress of the reaction for generating bisphenol F, improving the yield of bisphenol F and reducing the occurrence of side reactions.
In the present invention, the temperature of the addition reaction is preferably 40 to 55 ℃, more preferably 42 to 50 ℃. The invention controls the temperature of the addition reaction in the range, controls the system temperature of the addition reaction, promotes the reaction for generating bisphenol F to be carried out smoothly, improves the yield of bisphenol F and reduces the occurrence of side reaction. In the present invention, the time of the addition reaction is preferably 0.5 to 4 hours, more preferably 0.5 to 2 hours. The invention controls the time of the addition reaction in the range, promotes the formaldehyde and the phenol to fully react, improves the conversion rate, improves the yield of bisphenol F and reduces the occurrence of side reaction.
After obtaining the mixture containing bisphenol F, the invention mixes the mixture containing bisphenol F with ethanol and filters the mixture to obtain finished bisphenol F and filtrate.
The mixing mode of the mixture containing bisphenol F and ethanol is not particularly limited, and the mixture can be uniformly mixed.
In the present invention, the ethanol is preferably absolute ethanol. In the present invention, the mass ratio of the ethanol to the phenol is preferably (0.4 to 0.9): 1, more preferably (0.5 to 0.7): 1. the invention controls the mass ratio of the ethanol and the phenol in the range, is beneficial to reducing the viscosity of a system after the addition reaction is finished by using the ethanol, is convenient to transfer the reacted materials, is beneficial to the smooth proceeding of the subsequent operation, has a certain solubility in the ethanol, and avoids the bisphenol F loss caused by excessive ethanol.
The filtering mode is not particularly limited, and solid-liquid separation can be realized by adopting technical schemes well known in the art.
After the filtrate is obtained, the filtrate is separated to obtain an organic phase and recovered phosphoric acid.
The liquid separation mode is not particularly limited, and liquid-liquid separation can be realized by adopting technical schemes well known in the art.
After the recovered phosphoric acid is obtained, the recovered phosphoric acid is preferably subjected to reduced pressure distillation and recycling in this order.
The method of distillation under reduced pressure is not particularly limited, and phosphoric acid having a mass concentration of 85% or more may be obtained.
After the organic phase is obtained, the organic phase is recycled, and phenol, ethanol and bisphenol F mother liquor are respectively obtained.
In the present invention, the mode of the recovery treatment preferably includes reduced pressure distillation, rectification or column chromatography.
The mode of the reduced pressure distillation is not particularly limited, and the purpose of recovering phenol and ethanol can be achieved by adopting technical schemes well known in the art. The rectification mode is not particularly limited, and the purpose of recovering phenol and ethanol can be achieved by adopting technical schemes well known in the art. The method of the present invention is not particularly limited, and the purpose of recovering phenol and ethanol can be achieved by adopting technical schemes well known in the art. According to the invention, the recovery treatment is utilized to recover phenol and ethanol in the organic phase, so that the content of active ingredients (including 2, 2-bisphenol F, 2, 4-bisphenol F, 4-bisphenol F, triphenols, tetraphenols and the like) in the bisphenol F mother liquor is greatly improved, and the subsequent preparation of the epoxy resin with high yield is facilitated.
After bisphenol F mother liquor is obtained, the bisphenol F mother liquor and an organic solvent are mixed to obtain mixed liquor.
The mixing mode of the bisphenol F mother liquor and the organic solvent is not particularly limited, and the bisphenol F mother liquor and the organic solvent are uniformly mixed.
In the present invention, the organic solvent is preferably one or more of isopropanol, propylene glycol methyl ether, ethylene glycol butyl ether, MIBK, toluene, petroleum ether. In the present invention, the mass ratio of the organic solvent to the bisphenol F mother liquor is preferably (0.2 to 0.5): 1, more preferably (0.3 to 0.45): 1. the invention controls the mass ratio of the organic solvent and the bisphenol F mother liquor in the above range so as to effectively reduce the viscosity of the bisphenol F mother liquor by using the organic solvent, and the bisphenol F mother liquor is prepared into a solution with certain solid content, thereby being beneficial to the smooth proceeding of the subsequent operation.
After the mixed solution is obtained, the mixed solution is mixed with bisphenol compound, epichlorohydrin and sodium hydroxide aqueous solution, and then the polymerization reaction is carried out, so that the epoxy resin is obtained.
