CN105085868A - Method for synthesizing phenolic ketone epoxy resin through negative pressure water separation - Google Patents
Method for synthesizing phenolic ketone epoxy resin through negative pressure water separation Download PDFInfo
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- CN105085868A CN105085868A CN201510616668.3A CN201510616668A CN105085868A CN 105085868 A CN105085868 A CN 105085868A CN 201510616668 A CN201510616668 A CN 201510616668A CN 105085868 A CN105085868 A CN 105085868A
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- negative pressure
- phenolic ketone
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- dihydroxyphenyl propane
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Abstract
The invention discloses a method for synthesizing phenolic ketone epoxy resin through negative pressure water separation. Phenolic ketone resin and bisphenol A are taken as raw materials and dissolved in epoxy chloropropane, a phase transfer catalyst is added, the temperature is increased to 60-120 DEG C, after an etherification reaction is carried out for 1-10 hours, negative pressure water separation is carried out at the temperature of 10-90 DEG C under the vacuum degree of 0.001-0.05 MPa, alkali is dripped, alkali dripping is finished in 1-10 hours, and a closed-loop reaction is maintained for 0.5-4 hours; the epoxy chloropropane is recycled, vacuum is removed, a solvent is added to carry out alkali supplementation refining, lower layer salt and alkali are separated and neutralized to the pH of 6-7 through an acid addition agent, the solvent is removed, and the product is obtained after filtering. Due to the fact that the negative pressure water separation technology is used, side reactions are few in the closed loop, the epoxide equivalent of the product is low and can reach the range of 200-250 g/mol; meanwhile, the aged resin is little in the refining process and only accounts for 0.02-0.06% of the total weight of the product, liquid separation is easy, and industrialization production is facilitated.
Description
Technical field
The present invention relates to a kind of method of synthesizing phenolic ketone epoxy resin.
Background technology
Phenolic ketone resin is commonly called as dihydroxyphenyl propane residue, namely during industrial production dihydroxyphenyl propane, carries out catalytic pyrolysis to dihydroxyphenyl propane mother liquor, reclaims the dihydroxyphenyl propane cracking bottom product after phenol and isopropenyl phenol.Dihydroxyphenyl propane manufacturer nearly all at present all using it as solid waste incineration, not only waste energy, also can produce the environmental issue of dioxin.
Dihydroxyphenyl propane residue is fully utilized, not only solves environmental issue, can also economic benefit be produced.
Also there is both at home and abroad research in recent years by dihydroxyphenyl propane residue for the synthesis of epoxy resin, due to the processing method imperfection of synthesis, the problem of two aspects can be brought: one is that the epoxy resin equivalent that synthesizes is higher, general epoxy equivalent (weight) is in 260 ~ 310g/mol scope, such epoxy equivalent (weight) scope, limits its application at the numerous areas such as protective system, sizing agent; Two aged resin when being refining are many, and general aged resin amount accounts for 3% ~ 5% scope of product gross weight, and separatory difficulty, is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of epoxy resin synthesized to have epoxy equivalent (weight) low, the negative pressure that time refining, aged resin is few divides hydration to become the method for phenolic ketone epoxy resin.
Technical solution of the present invention is:
A kind of negative pressure divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: with phenolic ketone resin and dihydroxyphenyl propane for raw material, be dissolved in epoxy chloropropane, add phase-transfer catalyst, be warming up to 60 ~ 120 DEG C, etherification reaction is after 1 ~ 10 hour, 10 ~ 90 DEG C, carry out negative pressure under vacuum tightness 0.001 ~ 0.05MPa and divide water droplet to add alkali, within 1 ~ 10 hour, drip alkali complete, ring-closure reaction keeps 0.5 ~ 4 hour; Reclaim epoxy chloropropane, shed vacuum, add solvent and carry out adding soda finishing, separate lower floor saline and alkaline, use acid additive to be neutralized to pH=6 ~ 7, desolventizing, filter to obtain product.
Raw material phenolic ketone resin is the byproduct residue of dihydroxyphenyl propane, namely during industrial production dihydroxyphenyl propane, carries out catalytic pyrolysis to dihydroxyphenyl propane mother liquor, reclaims the dihydroxyphenyl propane cracking bottom product after phenol and isopropenyl phenol; Phenolic ketone weight resin is 10% ~ 100% of the weight of dihydroxyphenyl propane.The weight of epoxy chloropropane is 2 ~ 20 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
Phase-transfer catalyst is one or more in TEBA, tetramethyl-ammonia chloride, poly(oxyethylene glycol) 400; Phase-transfer catalyst weight is 0.001% ~ 5% of dihydroxyphenyl propane and phenolic ketone weight resin summation.
