CN111348989A - Bis-hydroxyethyl bisphenol A ether and preparation method thereof - Google Patents
Bis-hydroxyethyl bisphenol A ether and preparation method thereof Download PDFInfo
- Publication number
- CN111348989A CN111348989A CN202010334719.4A CN202010334719A CN111348989A CN 111348989 A CN111348989 A CN 111348989A CN 202010334719 A CN202010334719 A CN 202010334719A CN 111348989 A CN111348989 A CN 111348989A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- ether
- bis
- hydroxyethyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 339
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 200
- -1 Bis-hydroxyethyl Chemical group 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 54
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 claims abstract description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000007872 degassing Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims 25
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 5
- UQQWTEOWFCQTGZ-UHFFFAOYSA-N 2,3-bis(2-hydroxyethyl)-4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound OCCC=1C(=C(O)C=CC=1C(C)(C)C1=CC=C(C=C1)O)CCO UQQWTEOWFCQTGZ-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 38
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000004970 Chain extender Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000004811 liquid chromatography Methods 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to bis-hydroxyethyl bisphenol A ether and a preparation method thereof, wherein the bis-hydroxyethyl bisphenol A ether is prepared from bisphenol A, a zinc-magnesium oxide catalyst, bis-hydroxyethyl bisphenol A ether, a phosphoric acid auxiliary agent and ethylene oxide. Thus, bisphenol A is used as a raw material, zinc magnesium oxide is used as a catalyst, phosphoric acid is used as an auxiliary agent, bis-hydroxyethyl bisphenol A ether is used as a solvent, and ethylene oxide is used as a chain extender to synthesize bis-hydroxyethyl bisphenol A ether. The method can reduce the cost of the solvent, does not need to remove the solvent, thoroughly solves the problems of complicated production procedures and environment caused by the solvent, greatly reduces the reaction temperature, also reduces the generation of byproducts, has stable product performance, does not have catalyst residue in reaction products, and greatly saves the purification cost of the products.
Description
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to bis-hydroxyethyl bisphenol A ether and a preparation method thereof.
Background
The bis-hydroxyethyl bisphenol A ether is mainly used as a structural unit of polyurethane, polyester and epoxy resin, and can be esterified with unsaturated acids such as acrylic acid, methacrylic acid and the like to prepare various functional high-molecular polymerization monomers. The elastic resin synthesized by condensation of bis-hydroxyethyl bisphenol A ether and aromatic dicarboxylic acid can isolate noise and reduce harmful vibration. The bis-hydroxyethyl bisphenol A ether is bonded into a high molecular polymer chain according to a certain proportion, so that the polymer has better strength, elasticity, adhesive force and processability. The bis-hydroxyethyl bisphenol A ether is mainly applied to the fields of paint, coating, printing ink, composite material, adhesive and the like.
At present, the research reports on bis-hydroxyethyl bisphenol A ether at home and abroad are more, most of the research reports are preparation methods of bisphenol A ether, and a small amount of patents are related to refining methods of bisphenol A ether. Such as:
chinese patent CN104203568B discloses an alkoxylated material with low bisphenol a residue, its preparation and use, wherein an alkali catalyst or an alkali metal catalyst is used as a catalyst, and molten BPA is used as a raw material for reaction. Because the melting point of the bisphenol A is about 158 ℃, the heating medium of the bisphenol A must be at least higher than 10 ℃ to melt the bisphenol A, and the melted bisphenol A is easy to have isomerization and decomposition reactions above 158 ℃, so that the by-products of the ethoxylation products of the bisphenol A are increased, and the color and luster of the products are difficult to ensure at high temperature.
