CN103772154A - Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite - Google Patents
Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite Download PDFInfo
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- CN103772154A CN103772154A CN201410033045.9A CN201410033045A CN103772154A CN 103772154 A CN103772154 A CN 103772154A CN 201410033045 A CN201410033045 A CN 201410033045A CN 103772154 A CN103772154 A CN 103772154A
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- 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
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- 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
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- 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
- B01J27/1817—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 copper, silver or gold
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- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a method for the catalyzed synthesis of bisphenol F by using modified hydroxyapatite. The method is implemented by taking phenol and formaldehyde as raw materials and taking modified hydroxyapatite as a catalyst through a step of carrying out a condensation reaction on the raw materials and the catalyst so as to obtain bisphenol F. The adopted catalyst is prepared by carrying out load modification by taking hydroxyapatite subjected to preliminary pretreatment as a carrier and taking any one or more of aluminium chloride, zinc chloride, copper chloride, titanium tetrachloride or ferric chloride as modifiers. The adopted catalyst is cheap and easy to obtain, the catalyst is good in dispersibility, high in catalytic efficiency, easy to separate and reusable in the reaction, and overcomes the defects of too high by-products, strong corrosivity, and the like in the process of synthesizing bisphenol F by using other catalysts; and in the process of reaction, other organic solvents are not required to be added, therefore, the method conforms to the principle of green economy.
Description
Technical field
The present invention relates to a kind of preparation method of Bisphenol F.
Background technology
Bisphenol F, chemical name is dihydroxyl ditan, due to its chemical structure feature, be suitable for preparing low viscosity epoxy resin, its finished product is all better than bisphenol A epoxide resin at aspect of performances such as thermotolerance, wet fastness, insulativity, processibility and injection moulding casting, and it is mobile that especially it is convenient to injection moulding casting, can add less the feature that does not even add thinner, be particularly suitable for the machine-shaping of large-scale wind electricity blade ring epoxy resins, also greatly reduced environmental pollution, improved processing environment.
The prior art of having reported is all that difference is the difference of used catalyst, generally has the catalysis process such as mineral acid, organic acid, molecular sieve, ion exchange resin, ionic liquid and heteropolyacid take phenol, formaldehyde as catalytic material bisphenol synthesis F.
Patent US4400554 has reported the synthetic method take phosphoric acid as catalyzer, and phenol formaldehyde ratio is 4～6,40～50 ℃ of temperature, and the method is simple, and output is higher.CN200810072071 has introduced the method for synthetic 4, the 4-Bisphenol F take phosphoric acid as catalyzer single stage method, but its yield only has 60% left and right.Patent JP58177928 etc. have reported the method that catalyzes and synthesizes Bisphenol F with the mineral acid such as hydrochloric acid, sulfuric acid.Method using these mineral acids such as phosphoric acid, hydrochloric acid, sulfuric acid as catalyst bisphenol synthesis F, exist to production unit corrodibility compared with strong, by product is many, reaction is violent and be difficult to the shortcomings such as control.
Patent JP9255606, JP08198790, JP08268943, JP55124730 have reported the synthetic method take oxalic acid and oxalate as catalyzer, and phenol formaldehyde ratio is 5～50, and temperature is 60～100 ℃.The method reaction conditions gentleness, to equipment corrosion also a little less than, but by product is many, phenol formaldehyde ratio is too high, productive rate is relatively low.Organic acid and oxalic acid is as catalyzer, its acidity generally a little less than, be to improve fast the proton hydrogen concentration in reaction, must make reaction carry out at relatively high temperature.But temperature is higher, side reaction is just more, and yield is corresponding being affected also.
Patent JP11269113 has reported the method take zeolite molecular sieve as catalyzer bisphenol synthesis F, patent CN101987812A discloses a kind of method take the silica alumina ratio mesopore molecular sieve of 60: 1～150: 1 as catalyst bisphenol synthesis F, this class methods product separation and catalyst recovery ratio are easier to, but phenol formaldehyde ratio and temperature of reaction are higher, react restive, raw material consumption and energy consumption are larger.
Patent JP6340565 has introduced the technology of acid catalyst and urea-formaldehyde resin co-catalysis bisphenol synthesis F, the feature of this technology is to improve the selectivity of 4,4-isomer, after urea-formaldehyde resin reaction simultaneously, easily reclaims, but resin repeat usage is low, realize recycle difficulty.
Patent CN102491879A has reported that phenol, formaldehyde are the method for raw material bisphenol synthesis F using aluminum chloride and titanium tetrachloride modified synergic Zeo-karb as catalyzer.Patent CN102584541A has reported a kind of method of preparing Bisphenol F with the catalysis of 1-alkyl-3-methylimidazole acidic ionic liquid.
