CN103554432A - Method for producing bisphenol A novolac epoxy resin through BPA (bisphenol A) heavy ends - Google Patents
Method for producing bisphenol A novolac epoxy resin through BPA (bisphenol A) heavy ends Download PDFInfo
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- CN103554432A CN103554432A CN201310530655.5A CN201310530655A CN103554432A CN 103554432 A CN103554432 A CN 103554432A CN 201310530655 A CN201310530655 A CN 201310530655A CN 103554432 A CN103554432 A CN 103554432A
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Abstract
The invention discloses a method for producing bisphenol A novolac epoxy resin through BPA (bisphenol A) heavy ends. The method comprises the following steps: with BPA heavy ends, formaldehyde and n-butanol as raw materials, firstly reacting to prepare bisphenol A phenolic resin; and with the bisphenol A phenolic resin and epoxy chloropropane as raw materials, reacting to prepare the bisphenol A novolac epoxy resin. The bisphenol A novolac epoxy resin produced by the method disclosed by the invention is epoxy resin with upgraded high heat resistance and is mainly applied on PCB (Printed Circuit Board) laminated boards with high TG, wind-power composite materials, as well as photosensitive solder resist ink, thermosetting solder resist ink, such heat-resistant materials as heat-resistant vinylite and the like, molding materials, coating, adhesives, etc.
Description
Technical field
The present invention relates to a kind of method of producing bisphenol-A phenolic epoxy resin.
Background technology
The inexorable trend of the unleaded development of global electronic industry, by having pulled fast unleaded the wait demand of associated materials and the enhancement of series product, adjusts the product mix and becomes the demand that copper-clad plate industry adapts to market.Bisphenol A phenolic resin and bisphenol-A phenolic epoxy resin, as the starting material of manufacturing halogen-free copper-clad plate, have broad application prospects.The resource that our factory has a large amount of BPA heavy endss needs digestion, and with BPA heavy ends, producing bisphenol-A phenolic epoxy resin just becomes a kind of possibility.
Summary of the invention:
The object of the present invention is to provide a kind of synthetic method of producing bisphenol-A phenolic epoxy resin with BPA heavy ends.
Technical solution of the present invention is:
BPA heavy ends is produced a method for bisphenol-A phenolic epoxy resin, it is characterized in that: comprise the following steps:
(1) take BPA heavy ends (BPA Heavy Ends), formaldehyde and butanols is raw material, through reaction, first makes bisphenol A phenolic resin;
(2) take bisphenol A phenolic resin, epoxy chloropropane is raw material, through reaction, makes bisphenol-A phenolic epoxy resin.
In step (1), the consumption mol ratio of BPA heavy ends, butanols and formaldehyde is 1.0:1.6～1.9:0.9～1.3; First under oxalic acid, react 2～3 hours, after under hydrochloric acid, react 2～4 hours, then with sodium hydroxide, neutralize neutrality, excessive butanols and the BPA heavy ends of reaction Bi Huishou makes bisphenol A phenolic resin; Above-mentioned temperature of reaction is 98～102 ℃.
In step (2), the consumption mol ratio of bisphenol A phenolic resin, epoxy chloropropane is 1.0:20～30, under basic catalyst reaction, reacts 4～7 hours, and vacuum tightness is-0.08～0.09Mpa, 50～65 ℃ of temperature of reaction; The excessive epoxy chloropropane of reaction Bi Huishou, adds toluene butanols mixed solvent, 50～65 ℃ of temperature, drips diluted alkaline reaction 4～7 hours, obtains rough bisphenol-A phenolic epoxy resin; Add again toluene butanols mixed solvent to dilute rough bisphenol-A phenolic epoxy resin, finally slough mixed solvent and obtain bisphenol-A phenolic epoxy resin finished product.
Described mixed solvent is the mixed solution of toluene and butanols, and weight ratio toluene: butanols=4:1.