Japanese patent JP 2011037792A discloses a process for producing a high-purity dihydroxyethyl ether of bisphenol by using water, toluene and xylene solvents for the production of the dihydroxyethyl ether. Alkali metal hydroxide, alkaline earth metal hydroxide, amine, quaternary ammonium salt and the like are used as catalysts. The preferred water solvent is water which can produce byproducts such as polyethylene glycol and the like under the action of an alkali metal hydroxide catalyst. Furthermore, amine catalysts tend to produce yellow color and produce amine ethoxylates as by-products. The bis-hydroxyethyl bisphenol A ether has high viscosity and is difficult to remove when the solvent water is removed. The toluene and the xylene can bring about complicated production procedures and environmental protection problems.
Chinese patent CN107216453A discloses a method for preparing bis-hydroxyethyl bisphenol A ether, which comprises the steps of reacting bisphenol A with ethylene oxide, and reacting at 120-150 ℃ by using KOH as a catalyst. Although the process can obtain high-purity bis-hydroxyethyl bisphenol A ether with low water content, the color is poor and is generally light yellow due to the alkali catalyst.
Japanese patent JP2008143854A discloses a method and a composition for preparing dioxy vinyl ether of bisphenol, which uses trialkylamine as a catalyst, lithium hydroxide and other amines as catalysts, and toluene as a solvent to synthesize a bisphenol A adduct at a temperature of 80-150 ℃. Although the synthesis method disclosed by the patent can obtain hydroxyethylated bisphenol A with the purity of 97.8%, the catalyst residue can influence the color of the product and deepen the color of the product by using the alkylamine catalyst, and the catalyst is not removed, so that the downstream application is influenced. The adopted solvents such as toluene and the like bring the problems of complicated production process and environmental protection.
US6342641 discloses a purified bisphenol a ethoxylate and a process for its purification by neutralization with a mineral acid, i.e. phosphoric acid, followed by treatment with a colloidal metal silicate. Because the direct neutralization method is adopted, the generated crystals are very fine and are difficult to be absorbed by magnesium silicate and other adsorbents, and the defects of difficult filtration, large product residual quantity in filter residues, high metal ion residue in products and the like are caused due to the high viscosity of the ethoxylated bisphenol A ether.
The synthesis of the technical scheme for preparing bis-hydroxyethyl bisphenol A ether disclosed at present mainly has the following three defects:
firstly, the melting point of bisphenol A is about 158 ℃, and two methods are generally adopted: the method is a high-temperature melting method (at least requiring high-temperature melting above 160 ℃), which can cause the color and luster of the product to be dark, and can easily cause the side reaction of bisphenol A under the high-temperature condition at high temperature, so that the by-products are increased; the second method adopts a solvent dissolving method, but the method needs complicated solvent removing procedures to increase the production cost, and most solvents have toxicity and great influence on the environment.
Secondly, the distribution of the components of the product synthesized by the catalysts of alkali metal hydroxide, amine and the like is wide, the distribution of the components of the product is difficult to control, and the requirements of certain products with high quality and high performance, such as UV curing coating reactive diluent, can not be met.
The product has high viscosity and high melting point, the catalyst for removing alkali metal hydroxide and alkaline earth metal hydroxide by the conventional method is difficult to remove, the catalyst removal cost is high, and the product loss is large.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the bis-hydroxyethyl bisphenol A ether and the preparation method of the bis-hydroxyethyl bisphenol A ether, wherein the reaction temperature is low, the problems of complicated production procedures and environment caused by solvents are effectively solved, no catalyst residue exists in reaction products, and the purification cost of the products is greatly saved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a bis-hydroxyethyl bisphenol A ether is prepared from bisphenol A, a zinc-magnesium oxide catalyst, bis-hydroxyethyl bisphenol A ether, a phosphoric acid additive and ethylene oxide; wherein the sum of the mass percentages of the bisphenol A, the zinc magnesium oxide catalyst, the bis-hydroxyethyl bisphenol A ether and the ethylene oxide is 99.5%, the mass percentage of the phosphoric acid assistant is 0.5%, the mass ratio of the bisphenol A to the zinc magnesium oxide catalyst is 100: 1-100: 10, the mass ratio of the bisphenol A to the bis-hydroxyethyl bisphenol A ether is 10: 3-10: 8, and the mass ratio of the bisphenol A to the ethylene oxide is 100: 42.05.
