CN109456286A - A kind of phenolic hydroxyl group epoxidation preparation process - Google Patents
A kind of phenolic hydroxyl group epoxidation preparation process Download PDFInfo
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- CN109456286A CN109456286A CN201811158726.2A CN201811158726A CN109456286A CN 109456286 A CN109456286 A CN 109456286A CN 201811158726 A CN201811158726 A CN 201811158726A CN 109456286 A CN109456286 A CN 109456286A
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- 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
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- 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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- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
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- 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
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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- 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
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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Abstract
The invention discloses a kind of phenolic hydroxyl group epoxidation preparation processes, using phenolic hydroxy group compound and epoxychloropropane as raw material, under the action of catalyst, etherified ring-opening reaction prepares chloropharin ether, phenolic hydroxyl group epoxidation product is prepared through ring-closure reaction again, the catalyst is the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride, preparation step are as follows: be first modified mesopore molecular sieve, modified mesopore molecular sieve is mixed with benzyltriethylammoinium chloride aqueous solution again, immobilized method is heated through ultrasonic-microwave and prepares.Using phenolic hydroxyl group epoxidation preparation process, the low epoxy product of hydrolyzable chlorine content can be directly prepared, without complicated aftertreatment technology, and process stabilizing, material consumption, low energy consumption, and by-product is few, and the recyclable recycling of catalyst can be used for large-scale industrial production.
Description
Technical field
The present invention relates to epoxy resin preparation processes, and in particular to a kind of phenolic hydroxyl group epoxidation preparation process.
Background technique
Epoxy resin develops into a major class of thermosetting resin and extensive because of mechanical performance and excellent electric properties
It applies in fields such as adhesive, structural composite material, electronic semi-conductor's encapsulation.
Currently, epoxy resin preparation process is prepared using phenolic hydroxy group compound and epichlorohydrin reaction, preparation
Technical process has a great impact for the generation of epoxychloropropane effective rate of utilization, product yield, closed loop rate and waste water.With
National environmental protection policy it is increasingly stringent, the exploitation of efficient, environmentally protective technique becomes extremely urgent.
Conventional preparation techniques only with alkali, as sodium hydrate aqueous solution as single catalyst catalysis phenolic hydroxyl-compounds with
Epichlorohydrin reaction causes a large amount of epoxychloropropane to hydrolyze, and yield is relatively low.
A kind of system of hydrogenated bisphenol A epoxy resin is disclosed in the Chinese patent literature of 102766113 A of Publication No. CN
Preparation Method uses hydrogenated bisphenol A and epoxychloropropane for raw material, and solvent is added, and carries out open loop ether by catalyst of lewis acid
Change reaction, produces chloropharin ether intermediate；Aqueous slkali is added after recovery section solvent and carries out closed loop dechlorination reaction；By neutralizing, extracting
It takes, wash, the post-processing steps such as vacuum desolvation agent, preparing hydrogenated bisphenol A epoxy resin.Louis disclosed in the technical solution
Acid-specific is selected from one or more of aluminium chloride, iron chloride, boron trifluoride or tin tetrachloride.The preparation of above-mentioned catalyst guarantees
Reaction effect in early period etherification procedure, but in the product finally prepared hydrolyzable chlorine content it is higher, all higher than
463ppm is unable to satisfy national standard GB4613 (measuring method of epoxy resin and ethylene oxidic ester inorganic chlorine) and national standard GB4618
(epoxy resin and the measurement that chlorine is easily saponified in relation to material).
For another example a kind of hydrogenated bisphenol A epoxy resin is disclosed in the Chinese patent literature of 104193961 A of Publication No. CN
Preparation method, etherificate open loop is first also carried out as catalyst using lewis acid, then plus alkali progress ring-closure reaction.?
The product arrived need to be by washing desalination plus the post-processing steps such as alkali refining and washing, neutralization, filtering, desolventizing, to reduce it
In hydrolyzable chlorine content, minimum hydrolyzable chlorine content can reach 68.9ppm, but above-mentioned last handling process generates a large amount of waste water
And VOC, environmental pollution are larger.
Therefore, presently disclosed phenolic hydroxyl group epoxidation technique, can not still directly obtain the epoxy of low hydrolyzable chlorine content
Product.