In the present invention, the bisphenol compound is preferably one or more of 4, 4-bisphenol F, 2-bisphenol F, bisphenol A, bisphenol S, tetrabromobisphenol A. In the present invention, the purity of the bisphenol compound is preferably not less than 99%. In the present invention, the mass ratio of the bisphenol compound to the bisphenol F mother liquor is preferably (0.1 to 0.4): 1, more preferably (0.15 to 0.35): 1. the invention increases the concentration of bisphenol compound reactant in the reaction system by adding high-purity bisphenol compound and controlling the mass ratio of bisphenol compound and bisphenol F mother liquor in the above range, thereby facilitating the subsequent preparation to obtain qualified epoxy resin products.
In the present invention, the mass ratio of epichlorohydrin to bisphenol F mother liquor is preferably (0.5 to 3): 1, more preferably (0.6 to 2.8): 1. the invention controls the mass ratio of the epoxy chloropropane and the bisphenol F mother liquor in the above range so as to adjust the reaction ratio of the epoxy chloropropane and the bisphenol compound, and the hydroxyl contained in the bisphenol compound and the epoxy group of the epoxy chloropropane fully react to generate the epoxy resin, thereby adjusting the performance index of the prepared epoxy resin.
In the present invention, the mass concentration of sodium hydroxide in the aqueous sodium hydroxide solution is preferably 40% to 52%, more preferably 48% to 50%. In the invention, the mass ratio of the sodium hydroxide to the bisphenol F mother liquor in the sodium hydroxide aqueous solution is preferably 3-10: 1, more preferably 5 to 7:1. the invention controls the mass ratio of sodium hydroxide and bisphenol F mother liquor in the sodium hydroxide aqueous solution in the above range to ensure that the effective components in the bisphenol F mother liquor fully react to generate epoxy resin.
In the present invention, the temperature of the polymerization reaction is preferably 55 to 80 ℃, more preferably 60 to 70 ℃, still more preferably 62 to 65 ℃. In the present invention, the polymerization time is 2 to 8 hours, more preferably 3 to 5 hours. The invention controls the temperature and time of the polymerization reaction in the above range, so as to ensure the yield of the epoxy resin and reduce the occurrence of side reaction.
After the polymerization reaction is completed, the invention preferably carries out post-treatment on the product of the polymerization reaction to obtain the epoxy resin.
In the present invention, the post-treatment preferably includes a removal of epichlorohydrin, a purification, a neutralization water washing, a toluene removal and a filtration.
The method for removing the epoxy chloropropane is not particularly limited, and the purpose of removing the epoxy chloropropane can be achieved.
The purification method of the present invention is not particularly limited, and the purpose of reducing the hydrolysis chlorine may be achieved.
The method of the invention is not particularly limited, and the purpose of neutral pH value of the product after the neutralization and the water washing is achieved.
The mode of removing toluene is not particularly limited, and the purpose of removing toluene can be achieved.
The filtering mode is not particularly limited, and the purpose of solid-liquid separation can be achieved.
The method for preparing the epoxy resin by using the bisphenol F mother liquor provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The flow chart of the method for preparing epoxy resin by using bisphenol F mother liquor provided by the invention is shown in figure 1, and specifically comprises the following steps: mixing phenol and phosphoric acid, then dropwise adding formaldehyde aqueous solution, performing addition reaction to obtain a mixture containing bisphenol F, adding ethanol, mixing, filtering to obtain a filter cake finished bisphenol F and a filter liquor respectively, separating the filter liquor to obtain an organic phase and recovered phosphoric acid respectively, recovering the organic phase to obtain phenol, ethanol and bisphenol F mother liquor respectively, mixing the bisphenol F mother liquor and an organic solvent to obtain a mixed solution, mixing the mixed solution with bisphenol compounds, epichlorohydrin and sodium hydroxide aqueous solution, and performing polymerization reaction to obtain epoxy resin.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for preparing epoxy resin by bisphenol F mother liquor comprises the following steps:
(1) Mixing 500g of phenol and 202g of 85% phosphoric acid aqueous solution with mass concentration in a 2000mL four-necked flask, heating and stirring uniformly, dropwise adding 180g of formaldehyde aqueous solution at a constant speed under the condition of controlling the temperature to be 42 ℃, keeping the temperature at 50 ℃ after 5h dropwise adding, and carrying out addition reaction for 2h to obtain a mixture containing bisphenol F;
the mass percentage concentration of the formaldehyde aqueous solution is 37%;