Further, the mass ratio of the bisphenol A to the bis-hydroxyethyl bisphenol A ether is 2: 1.
A method for preparing bis-hydroxyethyl bisphenol A ether comprises the following steps:
A1. pretreatment of raw materials: sequentially adding bisphenol A and a zinc-magnesium oxide catalyst into a first reaction kettle filled with nitrogen, and heating;
A2. solvent pretreatment: using bis-hydroxyethyl bisphenol A ether as a solvent, adding the bis-hydroxyethyl bisphenol A ether into a second reaction kettle, and heating to melt and stir the bis-hydroxyethyl bisphenol A ether;
A3. mixing and dissolving: putting bisphenol A and a zinc-magnesium oxide catalyst in a first reaction kettle into a second reaction kettle which is subjected to bis-hydroxyethyl bisphenol A ether pretreatment, and heating until the bisphenol A is completely dissolved;
A4. reaction: adding a phosphoric acid auxiliary agent into a second reaction kettle, starting to input a small amount of ethylene oxide into the second reaction kettle, starting to stably input the ethylene oxide when the temperature is raised to the reaction temperature, and keeping the temperature to continue reacting after the ethylene oxide is completely input until the pressure in the second reaction kettle is not reduced any more;
A5. degassing: and after the heat preservation continuous reaction is finished, cooling and degassing the second reaction kettle, and then filtering the zinc-magnesium oxide catalyst to obtain a finished product.
Further, the heating in the step a1 is heating the first reaction kettle to heat the material in the first reaction kettle to 80-130 ℃, preferably to 110 ℃.
Further, in the step A2, adding the bis-hydroxyethyl bisphenol A ether into a second reaction kettle, heating to 100-180 ℃, preferably heating to 130 ℃.
Further, in the step A4, the reaction temperature is 110-180 ℃, preferably 140 ℃, and the pressure of the second reaction kettle is controlled within 0.4 MPa.
Further, in step A5, the temperature of the second reaction kettle was lowered to 110 ℃ and the second reaction kettle was degassed for 30 min.
Through the technical scheme, the invention mainly has the following beneficial effects:
1. the method selects the reaction product of bis-hydroxyethyl bisphenol A ether as the solvent of the reaction material, has lower cost than other solvents mentioned in the prior patent, does not need to be removed, and thoroughly solves the problems of complicated production procedures and environment caused by the solvent.
2. The zinc-magnesium oxide with very high selectivity is used as a main catalyst, phosphoric acid is used as an auxiliary catalyst, the reaction temperature is greatly reduced, the generation of byproducts is reduced properly due to the reaction activity, and the prepared product has stable performance.
3. The filtered zinc-magnesium oxide can be repeatedly used as a main catalyst through the reaction kettle, and no catalyst residue exists in a reaction product, so that the product purification cost is greatly saved.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing bis-hydroxyethyl bisphenol A ether according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to bis-hydroxyethyl bisphenol A ether, which is prepared from bisphenol A, a zinc magnesium oxide catalyst, bis-hydroxyethyl bisphenol A ether, a phosphoric acid additive and ethylene oxide; wherein the sum of the mass percentages of the bisphenol A, the zinc magnesium oxide catalyst, the bis-hydroxyethyl bisphenol A ether and the ethylene oxide is 99.5%, the mass percentage of the phosphoric acid promoter is 0.5%, the mass ratio of the bisphenol A to the zinc magnesium oxide catalyst is 100: 1-100: 10, the mass ratio of the bisphenol A to the bis-hydroxyethyl bisphenol A ether is 10: 3-10: 8 (the best mass ratio is 2: 1), and the mass ratio of the bisphenol A to the ethylene oxide is 100: 42.05.
The bis-hydroxyethyl bisphenol A ether and the preparation method thereof provided by the embodiment of the invention are specifically shown as 1, and the preparation method comprises the following steps:
s100, raw material pretreatment: sequentially adding bisphenol A and a zinc-magnesium oxide catalyst into a first reaction kettle filled with nitrogen, and heating; and heating the first reaction kettle to heat the materials to 80-130 ℃, preferably to 110 ℃.