Summary of the invention
Based on the above issues, the invention discloses a kind of phenolic hydroxyl group epoxidation preparation process, hydrolyzable can directly be prepared
The low epoxy product of chlorinity, without complicated aftertreatment technology, and process stabilizing, material consumption, low energy consumption, and by-product is few, catalysis
The recyclable recycling of agent, can be used for large-scale industrial production.
Specific technical solution is as follows:
A kind of phenolic hydroxyl group epoxidation preparation process, using phenolic hydroxy group compound and epoxychloropropane as raw material, in catalyst
Under effect, etherified ring-opening reaction prepares chloropharin ether, then phenolic hydroxyl group epoxidation product, the catalysis is prepared through ring-closure reaction
Agent is the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride.
The present invention is catalyzed hydroxyl containing phenol for the first time using the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride as catalyst
Based compound and epoxychloropropane carry out etherificate ring-opening reaction.It is found through experiment that the catalyst not only has excellent catalytic
Can, it is reusable, most special is that can substantially reduce hydrolyzable chlorine content and content of inorganic chlorine in final product, finally
Product only needs stewing process, collects the organic phase of lower layer, avoids complicated aftertreatment technology, greatly reduces environmentally friendly pressure
Power.
Mesopore molecular sieve in the catalyst has porous structure, with benzyltriethylammoinium chloride it is compound before also need
It is pre-processed, the specific preparation process of the catalyst is as follows:
A, mesopore molecular sieve is immersed in silane coupling agent hydrolyzate, takes out drying after standing hydrolysis, obtain modified Jie
Porous molecular sieve；
B, the modified mesoporous molecular sieve that step A is obtained is mixed with benzyltriethylammoinium chloride aqueous solution, it will by evaporation
Moisture except dry, surplus materials be placed in ultrasonic-microwave device 120~180 DEG C of 20~40min of heating to get.
In step A, the mesopore molecular sieve is preferably hexagon straight pore structure, the pore diameter range 5 with high-sequential
The SBA-15 mesopore molecular sieve of~50nm.
In step A, the silane coupling agent hydrolyzate is to be mixed by silane coupling agent and water by the weight ratio of 1~5:100
It closes, then adjusts its pH to 4.5~5.5, obtained after standing；
The silane coupling agent is selected from aminopropyl triethoxysilane or aminopropyl trimethoxysilane, and by the way that ice is added
Acetic acid adjusts its pH value, and time of repose is 1~3h.
Preferably, the weight ratio of the mesopore molecular sieve and silane coupling agent hydrolyzate is 1:2~200；Further preferably
For 1:20~50.
Soaking time of the mesopore molecular sieve in silane coupling agent hydrolyzate is 1~10h, is dried after taking-up
Temperature is 100~160 DEG C, and the time is 1~6h.
Preferably, in step B, the concentration of the benzyltriethylammoinium chloride aqueous solution is 10~1500g/L；
The benzyltriethylammoinium chloride aqueous solution is using benzyltriethylammoinium chloride as solute, it is preferable that the benzyl three
The weight ratio of ethyl ammonium chloride and modified mesoporous molecular sieve is 1:0.05~5.
Further preferably, the concentration of the benzyltriethylammoinium chloride aqueous solution is 20~1500g/L, benzyl triethyl ammonium chlorine
The weight ratio for changing ammonium and modified mesoporous molecular sieve is 1:0.2~2.5.
It is found through experiment that in final product using the catalyst preparation further preferably formed, hydrolyzable chlorine content
72ppm is can be controlled in hereinafter, minimum can be to 60ppm.
It is found through experiment that having three second of benzyl using immobilized compared to individually using benzyltriethylammoinium chloride as catalyst
Epoxidation product yield can be further improved as catalyst in the mesopore molecular sieve of ammonium chloride, and reduces in final product
Hydrolyzable chlorine content.Analyzing its reason may be, mesopore molecular sieve inner surface after silane coupling agent is handled with benzyl three
Ethyl ammonium chloride forms stable hydrogen bond, and along with high-specific surface area inside its duct, catalysis reaction efficiency is greatly improved.