the ratio of the amounts of formaldehyde and phosphoric acid in the phenol, formaldehyde aqueous solution was 2.4:1:0.8;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with 300g of absolute ethyl alcohol, transferring the materials out after the system is uniformly stirred, filtering the materials by using filter paper, and respectively collecting filter cakes, namely 424g of finished bisphenol F and 758g of filtrate;
the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is 0.6:1, a step of;
(3) Transferring the filtrate obtained in the step (2) into a separating funnel, standing for layering, separating liquid, and respectively collecting 443g of organic phase and recycling phosphoric acid;
the organic phase is subjected to reduced pressure distillation, phenol and ethanol are respectively recovered, and 71g of phenol, 275g of ethanol and 97g of bisphenol F mother liquor are respectively obtained;
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with 42g of isopropanol serving as an organic solvent to obtain a mixed liquor;
the mass ratio of the isopropyl alcohol organic solvent to the bisphenol F mother liquor is 0.43:1, a step of;
(5) Adding 21g of 4, 4-bisphenol F (purity is more than 99%) into the mixed solution obtained in the step (4), then adding 138g of epichlorohydrin and sodium hydroxide aqueous solution, carrying out polymerization reaction for 4 hours at 62 ℃, and then sequentially carrying out epichlorohydrin removal, refining, neutralization water washing, toluene removal and filtration to obtain epoxy resin;
the mass ratio of 4, 4-bisphenol F (i.e. bisphenol compound) in the step (5) to bisphenol F mother liquor in the step (4) is 0.22:1, a step of;
the mass ratio of the epichlorohydrin in the step (5) to the bisphenol F mother liquor in the step (4) is 1.42:1, a step of;
the mass ratio of the sodium hydroxide in the sodium hydroxide aqueous solution in the step (5) to the bisphenol F mother liquor in the step (4) is 6:1.
the epoxy resin product prepared in example 1 was tested by the methods of GB/T4612-1984, GB/T12007.4-1989 and GB/T4618-1984, respectively, to have an epoxy equivalent of 194g/eq, a viscosity of 9331cps and a hydrolysis chlorine of 367ppm, and belongs to a high equivalent low viscosity liquid epoxy resin.
400g of the epoxy resin prepared in example 1 was mixed with 100g of polyetheramine D230 hardener and coated on a tinplate to give a coating film-1, which was cured at 25℃for 72 hours, and then various properties of the coating film-1 were tested, as shown in Table 1.
Example 2
A method for preparing epoxy resin by bisphenol F mother liquor comprises the following steps:
(1) Mixing 1000g of phenol and 236g of 85% phosphoric acid aqueous solution with mass concentration in a 3000mL four-necked flask, heating and stirring uniformly, dropwise adding 350g of formaldehyde aqueous solution at a constant speed under the condition of controlling the temperature to be 40 ℃, after 8h of dropwise adding, carrying out addition reaction for 1.5h at 45 ℃ in a heat preservation way to obtain a mixture containing bisphenol F;
the mass percentage concentration of the formaldehyde aqueous solution is 35%;
the ratio of the amounts of formaldehyde and phosphoric acid in the phenol, formaldehyde aqueous solution was 2.6:1:0.7;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with 500g of absolute ethyl alcohol, transferring the materials out after the system is uniformly stirred, filtering the materials by using filter paper, and respectively collecting filter cakes, namely 559g of finished bisphenol F, and 1527g of filtrate;
the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is 0.5:1, a step of;
(3) Transferring the filtrate obtained in the step (2) into a separating funnel, standing for layering, separating liquid, and respectively collecting 792g of organic phase and recycling phosphoric acid;
rectifying the organic phase, and respectively recovering phenol and ethanol to obtain 143g of phenol, 446g of ethanol and 203g of bisphenol F mother liquor;
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with 71g of toluene serving as an organic solvent to obtain a mixed liquor;
the mass ratio of toluene to bisphenol F mother liquor of the organic solvent is 0.35:1, a step of;
(5) Adding 61g of 4, 4-bisphenol A (purity is more than 99%) into the mixed solution obtained in the step (4), then adding 122g of epichlorohydrin and sodium hydroxide aqueous solution, carrying out polymerization reaction for 8 hours at 60 ℃, and then sequentially carrying out epichlorohydrin removal, refining, neutralization water washing, toluene removal and filtration to obtain epoxy resin;
the mass ratio of the 4, 4-bisphenol A (i.e. bisphenol compound) in the step (5) to the bisphenol F mother liquor in the step (4) is 0.30:1, a step of;
the mass ratio of the epichlorohydrin in the step (5) to the bisphenol F mother liquor in the step (4) is 0.60:1, a step of;
the mass ratio of the sodium hydroxide in the sodium hydroxide aqueous solution in the step (5) to the bisphenol F mother liquor in the step (4) is 3:1.