S200, solvent pretreatment: and (3) adding the bis-hydroxyethyl bisphenol A ether into a second reaction kettle to be heated (the temperature is raised to 100-180 ℃, preferably 130 ℃) by taking the bis-hydroxyethyl bisphenol A ether as a solvent, so as to melt and stir the bis-hydroxyethyl bisphenol A ether.
Step S300, mixing and dissolving: and putting the bisphenol A and the zinc-magnesium oxide catalyst in the first reaction kettle into a second reaction kettle which is subjected to the bis-hydroxyethyl bisphenol A ether pretreatment, and heating until the bisphenol A is completely dissolved.
Step S400, reaction: adding a phosphoric acid auxiliary agent into a second reaction kettle, beginning to input a small amount of ethylene oxide into the second reaction kettle, beginning to stably input the ethylene oxide when the temperature is raised to the reaction temperature (the reaction temperature is 110-180 ℃, preferably the reaction temperature is 140 ℃, and the pressure of the second reaction kettle is controlled within 0.4 MPa), and preserving the temperature after the ethylene oxide is completely input to continue to react until the pressure in the second reaction kettle is not reduced any more.
Step S500, degassing: after the heat preservation continuous reaction is finished, cooling and degassing the second reaction kettle (specifically, cooling to 110 ℃ and degassing for 30min), and then filtering the zinc-magnesium oxide catalyst (for example, filtering the zinc-magnesium oxide catalyst through a filter at the bottom end of the second reaction kettle) to obtain a finished product. In addition, a certain amount of bis-hydroxyethyl bisphenol A ether can be continuously left in the second reaction kettle for the next reaction to be used as a solvent.
The bis-hydroxyethyl bisphenol A ether is synthesized by taking bisphenol A as a raw material, zinc magnesium oxide as a catalyst, phosphoric acid as an auxiliary agent, the bis-hydroxyethyl bisphenol A ether as a solvent and ethylene oxide as a chain extender. Thus, the method thoroughly solves the problems of complicated production procedures and environment caused by the solvent by using the bis-hydroxyethyl bisphenol A ether as the solvent of the reaction material without removing the solvent, greatly reduces the reaction temperature by using the zinc-magnesium oxide with very high selectivity as the main catalyst and phosphoric acid as the auxiliary catalyst, properly reduces the generation of byproducts in reaction activity, and ensures that the prepared product has stable performance (specifically, because the zinc-magnesium oxide has small apparent alkalinity and the alkalinity is related to the alkalinity corresponding to divalent metal ions in the composition, the alkalinity can be adjusted by the proportion of zinc and aluminum to achieve the effect of catalyst activity, meanwhile, the acid-base center on the surface of the zinc-magnesium oxide is exposed by high-temperature roasting to show stronger acid-base property, and the catalytic performance on the surface of the zinc-magnesium oxide is adjusted by the phosphoric acid auxiliary agent, finally, after the zinc-magnesium oxide catalyst is filtered by the reaction kettle, no catalyst residue exists in a reaction product, and the zinc-magnesium oxide serving as a main catalyst can be recycled, so that the product purification cost is greatly saved. )
The bis-hydroxyethyl bisphenol A ether and the preparation method thereof according to the present invention are further illustrated by the following specific examples.
In the following examples, the content of bis-hydroxyethyl bisphenol A ether and the residual amount of bisphenol A in the product were obtained by high performance liquid chromatography, the hydroxyl value detection method refers to GB/T7383-2007, and the color and luster is obtained by comparison with a standard colorimetric tube.
Best embodiment 1:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were sequentially added to a first reaction vessel, the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether was 92.1%, the residual amount of bisphenol A was 0ppm, the color was No. 20 (Pt-Co units), and the hydroxyl value measured by a chemical method was 346 mgKOH/g.