If benzyltriethylammoinium chloride and mesopore molecular sieve progress is not compound in advance, but the two is directly blended to addition
In reaction system, it is found through experiment that, yield, hydrolyzable chlorine content be used alone benzyltriethylammoinium chloride have no it is obvious poor
It is different.
If modified mesoporous molecular sieve is replaced with the common carrier with porous structure of catalyst field, such as carbon nanometer
Pipe.It is found through experiment that the hydrolyzable chlorine content of final product is greater than 600ppm.
Thus illustrate, the combination of benzyltriethylammoinium chloride and modified mesoporous molecular sieve has particularity in the present invention, obtains
The yield for significantly improving phenolic hydroxyl group epoxidation product was obtained, and reduces the hydrolyzable chlorine of final product phenolic hydroxyl group epoxidation product
This unexpected technical effect of content, and the difference of the two hybrid mode also significantly affects the realization of the technical effect.
Based on above-mentioned catalyst, the specific steps of the phenolic hydroxyl group epoxidation preparation process include:
1) phenolic hydroxy group compound and epoxychloropropane are added under normal pressure；
2) it is proportionally added into the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride and makees catalyst, at 90~120 DEG C
Etherificate ring-opening reaction is carried out, the reaction time is 0.5~12h, obtains chloropharin ether；
3) system obtained to step 2) reaction is cooled to 40~80 DEG C, and alkali, 1~12h of insulation reaction are added into system；
4) system that step 3) reaction obtains is stood into cooling layering, obtained organic phase product is phenolic hydroxyl group epoxidation
Product.
Preferably, in step 1)~step 3):
The molar ratio of the phenolic hydroxyl-compounds and epoxychloropropane is 1:0.8~3；
The molar ratio of the phenolic hydroxyl-compounds and catalyst is 1:0.005~0.1；
The molar ratio of the phenolic hydroxyl-compounds and alkali is 1:0.8~2.2.
It is further preferred:
The molar ratio of the phenolic hydroxyl-compounds and epoxychloropropane is 1:1.2~2.1；
The molar ratio of the phenolic hydroxyl-compounds and catalyst is 1:0.005~0.02；
The molar ratio of the phenolic hydroxyl-compounds and alkali is 1:1.2~2.2.
In step 1), the phenolic hydroxy group compound is selected from common kind, such as bisphenol-A, Bisphenol F, phenol, eugenol
The aromatic compound of phenolic hydroxy group.
In step 3), the alkali is selected from one of sodium hydroxide, potassium hydroxide, ammonium hydroxide etc. or several, can be directly added into
Solid adds after can also being first configured to alkaline solution.Preferably, the alkali is added portionwise described in 0.5~5h
In system.
Preferably, the alkali is selected from sodium hydroxide, after being first configured to the sodium hydrate aqueous solution that concentration is 20wt%
It adds.
Compared with prior art, the present invention has the advantage that
Preparation process disclosed by the invention, using immobilized this specific group of the mesopore molecular sieve for having benzyltriethylammoinium chloride
At compound as catalyst, which has excellent catalytic properties etherificate ring-opening reaction, is reusable, can
To significantly improve the yield of phenolic hydroxyl group epoxidation product, most special is that the catalyst can substantially reduce can water in final product
Solution chlorinity and content of inorganic chlorine, final product only need stewing process, collect the organic phase of lower layer, avoid complicated
Aftertreatment technology greatly reduces environmental protection pressure.
Preparation process disclosed by the invention, process stabilizing, material consumption, low energy consumption, and by-product is few, and catalyst is recyclable to repeat benefit
With can be used for large-scale industrial production.
Specific embodiment
Embodiment 1
5g SBA-15 mesopore molecular sieve is immersed in 100mL aminopropyl triethoxysilane coupling agent hydrolyzate, and (concentration is
1wt% with glacial acetic acid tune pH to 5 and stands 2 hours)；Drying is taken out after impregnating 2 hours；
By benzyltriethylammoinium chloride aqueous solution (concentration 20g/L, 100mL) and treated SBA-15 mesoporous molecular
(5g) mixing is sieved, by evaporation by moisture except doing, surplus materials is placed in 120 DEG C of heating 20min in ultrasonic-microwave device, consolidate
It is loaded with the SBA-15 mesoporous molecular sieve catalyst of benzyltriethylammoinium chloride.
