CN105536827A - Composite acid supported catalyst and catalytic synthesis method of bisphenol F - Google Patents
Composite acid supported catalyst and catalytic synthesis method of bisphenol F Download PDFInfo
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- CN105536827A CN105536827A CN201510753553.9A CN201510753553A CN105536827A CN 105536827 A CN105536827 A CN 105536827A CN 201510753553 A CN201510753553 A CN 201510753553A CN 105536827 A CN105536827 A CN 105536827A
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Abstract
The invention discloses a composite acid supported catalyst and a catalytic synthesis method of bisphenol F. A synthesis method of the composite acid supported catalyst comprises the following steps: adding phosphoric acid, diatomite, LiCl and titanium dioxide to ethanol according to a certain ratio, and refluxing and stirring above raw materials overnight (for 12-24h); and recovering ethanol after the above reaction ends, washing the obtained material with water 3 times, and carrying out vacuum drying for 12h to obtain the composite acid supported catalyst. The synthesis method of bisphenol F comprises the following steps: adding phenol and the composite acid catalyst to a reaction container, adding xylene, stirring above materials at room temperature, adding 37% of an aqueous formaldehyde solution in a dropwise manner, and heating the obtained solution to 100-150DEG C, wherein the temperatures are 100DEG C, 125DEG C and 150DEG C respectively, toluene is adopted as a solvent, and the reaction time is 2-8h; and recovering the catalyst, the solvent and phenol, and re-crystallizing the above obtained product with the recovered solvent to obtain pure bisphenol F. The catalyst has the advantages of increase of the bisphenol F yield, simple synthesis method, low cost, high catalysis activity and reusability.
Description
Technical field
The present invention relates to the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, the downstream product derived by Bisphenol F is better than in a lot of taking bisphenol-A as the like product of raw material, the aspects such as such as heat-moisture resistance, insulating properties, processing and mechanical property, the performance requirements such as flame-retardant materials, casting and cast molding, electron level epoxy resin, large-scale wind electricity epoxy resin can be met, have a good application prospect, belong to chemical material and drug world.
Background technology
Bisphenol F (BPF) is the important chemical intermediate of one that phenol and formaldehyde obtain through hydroxyalkylation condensation reaction, has 2,2 '-Bisphenol F, 2,4 '-Bisphenol F and 4,4 '-Bisphenol F, amounts to three kinds of isomers, wherein best with 4,4 '-Bisphenol F isomers performance.Bisphenol F epoxy resin can be widely used in automobile, shipbuilding, aviation, machinery, electric, the industry such as chemical industry, national defence, because the mechanicalness that its rotproofness, high electrical insulating properties, low viscosity, cementability are good, solidfied material is excellent.
Because bisphenol f type epoxy resin has the performance of its uniqueness, there is the product of bisphenol f type epoxy resin in the external dominant company producing epoxy resin, and variety protection is complete.At present, the production of bisphenol F epoxy resin is little scale.Such as japan epoxy resin industry, the output of the non-bisphenol A type epoxy resin such as Bisphenol F has reached 1/4th of total output, and ratio is also in growth.The suitability for industrialized production of Bisphenol F still belongs to blank in China, still be in order trial production state on a small scale now, more seriously the downstream product of Bisphenol F also most dependence on import, the various trade mark bisphenol F epoxy resin raw materials of synthesis need import, impact is had, so the industrialization of Bisphenol F synthesis is very important on the quality of bisphenol F epoxy resin and use cost.Bisphenol F is as Novel chemical raw material, and investment cost effectiveness is low, lucrative, and having quite high technology content, is import substitutes, improves the key source of corresponding successor quality, can form corresponding high-tech industry group.So Bisphenol F product has good researching value and application prospect.
In traditional handicraft, general acid catalysis phenol, the formaldehyde of adopting is through condensation reaction bisphenol synthesis F, has phosphoric acid, sulfuric acid catalysis method, but there is the problems such as corrosivity, separation difficulty, a large amount of inorganic wastewaters of generation; In recent years the catalysis process such as modified resin, modified zeolite, mesopore molecular sieve, ionic liquid, hydroxyapatite are had.In recent years the new development metal-organic framework material of getting up owing to having the feature such as high-specific surface area, solvent resistance, in order pore structure, the field such as be employed for catalysis, carrier, absorption and be separated.Compared to conventional carriers, metal-organic framework material has larger aperture, can introduce nanoparticle, metalloporphyrin and phosphotungstic acid etc. in framework vestibule.Design and synthesis of the present invention NEW TYPE OF COMPOSITE acid supported catalyst, employing lithium chloride is metal organic frame, introducing phosphoric acid and titanium dioxide are made, substantially increase the performance of catalyst, for the synthesis of Bisphenol F, can improve the productive rate of reaction, what is more important improves the selective of reaction, has saved cost; This catalyst has not yet to see report.