Example 2:
a. 2000g of bisphenol A and 20g of zinc-magnesium oxide catalyst were sequentially added to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of the bis-hydroxyethyl bisphenol A ether is 83.7 percent, the residual quantity of the bisphenol A is 0ppm, the color and luster is No. 60 (Pt-Co unit), and the hydroxyl value measured by a chemical method is 349 mgKOH/g.
Example 3:
a. 2000g of bisphenol A and 2g of zinc-magnesium oxide catalyst were added in sequence to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether is 61.4 percent, the residual quantity of bisphenol A is 369ppm, the color and luster is No. 30 (Pt-Co unit), and the hydroxyl value is 391mgKOH/g by chemical method.
Example 4:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were sequentially added to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 80 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 160 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is increased to 160 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether is 90.3 percent, the residual quantity of bisphenol A is 0ppm, the color is No. 60 (Pt-Co unit), and the hydroxyl value is 345mgKOH/g by chemical method.
Example 5:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were added in this order to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 130 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 110 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether was 82.6%, the residual amount of bisphenol A was 138ppm, the color was No. 50 (Pt-Co units), and the hydroxyl value measured by a chemical method was 358 mgKOH/g.
Example 6:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were added in sequence to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 1000g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 110 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether is 87.8 percent, the residual amount of bisphenol A is 153ppm, the color is No. 30 (Pt-Co unit), and the hydroxyl value is 348mgKOH/g by chemical method.
Example 7:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were added in sequence to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 1600g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and pumped down to vacuum.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether is 89.5 percent, the residual amount of bisphenol A is 0ppm, the color is No. 20 (Pt-Co unit), and the hydroxyl value is 342mgKOH/g by chemical method.
Example 8:
a. 2000g of bisphenol A and 6g of zinc-magnesium oxide catalyst were added in sequence to a first reaction vessel, and the air in the first reaction vessel was replaced with nitrogen, and then the contents of the first reaction vessel were heated to 110 ℃.
b. The second reactor containing 600g of bis-hydroxyethyl bisphenol A ether was heated to 130 ℃ to melt and stir bis-hydroxyethyl bisphenol A ether and a low vacuum was applied.
c. And (3) putting the bisphenol A and the zinc magnesium oxide catalyst in the first reaction kettle into a second reaction kettle containing bis-hydroxyethyl bisphenol A ether, heating until the bisphenol A is completely dissolved, and starting stirring.
d. Adding 1g of phosphoric acid assistant into a second reaction kettle, simultaneously starting to introduce a small amount of ethylene oxide, starting to stably introduce the ethylene oxide (the total amount of the added ethylene oxide is 841g) when the temperature is raised to 140 ℃, controlling the pressure of the second reaction kettle within 0.4MPa, and keeping the temperature to continue the reaction (referred to as continuation) after the ethylene oxide is added until the pressure is not reduced any more.
e. Degassing: and after the continuation is finished, cooling to 110 ℃, degassing for 30min, and filtering the zinc-magnesium oxide catalyst by a filter at the bottom end of the second reaction kettle to obtain a finished product.
And (3) analyzing a product by liquid chromatography: the content of bis-hydroxyethyl bisphenol A ether is 86.3 percent, the residual amount of bisphenol A is 27ppm, the color is No. 20 (Pt-Co unit), and the hydroxyl value is 350mgKOH/g by chemical method.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The bis-hydroxyethyl bisphenol A ether is characterized by being prepared from bisphenol A, a zinc magnesium oxide catalyst, bis-hydroxyethyl bisphenol A ether, a phosphoric acid assistant and ethylene oxide; wherein the sum of the mass percentages of the bisphenol A, the zinc magnesium oxide catalyst, the bis-hydroxyethyl bisphenol A ether and the ethylene oxide is 99.5%, the mass percentage of the phosphoric acid assistant is 0.5%, the mass ratio of the bisphenol A to the zinc magnesium oxide catalyst is 100: 1-100: 10, the mass ratio of the bisphenol A to the bis-hydroxyethyl bisphenol A ether is 10: 3-10: 8, and the mass ratio of the bisphenol A to the ethylene oxide is 100: 42.05.