Bisphenol-A and epoxychloropropane (molar ratio 1:2.1) are added under normal pressure, being added manufactured in the present embodiment immobilized has benzyl
The mesoporous molecular sieve catalyst (addition mole is the 0.005 of bisphenol-A) of triethylammonium chloride, is etherified at 100 DEG C
Ring-opening reaction, reaction time are 2 hours, obtain chloropharin ether；60 DEG C or so are cooled to system, and catalyst is filtered out into recycling, Xiang Ti
20wt% sodium hydrate aqueous solution (sodium hydroxide adds 2.05 times that mole is bisphenol-A) is added dropwise in system, drips off within 2 hours subsequent
Continuous insulation reaction 6 hours；System is stood into cooling layering, obtained lower layer's product is bisphenol A epoxide resin.Final product
The performance test results are listed in the table below in 1.
Embodiment 2
Raw material, the technological parameter of phenolic hydroxyl group epoxidation preparation process is identical with embodiment 1, and difference is only that use
Catalyst is to use 5 times in embodiment 1 and the immobilized SBA-15 mesopore molecular sieve for having benzyltriethylammoinium chloride that recycles is urged
Agent.The performance test results of final product are listed in the table below in 1.
Embodiment 3
10g SBA-15 mesopore molecular sieve is immersed in 500mL aminopropyl trimethoxysilane coupling agent hydrolyzate (concentration
3%, with glacial acetic acid tune pH to 5 and stand 1 hour)；Drying is taken out after impregnating 2 hours；
By benzyltriethylammoinium chloride aqueous solution (concentration 1000g/L, 50mL) and mesoporous point of treated SBA-15
Sub- sieve (10g) mixing, by evaporation by moisture except doing, surplus materials is placed in 140 DEG C of heating 40min in ultrasonic-microwave device, obtains
To the immobilized SBA-15 mesoporous molecular sieve catalyst for having benzyltriethylammoinium chloride.
Bisphenol F and epoxychloropropane (molar ratio 1:2) are added under normal pressure, being added manufactured in the present embodiment immobilized has benzyl
The mesoporous molecular sieve catalyst (addition mole is the 0.005 of bisphenol-A) of triethyl ammonium chloride, etherificate is carried out at 110 DEG C and is opened
Ring reaction, reaction time are 1 hour, obtain chloropharin ether；40 DEG C or so are cooled to system, and catalyst therein is filtered out into recycling,
20wt% sodium hydrate aqueous solution (sodium hydroxide adds 2.2 times that mole is Bisphenol F) is added dropwise into system again, drips within 2 hours
Complete subsequent continuous insulation reaction 3 hours；System is stood into cooling layering, obtained lower layer's product is bisphenol F epoxy resin.Finally
The performance test results of product are listed in the table below in 1.
Embodiment 4
50g SBA-15 mesopore molecular sieve is immersed in 1000mL aminopropyl triethoxysilane coupling agent hydrolyzate (concentration
5%, with glacial acetic acid tune pH to 4.5 and stand 3 hours)；Drying is taken out after impregnating 2 hours；
By benzyltriethylammoinium chloride aqueous solution (concentration 1500g/L, 20mL) and mesoporous point of treated SBA-15
Sub- sieve (50g) mixing, by evaporation by moisture except doing, surplus materials is placed in 180 DEG C of heating 15min in ultrasonic-microwave device, obtains
To the immobilized SBA-15 mesoporous molecular sieve catalyst for having benzyltriethylammoinium chloride.
Phenol and epoxychloropropane (molar ratio 1:1.2) are added under normal pressure, being added manufactured in the present embodiment immobilized has benzyl
The mesoporous molecular sieve catalyst (addition mole is the 0.02 of phenol) of triethylammonium chloride, is etherified at 80-100 DEG C
Ring-opening reaction, reaction time are 3 hours, obtain chloropharin ether；70 DEG C or so are cooled to by mesoporous molecular sieving therein to system
It recycles out, 20wt% sodium hydrate aqueous solution (sodium hydroxide adds 1.2 times that mole is bisphenol-A) is added dropwise into system, 2 is small
When drip off subsequent continuous insulation reaction 3 hours；System is stood into cooling layering, obtained lower layer's product is epoxidized phenol.Most
The performance test results of final product are listed in the table below in 1.