Solvent is one or more in benzene,toluene,xylene, butylacetate, methyl iso-butyl ketone (MIBK), hexanaphthene; The weight of solvent is 0.5 ~ 3 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
Described alkali is the NaOH aqueous solution, and concentration is 5% ~ 50%, and the weight of alkali is 0.2 ~ 2.0 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
Acid additive used is SODIUM PHOSPHATE, MONOBASIC, oxalic acid or phosphoric acid.
Negative pressure divides water droplet to add alkali use phase splitter, and lower floor's epoxy chloropropane is back to reactor, and upper water is collected in phase splitter; Negative pressure divides the condition of water: temperature 10 ~ 90 DEG C, vacuum tightness 0.001 ~ 0.05MPa.
The present invention divides water conservancy project skill owing to using negative pressure, and during closed loop, side reaction is few, and product epoxy equivalent (weight) is low, and product epoxy equivalent (weight) can reach 200 ~ 250g/mol scope; When refining, aged resin is few simultaneously, and aged resin amount only accounts for 0.02% ~ 0.06% scope of product gross weight, and separatory is easy, is conducive to suitability for industrialized production.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment 1: in the four-hole bottle with stirring, thermometer, prolong, adds 2000g epoxy chloropropane, adds 400g dihydroxyphenyl propane, 100g phenolic ketone resin and 5.0g TEBA, is warming up to 90 DEG C, then at 90 ~ 100 DEG C, maintains 6 hours.Utilize the phase splitter of customization, 45 ~ 50 DEG C, carry out negative pressure under vacuum tightness 0.002MPa and divide water droplet to add alkali (lower floor's epoxy chloropropane is back to reactor, and upper water is collected in phase splitter), the 500g48%NaOH aqueous solution, within 2 hours, dropwise, then at 50 ~ 55 DEG C, maintain 1.5 hours; Rising temperature reclamation epoxy chloropropane, sheds vacuum, adds 450g toluene and dissolves, add the 150g10%NaOH aqueous solution, be warming up to 80 DEG C, maintain 1.5 hours, leave standstill, separate lower floor saline and alkaline, add 1.5g phosphoric acid, feed liquid is neutralized to PH6 ~ 7.Desolventizing also filters to obtain product.Aged resin amount: 0.026%.
Product index is as follows:
Epoxy equivalent (weight): 203.6g/mol, softening temperature: 11 DEG C.
Embodiment 2: in the four-hole bottle with stirring, thermometer, prolong, adds 1500g epoxy chloropropane, adds 250g dihydroxyphenyl propane, 250g phenolic ketone resin and 20.0g poly(oxyethylene glycol) 400, is warming up to 100 DEG C, then at 100 ~ 110 DEG C, maintains 4 hours.Utilize the phase splitter of customization, 50 ~ 55 DEG C, carry out negative pressure under vacuum tightness 0.003MPa and divide water droplet to add alkali (lower floor's epoxy chloropropane is back to reactor, and upper water is collected in phase splitter), the 400g48%NaOH aqueous solution, within 3 hours, dropwise, then at 55 ~ 60 DEG C, maintain 2 hours; Rising temperature reclamation epoxy chloropropane, sheds vacuum, adds 360g toluene and dissolves, add the 120g15%NaOH aqueous solution, be warming up to temperature 85 DEG C, maintain 2 hours, leave standstill, separate lower floor saline and alkaline, add 2.0g SODIUM PHOSPHATE, MONOBASIC, feed liquid is neutralized to PH6 ~ 7.Desolventizing also filters to obtain product.Aged resin amount: 0.041%.
Product index is as follows:
Epoxy equivalent (weight): 231.0g/mol, softening temperature: 22 DEG C.
Embodiment 3: in the four-hole bottle with stirring, thermometer, prolong, adds 1800g epoxy chloropropane, adds 300g dihydroxyphenyl propane, 200g phenolic ketone resin and 2.0g tetramethyl-ammonia chloride, is warming up to 80 DEG C, then at 80 ~ 90 DEG C, maintains 8 hours.Utilize the phase splitter of customization, 65 ~ 70 DEG C, carry out negative pressure under vacuum tightness 0.004MPa and divide water droplet to add alkali (lower floor's epoxy chloropropane is back to reactor, and upper water is collected in phase splitter), the 450g48%NaOH aqueous solution, within 2 hours, dropwise, then at 70 ~ 75 DEG C, maintain 1.0 hours; Rising temperature reclamation epoxy chloropropane, sheds vacuum, adds 600g toluene and dissolves, add the 100g20%NaOH aqueous solution, be warming up to 75 DEG C, maintain 2.5 hours, leave standstill, separate lower floor saline and alkaline, add 2.5g oxalic acid, feed liquid is neutralized to PH6 ~ 7.Desolventizing also filters to obtain product.Aged resin amount: 0.032%.
Product index is as follows:
Epoxy equivalent (weight): 215.6g/mol, softening temperature: 17 DEG C.