2. The bis-hydroxyethyl bisphenol-A ether of claim 1, wherein the mass ratio of bisphenol-A to bis-hydroxyethyl bisphenol-A ether is 2: 1.
3. A process for the preparation of bis-hydroxyethyl bisphenol a ether as defined in claim 1 or 2, comprising the steps of:
A1. pretreatment of raw materials: sequentially adding bisphenol A and a zinc-magnesium oxide catalyst into a first reaction kettle filled with nitrogen, and heating;
A2. solvent pretreatment: using bis-hydroxyethyl bisphenol A ether as a solvent, adding the bis-hydroxyethyl bisphenol A ether into a second reaction kettle, and heating to melt and stir the bis-hydroxyethyl bisphenol A ether;
A3. mixing and dissolving: putting bisphenol A and a zinc-magnesium oxide catalyst in a first reaction kettle into a second reaction kettle which is subjected to bis-hydroxyethyl bisphenol A ether pretreatment, and heating until the bisphenol A is completely dissolved;
A4. reaction: adding a phosphoric acid auxiliary agent into a second reaction kettle, starting to input a small amount of ethylene oxide into the second reaction kettle, starting to stably input the ethylene oxide when the temperature is raised to the reaction temperature, and keeping the temperature to continue reacting after the ethylene oxide is completely input until the pressure in the second reaction kettle is not reduced any more;
A5. degassing: and after the heat preservation continuous reaction is finished, cooling and degassing the second reaction kettle, and then filtering the zinc-magnesium oxide catalyst to obtain a finished product.
4. The method for preparing bis (hydroxyethyl) bisphenol A ether according to claim 3, wherein the heating in step A1 is performed by heating the first reaction vessel to 80-130 ℃.
5. The method of claim 4, wherein the heating step A1 is carried out by heating the first reaction vessel to 110 ℃.
6. The method for preparing bis (hydroxyethyl) bisphenol A ether according to claim 3, wherein step A2 comprises heating bis (hydroxyethyl) bisphenol A ether in a second reaction vessel to 100-180 ℃.
7. The method of claim 6, wherein the bis-hydroxyethyl bisphenol A ether is heated to 130 ℃ in step A2 by adding the bis-hydroxyethyl bisphenol A ether to the second reaction vessel.
8. The method for preparing bis (hydroxyethyl) bisphenol A ether according to claim 3, wherein the reaction temperature in step A4 is 110 to 180 ℃, and the pressure in the second reaction vessel is controlled to be within 0.4 MPa.