The problems such as the bisphenol synthesis F method ubiquity phenol formaldehyde ratio reported is at present high, productive rate and selectivity is on the low side, by product is many, long reaction time, corrodibility is strong, catalyst separating is difficult and repeating utilization factor is low; thereby cause Bisphenol F production cost too high, affected the mass-producing application of this product.Therefore, a kind of catalytic activity of necessary exploitation is high, catalyzer is easy to separate and recycles, stability is high, the Bisphenol F of environmental protection catalyzes and synthesizes novel method.
The present invention utilizes hydroxyapatite to have the characteristics such as the ion-exchange capacity that surface acid alkalescence is adjustable, stronger, designs modified hydroxylapatite catalyzer and applies to catalyzing and synthesizing of Bisphenol F.The advantages such as this process for catalytic synthesis has catalyzer good dispersity and easily separated recycling, product post-processed is convenient, corrodibility is little, by product is few, meanwhile, Catalyst Production process is simple, cheap.Therefore, this Bisphenol F process for catalytic synthesis has broad prospects in commercial scale production, is a kind of Bisphenol F synthetic method of green high-efficient.
Summary of the invention
The object of this invention is to provide a kind of method take modified hydroxylapatite as catalyst bisphenol synthesis F.
Technical scheme of the present invention is, a kind of modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F: with phenol, formaldehyde is raw material, take modified hydroxylapatite as catalyzer, catalyze and synthesize Bisphenol F, catalyzer and formaldehyde mass ratio are 0.2-1: 1, phenol and formaldehyde mole ratio are 5-12: 1 the steps include: phenol and catalyzer to join in the reactor with magnetic stirring apparatus, stir, be heated to as after 50-90 ℃, slowly formaldehyde solution is added drop-wise in reaction system, reaction times is 1-4h, after reaction finishes, cooling leaving standstill, suction filtration separating catalyst, filtrate decompression Distillation recovery phenol, obtain the thick product of Bisphenol F.
The preparation of modified hydroxylapatite: get certain hydroxyl phosphatic rock through 120 ℃ of dry pre-treatment 24h, then join 60 ℃ of backflow 5h in the tetra-sodium acetone soln of 3～10.0mmol/L, suction filtration separates, washing with acetone, 50 ℃ of vacuum-drying 24h, for subsequent use.Getting the hydroxyapatite of above-mentioned processing, is that 0.5～4mmol/g carries out modification in the ratio of properties-correcting agent and hydroxyapatite, and properties-correcting agent is made to solution with dehydrated alcohol, add hydroxyapatite, backflow 5h, is then spin-dried for solvent, dry, obtain modified hydroxylapatite solid catalyst.
In described hydroxyapatite, the mol ratio of Ca and P is 1.2～2: 1, and preferred mol ratio is 1.5～1.7: 1.
Properties-correcting agent be aluminum chloride, zinc chloride, cupric chloride, titanium tetrachloride or iron(ic) chloride wherein any one or multiple.
The present invention has following technique effect: (1) by hydroxyapatite carrier synthetic with and the control of modifying process, reach the order ground of the reactivity worth of regulation and control catalyst bisphenol synthesis F, do not affecting under the prerequisite of yield, reduce byproduct of reaction, improved the selectivity of Bisphenol F; (2) present method is a kind of environmentally friendly Bisphenol F synthetic method, and equipment corrosion is little, and catalyzer is cheap and easy to get, and product separation and subsequent disposal convenience; (3) reaction process does not need to add other organic solvents, and catalyzer is nontoxic non-volatile, environmental protection.(4) synthesis technique is simple, is easy to realize industrial scale and produces.
Embodiment
Below by specific embodiment, the present invention is elaborated.
Embodiment 1
(1) preparation of modified hydroxylapatite catalyzer
Take respectively four water-calcium nitrate 49.56g and primary ammonium phosphate 14.26g, be configured to ca nitrate soln and ammonium dihydrogen phosphate with deionized water, then regulate ammonium dihydrogen phosphate to pH ≈ 10 left and right with ammoniacal liquor, under 80 ℃ of constant temperature whipped states, slowly ammonium dihydrogen phosphate is dropped in ca nitrate soln, dropwise, use again ammoniacal liquor regulation system pH ≈ 10 left and right, continuing constant temperature stirs 24 hours, then ageing for some time, throw out suction filtration separates, use respectively deionized water, washing with alcohol 3～4 times, dry, mill, then 600 ℃ of roastings approximately two hours, obtain hydroxyapatite.
