CN1279078C - Epoxy resin of containing fluorine, ramification, preparation method and application - Google Patents
Epoxy resin of containing fluorine, ramification, preparation method and application Download PDFInfo
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- CN1279078C CN1279078C CNB2003101194114A CN200310119411A CN1279078C CN 1279078 C CN1279078 C CN 1279078C CN B2003101194114 A CNB2003101194114 A CN B2003101194114A CN 200310119411 A CN200310119411 A CN 200310119411A CN 1279078 C CN1279078 C CN 1279078C
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Abstract
The present invention relates to fluoric epoxy resin, a derivative thereof, a preparation method thereof and an application thereof. The epoxy resin replaces alpha, alpha, alpha-acetylbenzotrifluoride to carry out a condensation reaction with phenol under acid catalysis to generate a replaced diphenol compound; the diphenol compound reacts with epichlorohydrin under acid-base catalysis to obtain a fluoric epoxide and a derivative thereof; the fluoric epoxide carries out a solidification reaction with organic estolide or amine to obtain fluoric epoxy resin. After solidification, the epoxy resin has superior electrical property and low water absorption rate.
Description
Technical field
The present invention relates to kind of fluorine-containing epoxy resin and derivative.
The invention still further relates to the preparation method of above-mentioned fluorine-containing epoxy resin and derivative.
The invention still further relates to the application of above-mentioned fluorine-containing epoxy fat and derivative.
Background technology
High-performance epoxy resin as the important microelectronics Packaging polymer materials of a class, has huge using value in microelectronics industry.Along with the fast development of unicircuit towards little, light, thin direction, the form of microelectronics Packaging also from traditional dual-in-line type (DIP) and four limits lead-in wire platypelloid type (QFP), develops towards flip chip ball grid array (FC-PBGA), chip scale encapsulation (CSP) and multi-chip module directions such as (MCM).Advanced microelectronic packaging technology is more and more higher to the performance requriements that Resins, epoxy proposes, and mainly comprises: 1) high heat-resistant stability energy; 2) high mechanical strength, low modulus; 3) low water-intake rate etc. low specific inductivity and dielectric loss, and 4).Specific inductivity that packaged material is low and dielectric loss can obviously reduce the loss of signal transmission in the unicircuit.Low water-intake rate can obviously reduce the influence of moisture content to dielectric material stability.Therefore, people are in the specific inductivity and the loss that reduce Resins, epoxy in recent years, and systematic research work has been carried out in aspects such as reduction water-intake rate.EP Patent0293889 discloses a series of preparation methods that contain the fluorine-containing epoxy resin of hexafluoro sec.-propyl; People such as Patrick [Patrick E.Cassidy; Tejraj M.Aminabhavi, et al Eur.Polym.J.1995,31,353-361] reported a series of based on 2-phenyl-1,1,1,3,3, the serial fluorine-containing epoxy resin of 3-HFC-236fa-2-phenol.
People such as Maruno [Maruno, T.; Nakamura, K.; Murata, N.Macromolecules 1996,29,2006-2010] reported a kind of novel fluorine Resins, epoxy that contains alicyclic structure; Find that these fluorine-containing Resins, epoxy can obviously reduce the specific inductivity and the dielectric loss of material.
Summary of the invention
The object of the invention is to disclose a kind of fluorine-containing epoxy resin and derivative thereof.
Another object of the present invention is to disclose the preparation method of above-mentioned Resins, epoxy and derivative.
Fluorine-containing epoxy resin disclosed by the invention and derivative have definite molecular weight, and oxirane value is consistent with theoretical value; Solidifying agent such as this epoxy compounds and derivative thereof and acid anhydrides or organic amine have lower specific inductivity, dielectric loss and lower water-intake rate through the cured resin that curing reaction forms.Therefore, having important use in high-technology fields such as microelectronics Packaging is worth.
Fluorine-containing epoxy resin of the present invention has chemical structure as follows:
Preparation process of the present invention is undertaken by following chemical synthesis route
1) with the α that replaces, α, α-trifluoromethyl acetophenone obtain fluorine-containing substituent diphenol with phenol generation condensation reaction under the catalysis of Lewis acid and HCl;
2) resulting two phenolic compound and epoxy chloropropane are reacted fluorine-containing epoxy of generation and derivative thereof under base catalysis;
3) with fluorine-containing epoxy compounds and derivative thereof, solidifying agent, curing catalyst, thinner uniform mixing by a certain percentage;
4) said mixture is poured in the mould be heating and curing, condition of cure is: 80-150 ℃ solidified 1-2 hour, 150-250 ℃ after fixing 1-3 hour;
5) cured article is slowly cooled to room temperature, peel off and obtain uniform and smooth, the no bubble in surface, flawless cured resin.
