CN103772154B - A kind of modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F - Google Patents
A kind of modified hydroxylapatite catalyzes and synthesizes the method for Bisphenol F Download PDFInfo
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- CN103772154B CN103772154B CN201410033045.9A CN201410033045A CN103772154B CN 103772154 B CN103772154 B CN 103772154B CN 201410033045 A CN201410033045 A CN 201410033045A CN 103772154 B CN103772154 B CN 103772154B
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- bisphenol
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of take modified hydroxylapatite as the method for catalyst bisphenol synthesis F.The method for raw material with phenol, formaldehyde, is catalyzer with modified hydroxylapatite, obtains Bisphenol F through condensation reaction.The catalyzer adopted is by being carrier through preliminary pretreated hydroxyapatite, with aluminum chloride, zinc chloride, cupric chloride, titanium tetrachloride or iron(ic) chloride wherein any one or multiple for properties-correcting agent, carry out loaded modified and obtained.The catalyzer that reaction adopts is more cheap and easy to get, this catalyzer in the reaction good dispersity, catalytic efficiency high, be easy to be separated, can reuse, and the shortcoming such as when overcoming other catalyzer bisphenol synthesis F, by product is too high, corrodibility is strong, do not need in simultaneous reactions process to add other organic solvents, meet green economy principle.
Description
Technical field
The present invention relates to a kind of preparation method of Bisphenol F.
Background technology
Bisphenol F, chemical name is dihydroxydiphenyl methane, 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 especially it is convenient to injection moulding casting flowing, the feature even not adding thinner can be added less, be particularly suitable for the machine-shaping of wind turbine blade epoxy resin, also greatly reduce environmental pollution, improve processing environment.
The prior art 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 with phenol, formaldehyde for catalytic material bisphenol synthesis F.
It is the synthetic method of catalyzer that patent US4400554 reports with phosphoric acid, and phenol formaldehyde ratio is 4 ~ 6, temperature 40 ~ 50 DEG C, and the method is simple, and output is higher.It is the method for catalyzer one-step synthesis method 4,4-Bisphenol F that CN200810072071 then describes with phosphoric acid, but its yield only has about 60%.Patent JP58177928 etc. report the method catalyzing and synthesizing Bisphenol F with the mineral acid such as hydrochloric acid, sulfuric acid.Using these mineral acids such as phosphoric acid, hydrochloric acid, sulfuric acid as the method for 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.
The synthetic method that it is catalyzer that patent JP9255606, JP08198790, JP08268943, JP55124730 report with oxalic acid and oxalate, phenol formaldehyde ratio is 5 ~ 50, and temperature is 60 ~ 100 DEG C.The method reaction conditions is gentle, also more weak to equipment corrosion, but by product is many, and phenol formaldehyde ratio is too high, and productive rate is relatively low.Organic acid and oxalic acid are as catalyzer, and it is acid general more weak, for improving the proton hydrogen concentration in reaction fast, reaction must be made to carry out at a relatively high temperature.But temperature is higher, side reaction is more, and yield is also corresponding to be affected.
It is the method for catalyzer bisphenol synthesis F that patent JP11269113 reports with zeolite molecular sieve, patent CN101987812A discloses the method that one take the mesopore molecular sieve of silica alumina ratio 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 higher, react restive, raw material consumption and energy consumption larger.
Patent JP6340565 describes the technology by acid catalyst and urea-formaldehyde resin co-catalysis bisphenol synthesis F, the feature of this technology is the selectivity that can improve 4,4-isomer, easily reclaims after urea-formaldehyde resin reaction simultaneously, but resin repeat usage is low, realize recycle difficulty.
Patent CN102491879A reports using aluminum chloride and titanium tetrachloride modified synergic Zeo-karb as catalyzer, and phenol, formaldehyde are the method for Material synthesis Bisphenol F.Patent CN102584541A reports the method that Bisphenol F is prepared in the catalysis of a kind of 1-alkyl-3-methylimidazole acidic ionic liquid.
The bisphenol synthesis F method ubiquity phenol formaldehyde ratio reported at present is high, productive rate and the problem such as selectivity is on the low side, by product is many, long reaction time, corrodibility are strong, catalyst separating is difficult and repeating utilization factor is low; thus cause Bisphenol F production cost too high, have impact on the mass-producing application of this product.Therefore, a kind of catalytic activity of necessary exploitation is high, catalyzer is easy to separation 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 adjustable, the stronger ion-exchange capacity of surface acidic-basic property, designs modified hydroxylapatite catalyzer and applies to catalyzing and synthesizing of Bisphenol F.This process for catalytic synthesis has the advantages such as catalyst dispersity is good and easily separated recycling, product post-processed convenient, corrodibility is little, by product is few, and 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 take modified hydroxylapatite as the method for 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 DEG C, slowly formaldehyde solution is added drop-wise in reaction system, reaction times is 1-4h, after reaction terminates, cooling leaves 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 DEG C of dry pre-treatment 24h, then join 60 DEG C of backflow 5h in the tetra-sodium acetone soln of 3 ~ 10.0mmol/L, suction filtration is separated, washing with acetone, and 50 DEG C of vacuum-drying 24h are for subsequent use.Get the hydroxyapatite of above-mentioned process, be that 0.5 ~ 4mmol/g carries out modification in the ratio of properties-correcting agent and hydroxyapatite, properties-correcting agent dehydrated alcohol is made solution, add hydroxyapatite, backflow 5h, is then spin-dried for solvent, drying, obtains 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) is passed through the synthesis of hydroxyapatite carrier and the control of its modifying process, reach the order ground of the reactivity worth of regulation and control catalyst bisphenol synthesis F, under the prerequisite not affecting yield, decrease byproduct of reaction, improve 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 are conveniently; (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 four water-calcium nitrate 49.56g and primary ammonium phosphate 14.26g respectively, ca nitrate soln and ammonium dihydrogen phosphate is configured to deionized water, then regulate ammonium dihydrogen phosphate to pH ≈ about 10 with ammoniacal liquor, under 80 DEG C of constant temperature whipped states, slowly ammonium dihydrogen phosphate is dropped in ca nitrate soln, dropwise, use ammoniacal liquor regulation system pH ≈ about 10 again, continue constant temperature and stir 24 hours, then ageing for some time, throw out suction filtration is separated, use deionized water respectively, washing with alcohol 3 ~ 4 times, dry, mill, then 600 DEG C of roastings about two hours, obtain hydroxyapatite.