Comparative example 1
Raw material, the technological parameter of phenolic hydroxyl group epoxidation preparation process is identical with embodiment 1, difference be only that directly with
Benzyltriethylammoinium chloride is catalyst.The performance test results of final product are listed in the table below in 1.
Comparative example 2
Raw material, the technological parameter of phenolic hydroxyl group epoxidation preparation process is identical with embodiment 1, and difference is only that benzyl not
Triethylammonium chloride and modified mesopore molecular sieve are compound in advance, but the two are directly added into reaction system, the two
Additional amount it is identical with the additional amount both in embodiment 1.The performance test results of final product are listed in the table below in 1.
Comparative example 3
Raw material, the technological parameter of phenolic hydroxyl group epoxidation preparation process is identical with embodiment 1, and difference is only that with immobilized
The multi-walled carbon nanotube for having benzyltriethylammoinium chloride is catalyst.
The preparation process of catalyst is as follows:
Benzyltriethylammoinium chloride aqueous solution (concentration 20g/L, 100mL) is mixed with multi-walled carbon nanotube (5g), is led to
For pervaporation by moisture except doing, surplus materials is placed in 120 DEG C of heating 20min in ultrasonic-microwave device, and obtaining load has three second of benzyl
The carbon nano-tube catalyst of ammonium chloride.
The performance test results of final product are listed in the table below in 1.
Comparative example 4
Bisphenol F and epoxychloropropane (molar ratio 1:2) are added under normal pressure, it is anti-that etherificate open loop is carried out at 100-110 DEG C
It answers, the reaction time is 1 hour, obtains chloropharin ether；40 DEG C or so are cooled to system, and 20wt% sodium hydroxide is added dropwise into system
Aqueous solution (sodium hydroxide adds 2.2 times that mole is Bisphenol F), drips off subsequent continuous insulation reaction for 2 hours 3 hours；By system
Cooling layering is stood, lower layer's product is collected.The performance test results of final product are listed in the table below in 1.
Table 1
Claims (9)
1. a kind of phenolic hydroxyl group epoxidation preparation process makees using phenolic hydroxy group compound and epoxychloropropane as raw material in catalyst
Under, etherified ring-opening reaction prepares chloropharin ether, then phenolic hydroxyl group epoxidation product is prepared through ring-closure reaction, and feature exists
In the catalyst is the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride；
The preparation step of the catalyst is as follows:
A, mesopore molecular sieve is immersed in silane coupling agent hydrolyzate, takes out drying after standing hydrolysis, obtains being modified mesoporous point
Son sieve；
B, the modified mesoporous molecular sieve that step A is obtained is mixed with benzyltriethylammoinium chloride aqueous solution, by evaporating moisture
Except dry, surplus materials be placed in ultrasonic-microwave device 120~180 DEG C of 20~40min of heating to get.
2. phenolic hydroxyl group epoxidation preparation process according to claim 1, which is characterized in that in step A, the mesoporous molecular
Screened from SBA-15 mesopore molecular sieve；
The weight ratio of the mesopore molecular sieve and silane coupling agent hydrolyzate is 1:2~200.
3. phenolic hydroxyl group epoxidation preparation process according to claim 1, which is characterized in that described silane coupled in step A
Agent hydrolyzate is mixed to get mixed liquor by the weight ratio of 1~5:100 by silane coupling agent and water, adjust the pH value of mixed liquor to
4.5~5.5, it obtains after standing；
The silane coupling agent is selected from aminopropyl trimethoxysilane or aminopropyl triethoxysilane.
4. phenolic hydroxyl group epoxidation preparation process according to claim 1, which is characterized in that in step B, three second of benzyl
The concentration of ammonium chloride aqueous solution is 10~1500g/L；
The weight of solute benzyltriethylammoinium chloride and modified mesoporous molecular sieve in the benzyltriethylammoinium chloride aqueous solution
Than for 1:0.05~5.