9. The method of claim 8, wherein the reaction temperature in step A4 is 140 ℃.
10. The method for preparing bis (hydroxyethyl) bisphenol A ether according to claim 3, wherein in step A5, the temperature of the second reaction vessel is lowered to 110 ℃ and the second reaction vessel is degassed for 30 min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010334719.4A CN111348989A (en) | 2020-04-24 | 2020-04-24 | Bis-hydroxyethyl bisphenol A ether and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010334719.4A CN111348989A (en) | 2020-04-24 | 2020-04-24 | Bis-hydroxyethyl bisphenol A ether and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111348989A true CN111348989A (en) | 2020-06-30 |
Family
ID=71191550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010334719.4A Pending CN111348989A (en) | 2020-04-24 | 2020-04-24 | Bis-hydroxyethyl bisphenol A ether and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111348989A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112876341A (en) * | 2021-01-11 | 2021-06-01 | 江苏钟山化工有限公司 | Preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1727516A (en) * | 2005-06-07 | 2006-02-01 | 浙江大学 | Low temperature method for preparing Nano crystal thin film of semiconductor in Znl-xMgxO structure of wurtzite |
CN104387247A (en) * | 2014-11-19 | 2015-03-04 | 浙江绿科安化学有限公司 | Method for preparing bis(hydroxyethyl) bisphenol A ether |
CN109534967A (en) * | 2019-01-04 | 2019-03-29 | 浙江皇马新材料科技有限公司 | A kind of bis-hydroxyethyl bisphenol A ether and preparation method thereof |
WO2019148731A1 (en) * | 2018-01-30 | 2019-08-08 | 北京铂阳顶荣光伏科技有限公司 | Zinc magnesium oxide material, preparation method therefor and solar cell |
-
2020
- 2020-04-24 CN CN202010334719.4A patent/CN111348989A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1727516A (en) * | 2005-06-07 | 2006-02-01 | 浙江大学 | Low temperature method for preparing Nano crystal thin film of semiconductor in Znl-xMgxO structure of wurtzite |
CN104387247A (en) * | 2014-11-19 | 2015-03-04 | 浙江绿科安化学有限公司 | Method for preparing bis(hydroxyethyl) bisphenol A ether |
WO2019148731A1 (en) * | 2018-01-30 | 2019-08-08 | 北京铂阳顶荣光伏科技有限公司 | Zinc magnesium oxide material, preparation method therefor and solar cell |
CN109534967A (en) * | 2019-01-04 | 2019-03-29 | 浙江皇马新材料科技有限公司 | A kind of bis-hydroxyethyl bisphenol A ether and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
马定连等: "高纯度乙氧基化双酚A醚(2)的合成研究", 《精细与专用化学品》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112876341A (en) * | 2021-01-11 | 2021-06-01 | 江苏钟山化工有限公司 | Preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid |
CN112876341B (en) * | 2021-01-11 | 2023-04-07 | 江苏钟山新材料有限公司 | Preparation method of nonionic-anionic composite bisphenol A ether carboxylic acid |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4463164A (en) | Process for preparing polyphenylene ethers | |
CN106397368B (en) | A kind of fatty alcohol polyoxyethylene ether glycidol ether and preparation method thereof | |
CN1332928C (en) | A multiple functional group (methyl) acrylate synthesis and purification method | |
CN102631930A (en) | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof | |
CN111348989A (en) | Bis-hydroxyethyl bisphenol A ether and preparation method thereof | |
WO2022062598A1 (en) | Supported solid super acidic catalyst, preparation method therefor and use thereof, and preparation method for ethoxylated trimethylolpropane | |
CN111499501A (en) | Bisphenol A bis (2, 3-dihydroxypropyl) ether and preparation method thereof | |
KR0145350B1 (en) | Preparation process for polyoxyalkylene polyol | |
CN111484395B (en) | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide | |
CN113024771A (en) | Preparation method of epoxy resin with low total chlorine content | |
CN109160880B (en) | Preparation method of ethyl benzoate | |
JPH06234700A (en) | Production of @(3754/24)meth)acrylic acid esters | |
CN110330428B (en) | Method for preparing diisobutyl phthalate | |
CN116082170A (en) | Preparation method of 4,4' -diaminodiphenyl ether | |
US2653162A (en) | Synthesis of alkylene cyanohydrins | |
CN109384654B (en) | Method for producing ethylene glycol mono-tert-butyl ether | |
CN115838474A (en) | Preparation method of bisphenol A polyether | |
JP4005301B2 (en) | Method for recovering active ingredients from polyester waste | |
CN103304413A (en) | Synthetic method of 2-hydroxyethyl methacrylate | |
CN116099522B (en) | Polyester alcoholysis catalyst and preparation method thereof | |
CN116262688B (en) | Method for preparing 1, 2-trimethoxy ethane at normal pressure | |
CN114292187B (en) | Organic compound extracted from waste generated in production of hydroxyalkyl acrylate and method thereof | |
CN216092327U (en) | Polyether polyol filter residue separation and recovery device | |
CN117050293A (en) | Synthesis method of high molecular weight pentaerythritol polyether | |
CN112679725B (en) | Method for acetylating low molecular polyether |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200630 |