the epoxy resin products prepared in example 2 were tested by the methods of GB/T4612-1984 and GB/T4618-1984, respectively, for an epoxy equivalent of 483g/eq and a hydrolysis chlorine of 602ppm, and belong to solid epoxy resins.
200g of the epoxy resin prepared in example 2 was mixed with 80g of polyetheramine D230 curing agent, coated on a tinplate to obtain a coating film-2, cured at 25℃for 72 hours, and then tested for various properties of the coating film-2, see Table 1 in particular.
Example 3
A method for preparing epoxy resin by bisphenol F mother liquor comprises the following steps:
(1) Mixing 200g of phenol and 41g of phosphoric acid in a 1000mL four-neck flask, heating and stirring uniformly, dropwise adding 53g of formaldehyde aqueous solution at a constant speed under the condition of controlling the temperature to be 55 ℃, keeping the temperature at 50 ℃ after 2h dropwise adding, and carrying out addition reaction for 2h to obtain a mixture containing bisphenol F;
the mass percentage concentration of the formaldehyde aqueous solution is 40%;
the ratio of the amounts of formaldehyde and phosphoric acid in the phenol and formaldehyde aqueous solution is 3:1:0.5;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with 140g of absolute ethyl alcohol, transferring the materials out after the system is uniformly stirred, filtering the materials by using filter paper, and respectively collecting filter cakes, namely 124g of finished bisphenol F, and 310g of filtrate;
the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is 0.7:1, a step of;
(3) Transferring the filtrate obtained in the step (2) into a separating funnel, standing for layering, separating liquid, and respectively collecting 197g of organic phase and recycling phosphoric acid;
subjecting the organic phase to column chromatography, and respectively recovering phenol and ethanol to obtain 36g of phenol, 103g of ethanol and 58g of bisphenol F mother liquor;
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with 26g of propylene glycol methyl ether serving as an organic solvent to obtain a mixed solution;
the mass ratio of the propylene glycol methyl ether and bisphenol F mother liquor of the organic solvent is 0.45:1, a step of;
(5) Adding 17g of tetrabromobisphenol A with the purity more than 99% into the mixed solution obtained in the step (4), then adding 162g of epichlorohydrin and sodium hydroxide aqueous solution, carrying out polymerization reaction for 2 hours at 70 ℃, and then sequentially carrying out the steps of epichlorohydrin removal, refining, neutralization water washing, toluene removal and filtration to obtain epoxy resin;
the mass ratio of tetrabromohighly pure bisphenol A (i.e. bisphenol compound) in the step (5) to bisphenol F mother liquor in the step (4) is 0.29:1, a step of;
the mass ratio of the epichlorohydrin in the step (5) to the bisphenol F mother liquor in the step (4) is 2.79:1, a step of;
the mass ratio of the sodium hydroxide in the sodium hydroxide aqueous solution in the step (5) to the bisphenol F mother liquor in the step (4) is 10:1.
the epoxy resin products prepared in example 3 were examined by the methods of GB/T4612-1984 and GB/T4618-1984, respectively, for an epoxy equivalent of 315g/eq and a hydrolysis chlorine of 182ppm, and belong to semi-solid epoxy resins.
160g of the epoxy resin prepared in example 3 was mixed with 60g of polyetheramine D230 hardener, coated on a tinplate to obtain a coating film-3, cured at 25℃for 72 hours, and then tested for various properties of the coating film-3, see Table 1 in particular.