The present invention's used Lewis acid in preparation process comprises: aluminum trichloride (anhydrous), Magnesium Chloride Anhydrous, Zinc Chloride Anhydrous etc.
The present invention's used solidifying agent in preparation process comprises organic amine curing agent and organic acid anhydride solidifying agent two classes.Organic amine curing agent comprises 4,4 '-diaminodiphenyl oxide (ODA), 4,4 '-diaminodiphenylmethane (DDM), 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 4,4 '-two (2,2 '-bis trifluoromethyl-4-amido phenoxy group) benzene (6FAPB), 3,3 ', 5,5 '-tetramethyl--4, the mixture of 4 '-diaminodiphenylmethane (TMDA) and any ratio thereof.The organic acid anhydride solidifying agent comprises the mixture of 4-methyl hexahydrophthalic anhydride (HMPA), 4-methyl tetrahydro phthalic anhydride (MeTHPA), HHPA (HHPA), tetrahydrophthalic anhydride (THPA) and any ratio thereof.
The present invention's used curing catalyst in preparation process comprises: 2,4,6-three (dimethylamine methyl) phenol (DMP-30), 1, the mixture of 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), 2-ethyl-4-methylimidazole, glyoxal ethyline, trolamine, 1-cyanoethyl-2-ethyl-4-methylimidazole and any ratio thereof.
The present invention's used thinner in preparation process comprises: the mixture of phenyl glycidyl ether (PGE), cresylglycidylether (CGE), n-butyl glycidyl ether (BGE), diglycidylaniline (DGA), glycerol triglycidyl ether (GGE) and any ratio thereof.
Fluorine-containing epoxy resin disclosed by the invention and derivative thereof have good heat-resistant stability, mechanical property, low specific inductivity and dielectric loss and lower water-intake rate; These excellent comprehensive performances make it to have the potential significant application value in microelectronics Packaging, and typically used comprises that solids epoxy plastic cement, liquid epoxy are sealed the end filler of material, epoxy conductive silver slurry, heat conduction slurry, upside-down mounting welding core etc.
Embodiment
Following embodiment 1-5 is the preparation method of fluorine-containing epoxy compounds and derivative thereof; Embodiment 6-11 is the solidification process of fluorine-containing epoxy compounds and derivative thereof.
Example 11, two (4-the hydroxy phenyl)-1-phenyl-2,2 of 1-, the preparation of 2-Halothane: induction stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding α, α, 50 parts of α-trifluoromethyl acetophenones, 5 parts of 300 parts of phenol and zinc chloride, reaction mixture is heated to 100 ℃, feeds HCl gas simultaneously, reacts 2-3 hour, obtain reddish-brown liquid, pressure reducing and steaming phenol, product gets white 1 with ethyl alcohol recrystallization, two (4-hydroxy phenyl)-1 phenyl-2,2 of 1-, 2-Halothane solid.
4,4 '-two (2,3-epoxypropyl phenyl)-and 1-phenyl-2,2, the preparation of 2-Halothane: with 40 part 1, two (4-the hydroxy phenyl)-1-(3-trifluoromethyl)-2 of 1-, 2,2-Halothane and 800 parts of epoxy chloropropane, 80 parts of 48%NaOH solution add in the there-necked flask, react three hours down at 65 ℃, product extracts with methyl iso-butyl ketone (MIBK), and washes with water.Organic phase boils off whole solvents, gets colourless 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,2-Halothane thick liquid.
Example 21, two (4-the hydroxy phenyl)-1-(3-trifluoromethyl)-2 of 1-, 2, the preparation of 2-Halothane: induction stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding 3-trifluoromethyl-α, α, 60 parts of α-trifluoromethyl acetophenones, 5 parts in 360 parts of phenol and aluminum chloride, reaction mixture is heated to 100 ℃, feed HCl gas simultaneously, reacted 2-3 hour, and obtained reddish-brown liquid, pressure reducing and steaming phenol, product gets white 1 with ethyl alcohol recrystallization, two (4-the hydroxy phenyl)-1-(3-trifluoromethyl)-2,2 of 1-, 2-Halothane solid.
