CN104557791A - Method for preparing plant bisphenol glycidyl ether - Google Patents
Method for preparing plant bisphenol glycidyl ether Download PDFInfo
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- CN104557791A CN104557791A CN201410719521.2A CN201410719521A CN104557791A CN 104557791 A CN104557791 A CN 104557791A CN 201410719521 A CN201410719521 A CN 201410719521A CN 104557791 A CN104557791 A CN 104557791A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method for preparing plant bisphenol glycidyl ether. The synthesis of the plant bisphenol glycidyl ether comprises two steps of ring opening addition etherification and ring closing epoxidization dechlorination, the method is high in yield, and the prepared plant bisphenol glycidyl ether is lower in equivalent weight and better in quality and is conducive to industrial production. The plant bisphenol glycidyl ether prepared in the invention is flexible epoxy resin, which can be independently cured and can also be used for perfecting the toughness of the traditional rigid epoxy resin, so that the application prospect and value are extensive.
Description
Technical field
The present invention relates to the method adopting plant bis-phenol to prepare epoxy resin, is the preparation method of a kind of plant bis-phenol glycidyl ether specifically.
Background technology
Plant bis-phenol to refine from vegetable oil for industry purpose through processes such as decarboxylations and the one obtained contains C
15the bisphenol compound of unsaturated straight chain, abundance, cheap, nonpoisonous and tasteless, there is huge application prospect and research and development are worth.The basic structure of plant bis-phenol is as follows:
Plant bis-phenol is the resorcinol derivatives chemical that a class contains two hydroxyl, has very high phenols reactive behavior, the same with other alkylation Resorcinol class monomer, has good activity of reacting with methylene radical donor.In addition, plant bis-phenol contains carbon 15 straight chain of unsaturated double-bond, can provide good toughness for system.
What reported take plant phenols as the patent of bisphenol epoxy prepared by the raw material method that to comprise with the single phenol of plant and dihydroxyphenyl propane or the single phenol of plant and phenol be raw material, and does not relate to plant bis-phenol for the report of bisphenol epoxy prepared by raw material.
CN 201110147347.5 discloses a kind of synthetic technology of epoxy resin, with plant single phenol, dihydroxyphenyl propane, epoxy chloropropane and sodium hydroxide for raw material, prepare plant phenols epoxy resin, but this epoxy resin can not solidify as independent component.
CN 103145649 A report a kind of with plant single phenol, phenol, epoxy chloropropane and sodium hydroxide for the method for plant phenols-phenol bisphenol epoxy prepared by raw material.
CN 103449979 A reports and prepares the plant phenols-phenol affixture with bis-phenol structure with the single phenol of plant and phenol, and with the plant phenols of this bis-phenol structure-phenol affixture for the method for bisphenol epoxy prepared further by raw material.Meanwhile, CN 103145649 A and CN 103449979 A carbon 15 linear chain structure that all make use of on the single phenol of plant improves the toughness of epoxy resin.
Technology not for plant bis-phenol glycidyl ether in prior art, based on bisphenol A type epoxy resin, after this based epoxy resin and solidifying agent react, condensate performance is more crisp, and toughness is not good.The present invention adopts plant bis-phenol to be raw material, obtains that a kind of epoxy equivalent (weight) is lower, quality good plant bis-phenol glycidyl ether; And because on plant bis-phenol, the introducing of carbon 15 chain improves the toughness of epoxy resin.
Summary of the invention
The object of the present invention is to provide that a kind of epoxy equivalent (weight) is lower, quality better, be conducive to the preparation method of industrialized plant bis-phenol glycidyl ether, the glycidyl ether simultaneously has good toughness.
The object of the invention is to be realized by following manner:
The preparation method of one kind of plant bis-phenol glycidyl ether, comprises the steps:
(1) open loop addition etherification step
With plant bis-phenol and epoxy chloropropane for raw material, under protection of inert gas, under quaternary ammonium salt catalyst exists, there is open loop addition etherification reaction, generate chlorine hydroxy ethers intermediate;
(2) closed loop epoxidation dechlorination step
Then add sodium hydroxide in the chlorine hydroxy ethers intermediate prepared to step (1) and carry out first closed loop epoxidation dechlorination reaction, the temperature of reaction of first closed loop epoxidation dechlorination reaction is 50 ~ 80 DEG C; After the product at reduced pressure fractionation by distillation of first closed loop epoxidation dechlorination reaction goes out solvent and excess epoxy chloropropane, add sodium hydroxide solution again and carry out second closed loop epoxidation dechlorination reaction, product again after underpressure distillation crude product, the temperature of second closed loop epoxidation dechlorination reaction is 60 ~ 90 DEG C;
(3) epoxy resin purification step
Plant bis-phenol glycidyl ether is obtained after the crude product refining that step (2) obtains;
Concrete reaction formula is as follows:
Open loop addition etherificate:
The dechlorination of closed loop epoxidation:
In a preferred embodiment of the invention, in described step (1), the purity of described plant bis-phenol is 40% ~ 70%.