Summary of the invention
1. the invention discloses the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F.
2. described in, the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, is characterized in that, comprise the steps:
The synthesis step of supported catalyst: the phosphoric acid (10g) by 85% joins in diatomite (100g), add LiCl (2.2g) and titanium dioxide (1.0-2.0g), add the ethanol of 0.5L, return stirring spends the night (12-24 hour).After reaction terminates, Distillation recovery ethanol, the solid matter obtained, wash 3 times, vacuum drying 12h, namely obtains Compound-acid supported catalyst.
The concrete steps of bisphenol synthesis F: phenol (8g), NEW TYPE OF COMPOSITE acid catalyst (2g) are joined in reaction vessel, add dimethylbenzene, stirred at ambient temperature is even, more slowly drips the formalin (5g) of 37%, is heated to 100-150 DEG C.Described reaction temperature is 100 DEG C, 125 DEG C, 150 DEG C, and solvent also can adopt toluene as the solvent of reaction.Reaction time is 2 ~ 8 hours.The reactant liquor obtained first filters, and reclaims solid catalyst.The liquid layered obtained, oil reservoir is the thick product of reaction.Thick for gained product is steamed recycling design, decompression distillation reclaim remaining phenol by revolving, remaining product recovered solvent recrystallization once, Bisphenol F that just can be pure.
Detailed description of the invention
The synthesis of a kind of Compound-acid supported catalyst as above and catalysis Bisphenol F.Compared with the phosphoric acid that NEW TYPE OF COMPOSITE acid catalyst provided by the invention and traditional handicraft adopt, there is higher catalytic performance, and environmental protection more.
Below, applicant has done some specific experiments to the present invention, describes a kind of preparation of Compound-acid supported catalyst, and lists the concrete steps with this type of supported catalyst bisphenol synthesis F.These only for elaborating the present invention, and limit scope of invention never in any form.
Embodiment one: the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, comprises following processing step:
The synthesis step of Compound-acid supported catalyst: the phosphoric acid (10g) by 85% joins in diatomite (100g), and the LiCl added (2.2g) and titanium dioxide (1.0g), add the ethanol of 0.5L, return stirring spends the night (12 hours).After reaction terminates, Distillation recovery ethanol, the solid matter obtained, wash 3 times, vacuum drying 12h, namely obtains Compound-acid supported catalyst.
The concrete steps of bisphenol synthesis F: by phenol (10.0g, 106.3mmol), NEW TYPE OF COMPOSITE acid supported catalyst (3g) joins in 250mL there-necked flask, add toluene, stirred at ambient temperature is even, slowly drip the formalin (2.5mL) of 37% again, be heated to 100 DEG C.Reaction time is 2 hours.The reactant liquor obtained first filters, and reclaims solid catalyst.The liquid layered obtained, oil reservoir is the thick product of reaction.Thick for gained product is revolved and steams recycling design, decompression distillation and reclaim remaining phenol, the simple and easy recrystallization of toluene of remaining product recovery once, Bisphenol F that just can be pure.Productive rate: 62%.
Embodiment two: the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, comprises following processing step:
The synthesis step of Compound-acid supported catalyst: the phosphoric acid (10g) by 85% joins in diatomite (100g), and the LiCl added (2.2g) and titanium dioxide (2.0g), add the ethanol of 0.5L, return stirring spends the night (12 hours).After reaction terminates, Distillation recovery ethanol, the solid matter obtained, wash 3 times, vacuum drying 12h, namely obtains Compound-acid supported catalyst.
The concrete steps of bisphenol synthesis F: by phenol (10.0g, 106.3mmol), NEW TYPE OF COMPOSITE acid supported catalyst (3g) joins in 250mL there-necked flask, add toluene, stirred at ambient temperature is even, slowly drip the formalin (2.5mL) of 37% again, be heated to 125 DEG C.Reaction time is 4 hours.The reactant liquor obtained first filters, and reclaims solid catalyst.The liquid layered obtained, oil reservoir is the thick product of reaction.Thick for gained product is revolved and steams recycling design, decompression distillation and reclaim remaining phenol, the simple and easy recrystallization of toluene of remaining product recovery once, Bisphenol F that just can be pure.Productive rate: 73%.