Get certain hydroxyl phosphatic rock through 120 ℃ of dry pre-treatment 24h, then join 60 ℃ of backflow 5h in the tetra-sodium acetone soln of 6mmol/L, suction filtration separates, washing with acetone, and 50 ℃ of dry 24h of vacuum-dryings, for subsequent use.Getting the hydroxyapatite of above-mentioned processing, is that 0.5mmol/g carries out modification in the ratio of aluminum chloride and hydroxyapatite, and aluminum chloride is made to solution with appropriate dehydrated alcohol, add hydroxyapatite, backflow 5h, is then spin-dried for solvent, dry, obtain modified hydroxylapatite solid catalyst.
(2) modified hydroxylapatite catalyzes and synthesizes Bisphenol F
Add phenol (30.08g to being furnished with in three mouthfuls of round-bottomed flasks of condensing reflux pipe, constant pressure funnel and magnetic agitation, 0.32mol) with 0.8g modified hydroxylapatite catalyzer, 85 ℃ of constant temperature, stir, the formaldehyde solution (3.24g, 0.04mol) that is 37% by massfraction with constant pressure funnel slowly joins in reaction system, after reaction 2h, sampling, calculates with efficient liquid phase chromatographic analysis, obtains Bisphenol F yield and be 27.4%, selectivity is 93.1%.
Embodiment 2
Operation steps is with embodiment 1, and its difference is to change catalyst levels into 1g.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 33.4%, and Bisphenol F selectivity is 92.8%.
Embodiment 3
Operation steps is with embodiment 1, and its difference is that the ratio of properties-correcting agent aluminum chloride and hydroxyapatite is 3mmol/g, and temperature of reaction is 80 ℃, and the reaction times is 3h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 62.7%, and Bisphenol F selectivity is 91.4%.
Embodiment 4
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is zinc chloride, and the ratio of properties-correcting agent zinc chloride and hydroxyapatite is 1.5mmol/g, and the reaction times is 2h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 47.3%, and Bisphenol F selectivity is 91.5%.
Embodiment 5
Operation steps is with embodiment 1, and its difference is that catalyzer raw materials primary ammonium phosphate changes 16.1g into, and properties-correcting agent and hydroxyapatite proportioning are 4mmol/g, and catalyst levels is 1.2g, and the reaction times is 4h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 71.3%, and Bisphenol F selectivity is 90.7%.
Embodiment 6
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is cupric chloride.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 38.2%, and Bisphenol F selectivity is 92.7%.
Embodiment 7
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is titanium tetrachloride.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 40.1%, and Bisphenol F selectivity is 93.4%.
Embodiment 8
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is iron(ic) chloride.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 37.5%, and Bisphenol F selectivity is 92.9%.
Embodiment 9
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is aluminum chloride and zinc chloride, and properties-correcting agent and hydroxyapatite proportioning are 3mmol/g, carries out modification by 1.5mmol aluminum chloride and 1.5mmol zinc chloride and 1g hydroxyapatite, and the reaction times is 4h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 65.3%, and Bisphenol F selectivity is 90.7%.
Embodiment 10
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is aluminum chloride and cupric chloride, and properties-correcting agent and hydroxyapatite proportioning are 3mmol/g, carries out modification by 1.5mmol aluminum chloride and 1.5mmol cupric chloride and 1g hydroxyapatite, and the reaction times is 4h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 75.5%, and Bisphenol F selectivity is 91.3%.
Embodiment 11
Operation steps is with embodiment 1, and its difference is that properties-correcting agent is aluminum chloride and iron(ic) chloride, and properties-correcting agent and hydroxyapatite proportioning are 3mmol/g, carries out modification by 1.5mmol aluminum chloride and 1.5mmol iron(ic) chloride and 1g hydroxyapatite, and the reaction times is 4h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 78.2%, and Bisphenol F selectivity is 92.1%.
Embodiment 12
Operation steps is with embodiment 1, its difference is that hydroxyapatite preprocessing process tetra-sodium acetone soln concentration is 10mmol/L, and the proportioning of properties-correcting agent aluminum chloride and hydroxyapatite is 3.5mmol/g, and phenol formaldehyde (PF) mol ratio is 12: 1, temperature of reaction is 90 ℃, and the reaction times is 4h.With efficient liquid phase chromatographic analysis calculating, obtaining Bisphenol F yield is 68.8%, and Bisphenol F selectivity is 90.4%.
The various concrete raw material that the present invention is cited, and the bound of each raw material, interval value, and the bound of processing parameter (as temperature, time, concentration etc.) can realize the present invention, do not enumerate embodiment at this.
Claims (4)
1. a modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F, it is characterized in that: with phenol, formaldehyde is raw material, take modified hydroxylapatite as catalyzer, catalyze and synthesize Bisphenol F, catalyzer and formaldehyde mass ratio are 0.2～1: 1, phenol and formaldehyde mole ratio are to the steps include: phenol and catalyzer join in reactor with magnetic stirring apparatus at 5～12: 1, stir, be heated to as after 50-90 ℃, slowly formaldehyde is added drop-wise in reaction system, reaction times is 1～4h, after reaction finishes, cooling leaving standstill, suction filtration separating catalyst, filtrate decompression Distillation recovery phenol, obtain the thick product of Bisphenol F.