In a preferred embodiment of the invention, in described step (1), described plant bis-phenol and the mass ratio of epoxy chloropropane are 1:2.5 ~ 3.5.
In a preferred embodiment of the invention, in described step (1), described quaternary ammonium salt catalyst consumption is 1 ‰ ~ 15 ‰ of plant bis-phenol quality.
In a preferred embodiment of the invention, in described step (1), described quaternary ammonium salt catalyst selects the one or more kinds of mixing of benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide, tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide.
In a preferred embodiment of the invention, in described step (2), the mass concentration of the sodium hydroxide solution that described first closed loop epoxidation dechlorination reaction uses is 30% ~ 60%, the consumption of sodium hydroxide solution and the mass ratio of plant bis-phenol are 0.9 ~ 1.7:1, adopt constant pressure funnel to drip, the time of dropping is 2 ~ 6h; After dropwising, keep temperature 50 ~ 80 DEG C, reaction 0.5 ~ 2h.
In a preferred embodiment of the invention, in described step (2), the mass concentration of the sodium hydroxide solution that described second closed loop epoxidation dechlorination reaction uses is 10% ~ 30%, and the consumption of sodium hydroxide solution and the mass ratio of plant bis-phenol are 0.2 ~ 0.5:1, directly add; After adding, keep temperature 60 ~ 90 DEG C, reaction 1 ~ 3h.
In a preferred embodiment of the invention, in described step (2), the reactant after second closed loop epoxidation dechlorination reaction is first through underpressure distillation, and after underpressure distillation, remaining cut obtains plant bis-phenol glycidyl ether crude product by centrifuging.
In a preferred embodiment of the present invention, in described step (3), the crude product that described step (2) obtains obtains plant bis-phenol Racemic glycidol ether product through washing, separatory, distillation, multiple times of filtration.The present invention compares with existing technology, and its effect is actively with obvious.The present invention adopts two step synthesis techniques, first under catalyst action, plant bis-phenol and epoxy chloropropane carry out open loop addition etherification reaction, generate chlorine hydroxy ethers intermediate, then carry out closed loop epoxidation dechlorination reaction with sodium hydroxide and generate plant bis-phenol glycidyl ether.Material source of the present invention in plant, have that cost is low, environmental protection, the advantage such as renewable, the plant bis-phenol glycidyl ether simultaneously generated has the characteristic of the lower and quality better of epoxy equivalent (weight).The glycidyl ether of the present invention's synthesis, owing to having long alkyl chain (carbon 15 straight chain), thus has good toughness.The plant bis-phenol glycidyl ether of the present invention's synthesis can solidify with common epoxy curing agent separately, also can the toughness of improving other epoxy resin mixed with other epoxy resin.
Embodiment
The present invention will be further described in conjunction with the embodiments:
Embodiment 1
Toward with stirring, in the 1L four-hole boiling flask of thermometer and condensation reflux unit, logical nitrogen, with displaced air, adds plant bis-phenol 100g, epoxy chloropropane 250g, tetraethylammonium bromide 0.5g, stirs and be warming up to 50 DEG C, open loop addition etherification reaction 2h.Keep homo(io)thermism, drip by constant pressure funnel the sodium hydroxide solution 170g that mass concentration is 30%, time for adding is 4h, drips rear maintenance 2h and completes first closed loop epoxidation dechlorination reaction.Underpressure distillation, recycle-water and excessive epoxy chloropropane.Be warming up to 60 DEG C, disposable add mass concentration be 30% sodium hydroxide solution 20g carry out second closed loop epoxidation dechlorination reaction, reaction 1h.Centrifuging obtains plant bis-phenol glycidyl ether crude product; Washing, separatory, distillation, multiple times of filtration obtain plant bis-phenol Racemic glycidol ether product.The epoxy equivalent (weight) of product is 315g/eq, and yield is 92.0%, and free EPI is at below 10ppm, and fugitive constituent is less than 0.1%, viscosity 130cps (25 DEG C), hydrolyzable chloride content lower than 0.1%, colourity 8 (Gardener Color).