Claims (7)
1. a negative pressure divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: with phenolic ketone resin and dihydroxyphenyl propane for raw material, be dissolved in epoxy chloropropane, add phase-transfer catalyst, be warming up to 60 ~ 120 DEG C, etherification reaction is after 1 ~ 10 hour, 10 ~ 90 DEG C, carry out negative pressure under vacuum tightness 0.001 ~ 0.05MPa and divide water droplet to add alkali, within 1 ~ 10 hour, drip alkali complete, ring-closure reaction keeps 0.5 ~ 4 hour; Reclaim epoxy chloropropane, shed vacuum, add solvent and carry out adding soda finishing, separate lower floor saline and alkaline, use acid additive to be neutralized to pH=6 ~ 7, desolventizing, filter to obtain product.
2. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin; it is characterized in that: raw material phenolic ketone resin is the byproduct residue of dihydroxyphenyl propane; namely during industrial production dihydroxyphenyl propane; catalytic pyrolysis is carried out to dihydroxyphenyl propane mother liquor, reclaims the dihydroxyphenyl propane cracking bottom product after phenol and isopropenyl phenol; Phenolic ketone weight resin is 10% ~ 100% of the weight of dihydroxyphenyl propane; The weight of epoxy chloropropane is 2 ~ 20 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
3. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: phase-transfer catalyst is one or more in TEBA, tetramethyl-ammonia chloride, poly(oxyethylene glycol) 400; Phase-transfer catalyst weight is 0.001% ~ 5% of dihydroxyphenyl propane and phenolic ketone weight resin summation.
4. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: solvent is one or more in benzene,toluene,xylene, butylacetate, methyl iso-butyl ketone (MIBK), hexanaphthene; The weight of solvent is 0.5 ~ 3 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
5. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: described alkali is the NaOH aqueous solution, and concentration is 5% ~ 50%, and the weight of alkali is 0.2 ~ 2.0 times of dihydroxyphenyl propane and phenolic ketone weight resin summation.
6. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: acid additive used is SODIUM PHOSPHATE, MONOBASIC, oxalic acid or phosphoric acid.
7. negative pressure according to claim 1 divides hydration to become the method for phenolic ketone epoxy resin, it is characterized in that: negative pressure divides water droplet to add alkali use phase splitter, and lower floor's epoxy chloropropane is back to reactor, and upper water is collected in phase splitter; Negative pressure divides the condition of water: temperature 10 ~ 90 DEG C, vacuum tightness 0.001 ~ 0.05MPa.
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| CN201510616668.3A CN105085868A (en) | 2015-09-25 | 2015-09-25 | Method for synthesizing phenolic ketone epoxy resin through negative pressure water separation |
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| CN201510616668.3A CN105085868A (en) | 2015-09-25 | 2015-09-25 | Method for synthesizing phenolic ketone epoxy resin through negative pressure water separation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898733A (en) * | 2019-12-03 | 2021-06-04 | 南通星辰合成材料有限公司 | Water-based polyphenol epoxy emulsion and preparation method thereof |
| CN116041667A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for synthesizing bisphenol A type liquid epoxy resin by catalysis of composite catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935767A (en) * | 2006-09-26 | 2007-03-28 | 蓝星化工新材料股份有限公司无锡树脂厂 | Method for preparing diphenolic propane diglycidol ether |
| CN102229530A (en) * | 2011-05-12 | 2011-11-02 | 山东中氟化工科技有限公司 | Clean production method for perfluoroalkyl acrylate |
| CN102276415A (en) * | 2011-05-16 | 2011-12-14 | 山东中氟化工科技有限公司 | Method for improving fluorine-containing alkyl alcohol yield |
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2015
- 2015-09-25 CN CN201510616668.3A patent/CN105085868A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935767A (en) * | 2006-09-26 | 2007-03-28 | 蓝星化工新材料股份有限公司无锡树脂厂 | Method for preparing diphenolic propane diglycidol ether |
| CN102229530A (en) * | 2011-05-12 | 2011-11-02 | 山东中氟化工科技有限公司 | Clean production method for perfluoroalkyl acrylate |
| CN102276415A (en) * | 2011-05-16 | 2011-12-14 | 山东中氟化工科技有限公司 | Method for improving fluorine-containing alkyl alcohol yield |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898733A (en) * | 2019-12-03 | 2021-06-04 | 南通星辰合成材料有限公司 | Water-based polyphenol epoxy emulsion and preparation method thereof |
| CN112898733B (en) * | 2019-12-03 | 2023-08-11 | 南通星辰合成材料有限公司 | Water-based polyphenol type epoxy emulsion and preparation method thereof |
| CN116041667A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for synthesizing bisphenol A type liquid epoxy resin by catalysis of composite catalyst |
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