The bisphenol-A phenolic epoxy resin that the present invention produces is a kind of epoxy resin of high heat resistance upgrading, is mainly used in the PCB veneer sheet of high TG, and wind-powered electricity generation matrix material, also can be used for photosensitive solder resist ink, thermofixation welding resistance ink; The heat-stable materials such as heat-resisting Vinylite, formed material, coating, caking agent etc.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment 1:
Take BPA heavy ends 263g, formaldehyde 105g, butanols 158g and oxalic acid 0.6g join in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heat to 80～90 ℃ and stop heating, reflux 2～3 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, add 1.8g hydrochloric acid to heat to 80～90 ℃ and stop heating, reflux 2～4 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, with sodium hydroxide, neutralize pH approximately 6.5～7, open heating under vacuum and reclaim excessive butanols, when vacuum tightness is-0.09～0.098Mpa temperature to 165～175 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol A phenolic resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 1 |
| Outward appearance | Brown transparent solid |
| Softening temperature ℃ | 126 |
| Fugitive constituent % | 1.2 |
Take bisphenol A phenolic resin 300g, epoxy chloropropane 1800g joins in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heats to 105～110 ℃ and stops heating, automatic heating to 113～120 ℃ etherificate 4 hours, cooling tune vacuum tightness exists
The lower reaction of 50～65 ℃ of dropping alkali of-0.08～0.09Mpa and temperature (10% sodium hydroxide 3ml) 4～7 hours.The excessive epoxy chloropropane of reaction Bi Huishou, add toluene: butanols=4:1(weight ratio) mixed solvent is 100 grams, 50～65 ℃ of temperature, drip diluted alkaline (sodium hydroxide that concentration is 0.09mol/L) 3ml reaction 4～5 hours, obtain rough bisphenol-A phenolic epoxy resin.Add again toluene: butanols=4:1(weight ratio) mixed solvent dilutes rough bisphenol-A phenolic epoxy resin, open heating under vacuum and reclaim mixed solvent, when vacuum tightness is-0.09～0.098Mpa temperature to 160～165 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol-A phenolic epoxy resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 1 |
| Outward appearance | Faint yellow transparent solid |
| Softening temperature ℃ | 85．5 |
| Epoxy equivalent (weight) g/mol | 239.6 |
| Hydrolysis chlorine % | 0.1354 |
| Fugitive constituent % | 0.59 |
Embodiment 2:
Take BPA heavy ends 270g, formaldehyde 105g, butanols 158g and oxalic acid 0.6g join in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heat to 80～90 ℃ and stop heating, reflux 2～3 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, add 1.8g hydrochloric acid to heat to 80～90 ℃ and stop heating, reflux 2～4 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, with sodium hydroxide, neutralize pH approximately 6.5～7, open heating under vacuum and reclaim excessive butanols, when vacuum tightness is-0.09～0.098Mpa temperature to 165～175 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol A phenolic resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 2 |
| Outward appearance | Brown transparent solid |
| Softening temperature ℃ | 108 |
| Fugitive constituent % | 0.9 |
Taking bisphenol A phenolic resin 300g, epoxy chloropropane 1600g and benzyl 2.1g joins in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heats to 105～110 ℃ and stops heating, automatic heating to 113～120 ℃ etherificate 4 hours, cooling tune vacuum tightness exists
The lower reaction of 50～65 ℃ of dropping alkali of-0.08～0.09Mpa and temperature (10% sodium hydroxide 3ml) 4～7 hours.The excessive epoxy chloropropane of reaction Bi Huishou, add toluene: butanols=4:1(weight ratio) mixed solvent is 100 grams, 50～65 ℃ of temperature, drip diluted alkaline (sodium hydroxide that concentration is 0.09mol/L) 3ml reaction 4～5 hours, obtain rough bisphenol-A phenolic epoxy resin.Add again toluene: butanols=4:1(weight ratio) mixed solvent dilutes rough bisphenol-A phenolic epoxy resin, open heating under vacuum and reclaim mixed solvent, when vacuum tightness is-0.09～0.098Mpa temperature to 160～165 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol-A phenolic epoxy resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 2 |
| Outward appearance | Faint yellow transparent solid |
| Softening temperature ℃ | 67.6 |
| Epoxy equivalent (weight) g/mol | 226.2 |
| Hydrolysis chlorine % | 0.117 |
| Fugitive constituent % | 0.45 |
Embodiment 3:
Take BPA heavy ends 280g, formaldehyde 105g, butanols 158g and oxalic acid 0.6g join in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heat to 80～90 ℃ and stop heating, reflux 2～3 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, add 1.8g hydrochloric acid to heat to 80～90 ℃ and stop heating, reflux 2～4 hours in automatic heating to 98～102 ℃, be cooled to below 90 ℃, with sodium hydroxide, neutralize pH approximately 6.5～7, open heating under vacuum and reclaim excessive butanols, when vacuum tightness is-0.09～0.098Mpa temperature to 165～175 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol A phenolic resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 3 |
| Outward appearance | Brown transparent solid |
| Softening temperature ℃ | 105 |
| Fugitive constituent % | 1.0 |
Taking bisphenol A phenolic resin 300g, epoxy chloropropane 1500g and benzyltriethylammoinium chloride 2.1g joins in there-necked flask, open and stir, rotating speed is controlled at 200 ± 10 revs/min, heat to 105～110 ℃ and stop heating, automatic heating to 113～120 ℃ etherificate 4 hours, cooling tune vacuum tightness exists
The lower reaction of 50～65 ℃ of dropping alkali of-0.08～0.09Mpa and temperature (10% sodium hydroxide 3ml) 4～7 hours.The excessive epoxy chloropropane of reaction Bi Huishou, add toluene: butanols=4:1(weight ratio) mixed solvent is 100 grams, 50～65 ℃ of temperature, drip diluted alkaline (sodium hydroxide that concentration is 0.09mol/L) 3ml reaction 4～5 hours, obtain rough bisphenol-A phenolic epoxy resin.Add again toluene: butanols=3:1(weight ratio) mixed solvent dilutes rough bisphenol-A phenolic epoxy resin, open heating under vacuum and reclaim mixed solvent, when vacuum tightness is-0.09～0.098Mpa temperature to 160～165 ℃, reclaims and finish, remove vacuum and take off reaction unit, the bisphenol-A phenolic epoxy resin making is poured in bottle and weighed.Detection data see the following form:
| Test item | Embodiment 3 |
| Outward appearance | Faint yellow transparent solid |
| Softening temperature ℃ | 62.5 |
| Epoxy equivalent (weight) g/mol | 227.6 |
| Hydrolysis chlorine % | 0.098 |
| Fugitive constituent % | 0.8 |
Visible, excellent properties of the present invention.