Example 4
A method for preparing epoxy resin by bisphenol F mother liquor comprises the following steps:
(1) Mixing 5000g of phenol and 2787g of phosphoric acid in a 20L four-neck flask, heating and stirring uniformly, controlling the temperature to be 48 ℃ and dripping 1960g of formaldehyde aqueous solution at a constant speed, keeping the temperature at 55 ℃ after 12h dripping, and carrying out addition reaction for 1h to obtain a mixture containing bisphenol F;
the mass percentage concentration of the formaldehyde aqueous solution is 37%;
the ratio of the amounts of formaldehyde and phosphoric acid in the phenol, formaldehyde aqueous solution was 2.1:1:1, a step of;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with 2500g of absolute ethyl alcohol, transferring the materials out after the system is uniformly stirred, filtering the materials by using filter paper, and respectively collecting filter cakes, namely 4542g of finished bisphenol F, and 7705g of filtrate;
the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is 0.5:1, a step of;
(3) Transferring the filtrate obtained in the step (2) into a separating funnel, standing for layering, separating liquid, and respectively collecting 4613g of organic phase and recycling phosphoric acid;
subjecting the organic phase to reduced pressure distillation, and recovering phenol and ethanol respectively to obtain 863g of phenol, 2026g of ethanol and 1724g of bisphenol F mother liquor;
(4) Mixing 604g of bisphenol F mother liquor obtained in the step (3) with petroleum ether serving as an organic solvent to obtain a mixed liquor;
the mass ratio of the petroleum ether serving as the organic solvent to the bisphenol F mother liquor is 0.35:1, a step of;
(5) Adding 340g of bisphenol S (purity is more than 99%) into the mixed solution obtained in the step (4), then adding 2586g of epoxy chloropropane and sodium hydroxide aqueous solution, carrying out polymerization reaction for 5 hours at 64 ℃, and then sequentially carrying out the steps of removing epoxy chloropropane, refining, neutralizing, washing with water, removing toluene and filtering to obtain epoxy resin;
the mass ratio of bisphenol S (i.e., bisphenol compound) in the step (5) to bisphenol F mother liquor in the step (4) is 0.20:1, a step of;
the mass ratio of the epichlorohydrin in the step (5) to the bisphenol F mother liquor in the step (4) is 1.5:1, a step of;
the mass ratio of the sodium hydroxide in the sodium hydroxide aqueous solution in the step (5) to the bisphenol F mother liquor in the step (4) is 7:1.
the epoxy resin products prepared in example 4 were tested by the methods of GB/T4612-1984 and GB/T4618-1984, respectively, for 203g/eq and 608ppm of hydrolyzed chlorine, and were liquid epoxy resins.
200g of the epoxy resin prepared in example 4 was mixed with 50g of polyetheramine D230 hardener and coated on a tinplate to give a coating film-4, which was cured at 25℃for 72 hours, and then various properties of the coating film-4 were tested, as shown in Table 1.
The results of the performance tests of each of the coating films-1 to-4 prepared by using the epoxy resins prepared in examples 1 to 4 as raw materials are shown in Table 1, wherein the surface drying time and the real drying time represent the concentration of the epoxy value in the epoxy resin, and the surface drying time and the real drying time are tested according to the method in national standard GB/T1728-1979; the bonding property between the epoxy resin and the base material is reflected by a cross-hatch test, which is tested according to the method in national standard GB/T9286-1998; the pencil hardness shows the mechanical strength of the epoxy resin after curing, and the pencil hardness is tested according to the method in national standard GB/T6739-2006.