Embodiment 2
Toward with stirring, in the 1L four-hole boiling flask of thermometer and condensation reflux unit, logical nitrogen, with displaced air, adds plant bis-phenol 80g, epoxy chloropropane 240g, 4 bromide 0.3g, tetraethylammonium bromide 0.3g, stirs and is warming up to 75 DEG C, open loop addition etherification reaction 1h.Keep homo(io)thermism, drip by constant pressure funnel the sodium hydroxide solution 100g that mass concentration is 50%, time for adding is 3h, drips rear maintenance 1.5h and completes first closed loop epoxidation dechlorination reaction.Underpressure distillation, recycle-water and excessive epoxy chloropropane.Be warming up to 70 DEG C, disposable add mass concentration be 20% sodium hydroxide solution 25g carry out second closed loop epoxidation dechlorination reaction, reaction 2h.Centrifuging obtains plant bis-phenol glycidyl ether crude product; Washing, separatory, distillation, multiple times of filtration obtain plant bis-phenol Racemic glycidol ether product.The epoxy equivalent (weight) of product is 305g/eq, and yield is 93.0%, and free EPI is at below 10ppm, and fugitive constituent is less than 0.1%, viscosity 125cps (25 DEG C), hydrolyzable chloride content lower than 0.1%, colourity 8 (Gardener Color).
Embodiment 3
Toward with stirring, in the 1L four-hole boiling flask of thermometer and condensation reflux unit, logical nitrogen is with displaced air, and add plant bis-phenol 60g, epoxy chloropropane 210g, benzyl triethyl ammonium bromide 0.6g stirs and is warming up to 80 DEG C, open loop addition etherification reaction 0.5h.Keep homo(io)thermism, drip by constant pressure funnel the sodium hydroxide solution 50g that mass concentration is 60%, time for adding is 2.5h, drips rear maintenance 3h and completes first closed loop epoxidation dechlorination reaction.Underpressure distillation, recycle-water and excessive epoxy chloropropane.Be warming up to 90 DEG C, disposable add mass concentration be 30% sodium hydroxide solution 10g carry out second closed loop epoxidation dechlorination reaction, reaction 1h.Centrifuging obtains plant bis-phenol glycidyl ether crude product; Washing, separatory, distillation, multiple times of filtration obtain plant bis-phenol Racemic glycidol ether product.The epoxy equivalent (weight) of product is 308g/eq, and yield is 92.8%, and free EPI is at below 10ppm, and fugitive constituent is less than 0.1%, viscosity 131cps (25 DEG C), hydrolyzable chloride content lower than 0.1%, colourity 8 (Gardener Color).
Embodiment 4
The cure test of plant bis-phenol glycidyl ether and solidifying agent
The plant bis-phenol glyceryl ether that the present embodiment adopts is obtain in embodiment 2, and the mass ratio of solidifying agent and plant bis-phenol glycidyl ether is 0.5 ~ 2:10, mixes rear standing 1 hour scraper plate, is cured experiment under being placed in normal temperature.After 24 hours, epoxy resin solidifies completely, has good toughness after solidification, soft durometer rubber like.Along with the increase of curing agent content, the time starting to solidify shortens.
Embodiment 5
The cure test of epoxy resin (828)-plant bis-phenol glycidyl ether hybrid resin and solidifying agent
The plant bis-phenol glyceryl ether that the present embodiment adopts is obtain in embodiment 2, and the mass ratio of solidifying agent and blending epoxy is 1:10, mixes rear standing 1 hour scraper plate, is cured experiment under being placed in normal temperature.
As can be seen from the table, along with the increase of plant bis-phenol glycidyl ether ratio, after solidification, toughness increases, and improves the toughness of rigid epoxy resin 828; Epoxy resin 828 and plant bis-phenol glycidyl ether mass ratio are that sample toughness and hardness after normal temperature places 24 hours of 4:6 has both.