Claims (4)
1. BPA heavy ends is produced a method for bisphenol-A phenolic epoxy resin, it is characterized in that: comprise the following steps:
(1) take BPA heavy ends, formaldehyde and butanols as raw material, through reaction, first make bisphenol A phenolic resin;
(2) take bisphenol A phenolic resin, epoxy chloropropane is raw material, through reaction, makes bisphenol-A phenolic epoxy resin.
2. BPA heavy ends according to claim 1 is produced the method for bisphenol-A phenolic epoxy resin, it is characterized in that: in step (1), the consumption mol ratio of BPA heavy ends, butanols and formaldehyde is 1.0:1.6～1.9:0.9～1.3; First under oxalic acid, react 2～3 hours, after under hydrochloric acid, react 2～4 hours, then with sodium hydroxide, neutralize neutrality, excessive butanols and the BPA heavy ends of reaction Bi Huishou makes bisphenol A phenolic resin; Above-mentioned temperature of reaction is 98～102 ℃.
3. BPA heavy ends according to claim 1 is produced the method for bisphenol-A phenolic epoxy resin, it is characterized in that: in step (2), the consumption mol ratio of bisphenol A phenolic resin, epoxy chloropropane is 1.0:20～30, under basic catalyst reaction, react 4～7 hours, vacuum tightness is-0.08～0.09Mpa, 50～65 ℃ of temperature of reaction; The excessive epoxy chloropropane of reaction Bi Huishou, adds toluene butanols mixed solvent, 50～65 ℃ of temperature, drips diluted alkaline reaction 4～7 hours, obtains rough bisphenol-A phenolic epoxy resin; Add again toluene butanols mixed solvent to dilute rough bisphenol-A phenolic epoxy resin, finally slough mixed solvent and obtain bisphenol-A phenolic epoxy resin finished product.
4. BPA heavy ends according to claim 3 is produced the method for bisphenol-A phenolic epoxy resin, it is characterized in that: described mixed solvent is the mixed solution of toluene and butanols, and weight ratio toluene: butanols=4:1.
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| CN201310530655.5A CN103554432B (en) | 2013-11-01 | 2013-11-01 | Method for producing bisphenol A novolac epoxy resin through BPA (bisphenol A) heavy ends |
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| CN103554432A true CN103554432A (en) | 2014-02-05 |
| CN103554432B CN103554432B (en) | 2015-07-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109719967A (en) * | 2018-12-29 | 2019-05-07 | 江苏联鑫电子工业有限公司 | High Tg lead-free copper-clad plate of high tenacity and preparation method thereof |
| CN112979922A (en) * | 2021-03-09 | 2021-06-18 | 福建准信新材料有限公司 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195676A (en) * | 2007-12-27 | 2008-06-11 | 东莞理工学院 | Phosphor A containing novolac epoxy and method for producing the same |
| CN102167659A (en) * | 2011-03-25 | 2011-08-31 | 南通星辰合成材料有限公司 | Method for realizing vacuum rectification and vacuum evaporation of bisphenol A by liquid ring vacuum pump |
-
2013
- 2013-11-01 CN CN201310530655.5A patent/CN103554432B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195676A (en) * | 2007-12-27 | 2008-06-11 | 东莞理工学院 | Phosphor A containing novolac epoxy and method for producing the same |
| CN102167659A (en) * | 2011-03-25 | 2011-08-31 | 南通星辰合成材料有限公司 | Method for realizing vacuum rectification and vacuum evaporation of bisphenol A by liquid ring vacuum pump |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109719967A (en) * | 2018-12-29 | 2019-05-07 | 江苏联鑫电子工业有限公司 | High Tg lead-free copper-clad plate of high tenacity and preparation method thereof |
| CN109719967B (en) * | 2018-12-29 | 2021-05-04 | 江苏联鑫电子工业有限公司 | High-toughness high-Tg lead-free copper-clad plate and preparation method thereof |
| CN112979922A (en) * | 2021-03-09 | 2021-06-18 | 福建准信新材料有限公司 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
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| CN103554432B (en) | 2015-07-22 |
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