Embodiment three: the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, comprises following processing step:
The synthesis step of Compound-acid supported catalyst: the phosphoric acid (10g) by 85% joins in diatomite (100g), and the LiCl added (2.2g) and titanium dioxide (2.0g), add the ethanol of 0.5L, return stirring spends the night (24 hours).After reaction terminates, Distillation recovery ethanol, the solid matter obtained, wash 3 times, vacuum drying 12h, namely obtains Compound-acid supported catalyst.
The concrete steps of bisphenol synthesis F: by phenol (10.0g, 106.3mmol), NEW TYPE OF COMPOSITE acid supported catalyst (3g) joins in 250mL there-necked flask, add dimethylbenzene, stirred at ambient temperature is even, slowly drip the formalin (2.5mL) of 37% again, be heated to 150 DEG C.Reaction time is 4 hours.The reactant liquor obtained first filters, and reclaims solid catalyst.The liquid layered obtained, oil reservoir is the thick product of reaction.Thick for gained product is revolved and steams recycling design, decompression distillation and reclaim remaining phenol, the simple and easy recrystallization of toluene of remaining product recovery once, Bisphenol F that just can be pure.Productive rate: 79%.
Claims (2)
1. the invention discloses the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F.
2. described in, the synthesis of a kind of Compound-acid supported catalyst and catalysis Bisphenol F, is characterized in that, comprise the steps:
The synthesis step of supported catalyst: the phosphoric acid (10g) by 85% joins in diatomite (100g), add LiCl (2.2g) and titanium dioxide (1.0-2.0g), add the ethanol of 0.5L, return stirring spends the night (12-24 hour).After reaction terminates, Distillation recovery ethanol, the solid matter obtained, wash 3 times, vacuum drying 12h, namely obtains Compound-acid supported catalyst.
The concrete steps of bisphenol synthesis F: phenol (8g), NEW TYPE OF COMPOSITE acid catalyst (2g) are joined in reaction vessel, add dimethylbenzene, stirred at ambient temperature is even, more slowly drips the formalin (5g) of 37%, is heated to 100-150 DEG C.Described reaction temperature is 100 DEG C, 125 DEG C, 150 DEG C, and solvent also can adopt toluene as the solvent of reaction.Reaction time is 2 ~ 8 hours.The reactant liquor obtained first filters, and reclaims solid catalyst.The liquid layered obtained, oil reservoir is the thick product of reaction.Thick for gained product is steamed recycling design, decompression distillation reclaim remaining phenol by revolving, remaining product recovered solvent recrystallization once, Bisphenol F that just can be pure.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146259A (en) * | 2016-08-09 | 2016-11-23 | 江南大学 | A kind of new method of Bisphenol F synthesis |
| CN106268873A (en) * | 2016-08-03 | 2017-01-04 | 江南大学 | A kind of composite magnetic catalyst for Bisphenol F |
| CN112264012A (en) * | 2020-11-02 | 2021-01-26 | 江南大学 | Magnetic silicon-lithium catalyst and preparation method and application 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 |
| CN116082124A (en) * | 2022-11-14 | 2023-05-09 | 江苏扬农锦湖化工有限公司 | Preparation method of 4, 4-dihydroxydiphenyl methane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319314A (en) * | 2013-06-09 | 2013-09-25 | 陕西师范大学 | Synthesis method of bisphenol F in salt bath system |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319314A (en) * | 2013-06-09 | 2013-09-25 | 陕西师范大学 | Synthesis method of bisphenol F in salt bath system |
Non-Patent Citations (1)
| Title |
|---|
| 王琳: "合成双酚F的工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268873A (en) * | 2016-08-03 | 2017-01-04 | 江南大学 | A kind of composite magnetic catalyst for Bisphenol F |
| CN106146259A (en) * | 2016-08-09 | 2016-11-23 | 江南大学 | A kind of new method of Bisphenol F synthesis |
| CN112264012A (en) * | 2020-11-02 | 2021-01-26 | 江南大学 | Magnetic silicon-lithium catalyst and preparation method and application 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 |
| CN116082124A (en) * | 2022-11-14 | 2023-05-09 | 江苏扬农锦湖化工有限公司 | Preparation method of 4, 4-dihydroxydiphenyl methane |
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