4,4 '-two (2,3-epoxypropyl phenyl)-and 1-(3-trifluoromethyl)-2,2, the preparation of 2-Halothane: with 30 part 1, two (4-the hydroxy phenyl)-1-(3-trifluoromethyl)-2 of 1-, 2,2-Halothane and 600 parts of epoxy chloropropane, 60 parts of 48%NaOH solution add in the there-necked flask, react three hours down at 65 ℃, product extracts with methyl iso-butyl ketone (MIBK), and washes with water.Organic phase boils off whole solvents, gets colourless 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,2-Halothane thick liquid.
Example 31,1 '-two (4-hydroxy phenyl)-1-(4-trifluoromethyl)-2,2, the preparation of 2-Halothane: induction stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, add 4-trifluoromethyl-α, α, 40 parts of α-trifluoromethyl acetophenones, 240 parts of phenol, 4 parts of zinc chloride, reaction mixture is heated to 100 ℃, feeds HCl gas simultaneously, reacts 3-4 hour, obtain reddish-brown liquid, pressure reducing and steaming phenol, product gets white 1 with ethyl alcohol recrystallization, two (4-the hydroxy phenyl)-1-(4-trifluoromethyl)-2 of 1-, 2,2-Halothane solid.
4,4 '-two (2,3-epoxypropyl phenyl)-and 1-(4-trifluoromethyl)-2,2,2-Halothane: with 40 part 1, two (4-the hydroxy phenyl)-1-(4-trifluoromethyl)-2 of 1-, 2,2-Halothane and 800 parts of epoxy chloropropane, 80 parts of 48%NaOH solution add in the there-necked flask, react three hours down at 65 ℃, product extracts with methyl iso-butyl ketone (MIBK), and washes with water.Organic phase boils off whole solvents and gets colourless 4,4 '-two (2,3-epoxypropyl phenyl)-1-(4-trifluoromethyl)-2,2,2-Halothane thick liquid.
Example 41, two (4-the hydroxy phenyl)-1-(4-fluorophenyl)-2,2 of 1-, the preparation of 2-Halothane: with 50 parts of 4-fluoro-α, α, α-trifluoromethyl acetophenone, 300 parts of phenol and 5 parts of magnesium chlorides add in the there-necked flask, reaction mixture is heated to 100 ℃, feeds HCl gas simultaneously, reacts 3-4 hour, obtain reddish-brown liquid, pressure reducing and steaming phenol, product gets white 1 with ethyl alcohol recrystallization, two (4-the hydroxy phenyl)-1-(4-fluorophenyl)-2 of 1-, 2,2-Halothane solid.
4,4 '-two (2,3-epoxypropyl phenyl)-and 1-(4-methyl fluoride phenyl)-2,2,2-Halothane: with 50 part 1, two (4-the hydroxy phenyl)-1-(4-trifluoromethyl)-2 of 1-, 2,2-Halothane and 800 parts of epoxy chloropropane, 100 parts of 48%NaOH solution add in the there-necked flask, react three hours down at 65 ℃, product extracts with methyl iso-butyl ketone (MIBK), and washes with water.Organic phase boils off whole solvents and gets colourless 4,4 '-two (2,3-epoxypropyl phenyl)-1-(4-trifluoromethyl)-2,2,2-Halothane thick liquid.
Example 51, two (4-the hydroxy phenyl)-1-(3,5-two trifluoromethyls)-2 of 1-, 2, the preparation of 2-Halothane: induction stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding 3,5-bis trifluoromethyl-α, α, 60 parts of α-trifluoromethyl acetophenones, 360 parts of phenol, 3 parts of 2 parts in aluminum chloride and zinc chloride, reaction mixture is heated to 100 ℃, feeds HCl gas simultaneously, reacts 2-3 hour, obtain reddish-brown liquid, pressure reducing and steaming phenol, product gets white 1 with ethyl alcohol recrystallization, two (4-the hydroxy phenyl)-1-(3-trifluoromethyl)-2 of 1-, 2,2-Halothane solid.