2. a kind of modified hydroxylapatite according to claim 1 catalyzes and synthesizes the method for Bisphenol F, it is characterized in that: the preparation of modified hydroxylapatite: get a certain amount of hydroxyapatite through 120 ℃ of dry pre-treatment 24h, then join 60 ℃ of backflow 5h in the tetra-sodium acetone soln of 3～10.0mmol/L, suction filtration separates, washing with acetone, 50 ℃ of vacuum-drying 24h, for subsequent use.Get the above-mentioned hydroxyapatite through preliminary treatment, in properties-correcting agent be that 0.5～4mmol/g carries out modification through the ratio of preliminary treatment hydroxyapatite, properties-correcting agent is made to solution with dehydrated alcohol, add hydroxyapatite, backflow 5h, then be spin-dried for solvent, dry, obtain modified hydroxylapatite solid catalyst.
3. a kind of modified hydroxylapatite according to claim 2 catalyzes and synthesizes the method for Bisphenol F, it is characterized in that: in described hydroxyapatite, the mol ratio of Ca and P is 1.2～2: 1, and preferred mol ratio is 1.5～1.7: 1.
4. a kind of modified hydroxylapatite according to claim 2 catalyzes and synthesizes the method for Bisphenol F, it is characterized in that: properties-correcting agent be aluminum chloride, zinc chloride, cupric chloride, titanium tetrachloride or iron(ic) chloride wherein any one or multiple.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119208A (en) * | 2014-08-04 | 2014-10-29 | 湘潭大学 | Method for catalytic synthesis of bisphenol F from phosphoric acid modified disordered mesoporous hydroxyapatite |
| CN107382670A (en) * | 2015-04-22 | 2017-11-24 | 江苏理工学院 | Preparation method of thymol |
| CN112569936A (en) * | 2020-12-14 | 2021-03-30 | 江南大学 | Novel metal-doped catalyst for selectively synthesizing bisphenol F, and preparation method and application thereof |
| CN113274969A (en) * | 2021-05-26 | 2021-08-20 | 广西大学 | Composite material with formaldehyde adsorption function and preparation method thereof |
| CN114835559A (en) * | 2022-07-04 | 2022-08-02 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400554A (en) * | 1982-03-29 | 1983-08-23 | Monsanto Company | Process for making bis(hydroxyphenyl)methanes |
| CN102491879B (en) * | 2011-11-14 | 2014-05-14 | 湘潭大学 | Preparation method for bisphenol F |
| CN103480401B (en) * | 2013-09-30 | 2015-05-13 | 江苏理工学院 | Preparation method of hydroxyapatite-supported aluminum trichloride catalyst |
-
2014
- 2014-01-21 CN CN201410033045.9A patent/CN103772154B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119208A (en) * | 2014-08-04 | 2014-10-29 | 湘潭大学 | Method for catalytic synthesis of bisphenol F from phosphoric acid modified disordered mesoporous hydroxyapatite |
| CN104119208B (en) * | 2014-08-04 | 2016-01-13 | 湘潭大学 | The unordered mesoporous hydroxyapatite of a kind of phosphoric acid modification catalyzes and synthesizes the method for Bisphenol F |
| CN107382670A (en) * | 2015-04-22 | 2017-11-24 | 江苏理工学院 | Preparation method of thymol |
| CN107398290A (en) * | 2015-04-22 | 2017-11-28 | 江苏理工学院 | catalyst for synthesizing thymol |
| CN107382670B (en) * | 2015-04-22 | 2020-12-08 | 江苏理工学院 | Preparation method of thymol |
| CN112569936A (en) * | 2020-12-14 | 2021-03-30 | 江南大学 | Novel metal-doped catalyst for selectively synthesizing bisphenol F, and preparation method and application thereof |
| CN112569936B (en) * | 2020-12-14 | 2022-04-15 | 江南大学 | Novel metal-doped catalyst for selectively synthesizing bisphenol F, and preparation method and application thereof |
| CN113274969A (en) * | 2021-05-26 | 2021-08-20 | 广西大学 | Composite material with formaldehyde adsorption function and preparation method thereof |
| CN113274969B (en) * | 2021-05-26 | 2024-02-06 | 青岛隆璂保温建材有限公司 | Composite material with formaldehyde adsorption function and preparation method thereof |
| CN114835559A (en) * | 2022-07-04 | 2022-08-02 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
| CN114835559B (en) * | 2022-07-04 | 2022-09-09 | 山东亿科化学有限责任公司 | Catalytic method for synthesizing bisphenol F |
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