Get certain hydroxyl phosphatic rock through 120 DEG C of dry pre-treatment 24h, then join 60 DEG C of backflow 5h in the tetra-sodium acetone soln of 6mmol/L, suction filtration is separated, washing with acetone, and 50 DEG C of dry 24h of vacuum-drying are for subsequent use.Get the hydroxyapatite of above-mentioned process, be that 0.5mmol/g carries out modification in the ratio of aluminum chloride and hydroxyapatite, the appropriate dehydrated alcohol of aluminum chloride is made solution, add hydroxyapatite, backflow 5h, is then spin-dried for solvent, drying, obtains modified hydroxylapatite solid catalyst.
(2) modified hydroxylapatite catalyzes and synthesizes Bisphenol F
Phenol (30.08g is added in the three mouthfuls of round-bottomed flasks being furnished with condensing reflux pipe, constant pressure funnel and magnetic agitation, 0.32mol) with 0.8g modified hydroxylapatite catalyzer, constant temperature 85 DEG C, stir, slowly join in reaction system by the formaldehyde solution (3.24g, 0.04mol) that massfraction is 37% by constant pressure funnel, after reaction 2h, sampling, calculates with efficient liquid phase chromatographic analysis, obtains that Bisphenol F yield is 27.4%, selectivity is 93.1%.
Embodiment 2
Operation steps is with embodiment 1, and its difference is to change catalyst levels into 1g.Calculate with efficient liquid phase chromatographic analysis, 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 DEG C, and the reaction times is 3h.Calculate with efficient liquid phase chromatographic analysis, 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.Calculate with efficient liquid phase chromatographic analysis, 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 catalyst preparation 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.Calculate with efficient liquid phase chromatographic analysis, 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.Calculate with efficient liquid phase chromatographic analysis, 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.Calculate with efficient liquid phase chromatographic analysis, 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.Calculate with efficient liquid phase chromatographic analysis, 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, and namely carry out modification by 1.5mmol aluminum chloride and 1.5mmol zinc chloride and 1g hydroxyapatite, the reaction times is 4h.Calculate with efficient liquid phase chromatographic analysis, 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, and namely carry out modification by 1.5mmol aluminum chloride and 1.5mmol cupric chloride and 1g hydroxyapatite, the reaction times is 4h.Calculate with efficient liquid phase chromatographic analysis, 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, and namely carry out modification by 1.5mmol aluminum chloride and 1.5mmol iron(ic) chloride and 1g hydroxyapatite, the reaction times is 4h.Calculate with efficient liquid phase chromatographic analysis, 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 DEG C, and the reaction times is 4h.Calculate with efficient liquid phase chromatographic analysis, obtaining Bisphenol F yield is 68.8%, and Bisphenol F selectivity is 90.4%.
Various concrete raw material cited by the present invention, 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, does not enumerate embodiment at this.
Claims (1)
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 catalyst bisphenol synthesis F, catalyzer and formaldehyde mass ratio are 0.2 ~ 1: 1, phenol and formaldehyde mole ratio are 5 ~ 12: 1, phenol and catalyzer is the steps include: to join in the reactor with magnetic stirring apparatus, stir, after being heated to 50 ~ 90 DEG C, slowly formaldehyde is added drop-wise in reaction system, reaction times is 1 ~ 4h, after reaction terminates, cooling leaves standstill, suction filtration separating catalyst, filtrate decompression Distillation recovery phenol, obtain the thick product of Bisphenol F,
The preparation method of described modified hydroxylapatite is: get certain hydroxyl phosphatic rock through 120 DEG C of dry pre-treatment 24h, then join 60 DEG C of backflow 5h in the tetra-sodium acetone soln of 3 ~ 10.0mmol/L, suction filtration is separated, washing with acetone, 50 DEG C of vacuum-drying 24h, for subsequent use; In properties-correcting agent be that 0.5 ~ 4mmol/g carries out modification through the ratio of the hydroxyapatite of above-mentioned preliminary treatment, properties-correcting agent dehydrated alcohol is made solution, adds hydroxyapatite, backflow 5h, be spin-dried for solvent, dry, obtain modified hydroxylapatite solid catalyst;
In described hydroxyapatite, the mol ratio of Ca and P is 1.5 ~ 1.7: 1;
Described properties-correcting agent is the composition of aluminum chloride and cupric chloride or iron(ic) chloride.
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| 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 |
| CN107398290B (en) * | 2015-04-22 | 2020-01-10 | 江苏理工学院 | Catalyst for synthesizing thymol |
| 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 |
| 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 |
| 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 |
Citations (3)
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| US4400554A (en) * | 1982-03-29 | 1983-08-23 | Monsanto Company | Process for making bis(hydroxyphenyl)methanes |
| CN102491879A (en) * | 2011-11-14 | 2012-06-13 | 湘潭大学 | Preparation method for bisphenol F |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
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Patent Citations (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 |
| CN102491879A (en) * | 2011-11-14 | 2012-06-13 | 湘潭大学 | Preparation method for bisphenol F |
| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
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