TABLE 1 Properties of coating films prepared using the epoxy resins of examples 1 to 4 as raw materials, respectively
As can be seen from examples and Table 1, by using the method provided by the present invention, the epoxy resins prepared in examples 1 to 4 as raw materials, the surface drying time of the prepared coating films-1 to-4 is as low as 2 to 3 hours, the real drying time is as low as 8 to 19 hours, indicating that the epoxy value concentration inside the epoxy resins prepared in examples 1 to 4 is 0.20 to 0.51mol/100g; the cross-cut test of coating films-1 to-4 is grade 0 or 1, which shows that the adhesion between the epoxy resins prepared in examples 1 to 4 and the base material tinplate is better; the pencil hardness of the coating film-1 to the coating film-4 is HB, H or 2H, and the epoxy resin prepared in the examples 1 to 4 and the curing agent polyether amine D230 are fully reacted to form a three-dimensional network structure, so that the mechanical strength of the coating film is improved, in a word, the bisphenol F mother liquor recovered in the examples 1 to 4 can be used for preparing the epoxy resin with the epoxy value concentration of 0.20 to 0.51mol/100g, better adhesion with the substrate tinplate and capability of providing the mechanical strength of the coating film, namely, the bisphenol F mother liquor recovered in the examples 1 to 4 meets the requirements of epoxy resin synthetic raw materials, and the method provided by the invention directly utilizes the bisphenol F mother liquor to prepare the epoxy resin, realizes the environment-friendly recovery treatment of the bisphenol F mother liquor and the recycling of resources.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing epoxy resin by using bisphenol F mother liquor, comprising the following steps:
(1) Mixing phenol and phosphoric acid, then dropwise adding formaldehyde aqueous solution, and carrying out addition reaction after the dropwise adding is finished to obtain a mixture containing bisphenol F;
(2) Mixing the mixture containing bisphenol F obtained in the step (1) with ethanol, and filtering to obtain bisphenol F and filtrate;
(3) Separating the filtrate obtained in the step (2) to obtain an organic phase and recovered phosphoric acid respectively;
recovering the organic phase to obtain phenol, ethanol and bisphenol F mother liquor respectively;
(4) Mixing the bisphenol F mother liquor obtained in the step (3) with an organic solvent to obtain a mixed solution;
(5) And (3) mixing the mixed solution obtained in the step (4) with bisphenol compound, epichlorohydrin and sodium hydroxide aqueous solution, and performing polymerization reaction to obtain the epoxy resin.
2. The method according to claim 1, wherein the ratio of the amounts of phenol, formaldehyde in the aqueous formaldehyde solution and phosphoric acid in step (1) is (2 to 3.5): 1: (0.3-1.5).
3. The method according to claim 1, wherein the temperature of the dropping in the step (1) is 40 to 55 ℃ and the time of the dropping is 1 to 14 hours.
4. The method according to claim 1, wherein the temperature of the addition reaction in the step (1) is 40 to 55 ℃, and the time of the addition reaction is 0.5 to 4 hours.
5. The method according to claim 1, wherein the mass ratio of the ethanol in the step (2) to the phenol in the step (1) is (0.4 to 0.9): 1.
6. the method according to claim 1, wherein the recovery treatment in the step (3) comprises reduced pressure distillation, rectification or column chromatography.
7. The method according to claim 1, wherein the mass ratio of the organic solvent to the bisphenol F mother liquor in the step (4) is (0.2 to 0.5): 1.
8. the method according to claim 1 or 7, wherein the mass ratio of bisphenol compound in the step (5) to bisphenol F mother liquor in the step (4) is (0.1 to 0.4): 1.
9. the method according to claim 1, wherein the mass ratio of epichlorohydrin in the step (5) and bisphenol F mother liquor in the step (4) is (0.5 to 3): 1.
10. the method according to claim 1, wherein the polymerization reaction in the step (5) is carried out at a temperature of 55 to 80 ℃ for a time of 2 to 8 hours.
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| US4221893A (en) * | 1978-01-11 | 1980-09-09 | Makhteshim Chemical Works Limited | Brominated bisphenol-a epoxy compositions |
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| CN111875778A (en) * | 2020-07-30 | 2020-11-03 | 江苏扬农化工集团有限公司 | Method for preparing epoxy resin from triglycidyl isocyanurate production by-product |
| CN112409573A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Byproduct polyphenol epoxy resin and preparation method and application thereof |
| CN112409139A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Bisphenol A production method and device |
| CN112409138A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Bisphenol A production method and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221893A (en) * | 1978-01-11 | 1980-09-09 | Makhteshim Chemical Works Limited | Brominated bisphenol-a epoxy compositions |
| US20030096939A1 (en) * | 2000-03-30 | 2003-05-22 | Michael Bodiger | Substance mixture containing bisphenol a |
| CN104447217A (en) * | 2014-12-05 | 2015-03-25 | 四川东材绝缘技术有限公司 | Synthesis method of 4,4-bisphenol F |
| CN112409573A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Byproduct polyphenol epoxy resin and preparation method and application thereof |
| CN112409139A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Bisphenol A production method and device |
| CN112409138A (en) * | 2019-08-23 | 2021-02-26 | 南通星辰合成材料有限公司 | Bisphenol A production method and device |
| CN111875778A (en) * | 2020-07-30 | 2020-11-03 | 江苏扬农化工集团有限公司 | Method for preparing epoxy resin from triglycidyl isocyanurate production by-product |
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