5. phenolic hydroxyl group epoxidation preparation process according to claim 1, which is characterized in that the benzyltriethylammoinium chloride
Weight ratio with modified mesoporous molecular sieve is 1:0.2~2.5.
6. phenolic hydroxyl group epoxidation preparation process described in any claim according to claim 1~5, which is characterized in that specific
Include:
1) phenolic hydroxy group compound and epoxychloropropane are added under normal pressure；
2) it is proportionally added into the immobilized mesopore molecular sieve for having benzyltriethylammoinium chloride and makees catalyst, carried out at 90~120 DEG C
It is etherified ring-opening reaction, the reaction time is 0.5~12h, obtains chloropharin ether；
3) system obtained to step 2) reaction is cooled to 40~80 DEG C, and the mesopore molecular sieve in system is taken out by filtering,
Alkali, 1~12h of insulation reaction is added into system again；
4) system that step 3) reaction obtains is stood into cooling layering, obtained organic phase product is that phenolic hydroxyl group epoxidation produces
Object.
7. phenolic hydroxyl group epoxidation preparation process according to claim 6, which is characterized in that in step 1)~step 3):
The molar ratio of the phenolic hydroxyl-compounds and epoxychloropropane is 1:0.8~3；
The molar ratio of the phenolic hydroxyl-compounds and catalyst is 1:0.005~0.1；
The molar ratio of the phenolic hydroxyl-compounds and alkali is 1:0.8~2.2.
8. phenolic hydroxyl group epoxidation preparation process according to claim 6, which is characterized in that in step 1), the hydroxyl containing phenol
Based compound is selected from least one of bisphenol-A, Bisphenol F, phenol, eugenol.
9. phenolic hydroxyl group epoxidation preparation process according to claim 6, which is characterized in that in step 3), the alkali is selected from
One of sodium hydroxide, hydrogen-oxygen agent, ammonium hydroxide are several, are added portionwise in the system in 0.5~5h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456287A (en) * | 2018-09-30 | 2019-03-12 | 江苏和和新材料股份有限公司 | A kind of preparation process of phenolic hydroxyl group epoxidation product |
| CN112409397A (en) * | 2020-11-12 | 2021-02-26 | 中国航空制造技术研究院 | Bio-based epoxy resin containing silicon phenylene structure, composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN102766113A (en) * | 2012-08-03 | 2012-11-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenated bisphenol A epoxy resin |
| CN103665321A (en) * | 2013-12-03 | 2014-03-26 | 山东圣泉化工股份有限公司 | Bisphenol A formaldehyde epoxy resin preparation method and copper-clad laminate |
| CN104193961A (en) * | 2014-09-17 | 2014-12-10 | 济南圣泉集团股份有限公司 | Preparation method for hydrogenated bisphenol A epoxy resin |
-
2018
- 2018-09-30 CN CN201811158726.2A patent/CN109456286A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613458A (en) * | 2008-06-25 | 2009-12-30 | 中国石油化工集团公司 | A kind of preparation method of bisphenol-A liquid epoxy resin |
| CN102766113A (en) * | 2012-08-03 | 2012-11-07 | 中国石油化工股份有限公司 | Preparation method of hydrogenated bisphenol A epoxy resin |
| CN103665321A (en) * | 2013-12-03 | 2014-03-26 | 山东圣泉化工股份有限公司 | Bisphenol A formaldehyde epoxy resin preparation method and copper-clad laminate |
| CN104193961A (en) * | 2014-09-17 | 2014-12-10 | 济南圣泉集团股份有限公司 | Preparation method for hydrogenated bisphenol A epoxy resin |
Non-Patent Citations (1)
| Title |
|---|
| CHENG LI等: "Biobased Epoxy Resin with Low Electrical Permissivity and Flame Retardancy: From Environmental Friendly High-Throughput Synthesis to Properties", 《ACS SUSTAINABLE CHEM. ENG.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456287A (en) * | 2018-09-30 | 2019-03-12 | 江苏和和新材料股份有限公司 | A kind of preparation process of phenolic hydroxyl group epoxidation product |
| CN112409397A (en) * | 2020-11-12 | 2021-02-26 | 中国航空制造技术研究院 | Bio-based epoxy resin containing silicon phenylene structure, composition and preparation method thereof |
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