Claims (9)
1. the preparation method of a kind of plant bis-phenol glycidyl ether, comprises the steps:
(1) open loop addition etherification step
With plant bis-phenol and epoxy chloropropane for raw material, under protection of inert gas, under quaternary ammonium salt catalyst exists, there is open loop addition etherification reaction, generate chlorine hydroxy ethers intermediate;
(2) closed loop epoxidation dechlorination step
Then add sodium hydroxide in the chlorine hydroxy ethers intermediate prepared to step (1) and carry out first closed loop epoxidation dechlorination reaction, the temperature of reaction of first closed loop epoxidation dechlorination reaction is 50 ~ 80 DEG C; After the product at reduced pressure fractionation by distillation of first closed loop epoxidation dechlorination reaction goes out solvent and excess epoxy chloropropane, add sodium hydroxide solution again and carry out second closed loop epoxidation dechlorination reaction, product again after underpressure distillation crude product, the temperature of second closed loop epoxidation dechlorination reaction is 60 ~ 90 DEG C;
(3) epoxy resin purification step
Plant bis-phenol glycidyl ether is obtained after the crude product refining that step (2) obtains;
Concrete reaction formula is as follows:
Open loop addition etherificate:
The dechlorination of closed loop epoxidation:
2. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, is characterized in that: in described step (1), and the purity of described plant bis-phenol is 40% ~ 70%.
3. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, is characterized in that: in described step (1), and described plant bis-phenol and the mass ratio of epoxy chloropropane are 1:2.5 ~ 3.5.
4. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, is characterized in that: in described step (1), and described quaternary ammonium salt catalyst consumption is 1 ‰ ~ 15 ‰ of plant bis-phenol quality.
5. the preparation method of the kind of plant bis-phenol glycidyl ether according to claim 1 or 4, it is characterized in that: in described step (1), described quaternary ammonium salt catalyst selects the one or more kinds of mixing of benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tributyl brometo de amonio, 4 bromide, tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide.
6. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, it is characterized in that: in described step (2), the mass concentration of the sodium hydroxide solution that described first closed loop epoxidation dechlorination reaction uses is 30% ~ 60%, the consumption of sodium hydroxide solution and the mass ratio of plant bis-phenol are 0.9 ~ 1.7:1, adopt constant pressure funnel to drip, the time of dropping is 2 ~ 6h; After dropwising, keep temperature 50 ~ 80 DEG C, reaction 0.5 ~ 2h.
7. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 6, it is characterized in that: in described step (2), the mass concentration of the sodium hydroxide solution that described second closed loop epoxidation dechlorination reaction uses is 10% ~ 30%, the consumption of sodium hydroxide solution and the mass ratio of plant bis-phenol are 0.2 ~ 0.5:1, directly add; After adding, keep temperature 60 ~ 90 DEG C, reaction 1 ~ 3h.
8. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, it is characterized in that: in described step (2), reactant after second closed loop epoxidation dechlorination reaction is first through underpressure distillation, and after underpressure distillation, remaining cut obtains plant bis-phenol glycidyl ether crude product by centrifuging.
9. the preparation method of a kind of plant bis-phenol glycidyl ether according to claim 1, it is characterized in that: in described step (3), the crude product that described step (2) obtains obtains plant bis-phenol Racemic glycidol ether product through washing, separatory, distillation, multiple times of filtration.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041506A (en) * | 2019-05-10 | 2019-07-23 | 河南省高新技术实业有限公司 | A kind of wood tar base epoxy, anticorrosive paint and preparation method thereof |
| CN115677623A (en) * | 2022-10-25 | 2023-02-03 | 常熟耐素生物材料科技有限公司 | Electronic-grade cashew nut bisphenol glycidyl ether and preparation process and application thereof |
| CN115716779A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Cardanol-based bisphenol as well as preparation method and application thereof |
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| CN110041506A (en) * | 2019-05-10 | 2019-07-23 | 河南省高新技术实业有限公司 | A kind of wood tar base epoxy, anticorrosive paint and preparation method thereof |
| CN110041506B (en) * | 2019-05-10 | 2021-08-24 | 河南省高新技术实业有限公司 | Wood tar-based epoxy resin, anticorrosive paint and preparation method thereof |
| CN115677623A (en) * | 2022-10-25 | 2023-02-03 | 常熟耐素生物材料科技有限公司 | Electronic-grade cashew nut bisphenol glycidyl ether and preparation process and application thereof |
| CN115716779A (en) * | 2022-11-28 | 2023-02-28 | 南京工业大学 | Cardanol-based bisphenol as well as preparation method and application thereof |
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