4,4 '-two (2,3-epoxypropyl phenyl)-1-(3, the 5-bis trifluoromethyl phenyl)-2,2, the preparation of 2-Halothane: with 40 part 1, two (4-the hydroxy phenyl)-1-(3 of 1-, the 5-bis trifluoromethyl phenyl)-2,2,2-Halothane and 800 parts of epoxy chloropropane, 80 parts of 48%NaOH solution add in the there-necked flask, react three hours down at 65 ℃, product extracts with methyl iso-butyl ketone (MIBK), and washes with water.Organic phase boils off whole solvents, gets colourless 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,2-Halothane thick liquid.4,4 '-diaminodiphenyl oxide (DDE), 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 4-methyl hexahydrophthalic anhydride (HMPA), 4,4 '-two (2,2 '-bis trifluoromethyl-4-amido phenoxy group) benzene (6FAPB), 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenylmethane (TMDA) etc.
Example 6 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-phenyl-2,2,100 parts of 2-Halothane Resins, epoxy, 4,25 parts of 4 '-diaminodiphenyl oxides (ODA), 2,4,0.5 part of 6-three (dimethylamine methyl) phenol, 10 parts of phenyl glycidyl ethers (PGE), be heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 200 ℃ solidified 2 hours, 250 ℃ of after fixing 2 hours.Under the room temperature slowly the cooling, peel off obtain the surface uniform and smooth, whole clearing is even, no bubble, flawless cured resin disk.Recording its volume specific resistance is 1.89 * 10
15Ω cm, 25 ℃ of specific inductivity 3.23 when recording 1MHz, dielectric loss 0.0072 (Q shows method, down with).Water-intake rate is 0.56% (immersion recorded after 24 hours under the room temperature, down together)
Example 7 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,100 parts of 2-Halothane, 4,25 parts of 4 '-diaminodiphenyl oxides (DDE), 2,4,0.5 part of 6-three (dimethylamine methyl) phenol, 12 parts of cresylglycidylethers (CGE), be heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 210 ℃ solidified 2 hours, 250 ℃ of after fixing 2 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 8.32 * 10
15Ω cm, 25 ℃ of specific inductivity 3.32 when recording 1MHz, dielectric loss 0.0057.Water-intake rate is 0.51%.
Example 8 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(4-trifluoromethyl)-2,2,80 parts of 2-Halothane, 4,20 parts of 4 '-diaminodiphenylsulfone(DDS)s (DDS), 1,0.3 part of 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), 15 parts of n-butyl glycidyl ethers (BGE) are heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 220 ℃ solidified 2 hours, 240 ℃ of after fixing 1 hour.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 9.56 * 10
15Ω cm, 25 ℃ of specific inductivity 3.21 when recording 1MHz, dielectric loss 0.0047.Water-intake rate 0.45%
Example 9 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(4-fluorophenyl)-2,2, and 100 parts of 2-Halothane, 85 parts of 4-methyl hexahydrophthalic anhydrides (HMPA), 0.3 part of 1-cyanoethyl-2-ethyl-4-methylimidazole heats and stirs.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 80 ℃ solidified 1 hour, and 150 ℃ solidified 2 hours, 170 ℃ of after fixing 1 hour.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 9.63 * 10
16Ω cm, 25 ℃ of specific inductivity 3.10 when recording 1MHz, dielectric loss 0.0013.Water-intake rate 0.36%
Example 10 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3, the 5-bis trifluoromethyl phenyl)-2,2, the 2-Halothane is 100 parts, 4,25 parts of 4 '-two (2,2 '-bis trifluoromethyl-4-amido phenoxy group) benzene (6FAPB), 1,0.3 part of 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), be heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 200 ℃ solidified 2 hours, 250 ℃ of after fixing 1 hour.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 1.93 * 10
15Ω cm, 25 ℃ of specific inductivity 3.30 when recording 1MHz, dielectric loss 0.0021.Water-intake rate 0.36%
Example 11 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,100 parts of 2-Halothane, 3,3 ', 5,5 '-tetramethyl--4,25 parts of 4 '-diaminodiphenylmethane (TMDA), 0.3 part of 1-cyanoethyl-2-ethyl-4-methylimidazole, 10 parts of n-butyl glycidyl ethers (BGE) are heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 200 ℃ solidified 2 hours, 250 ℃ of after fixing 1 hour.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 1.59 * 10
16Ω cm, 25 ℃ of specific inductivity 3.40 when recording 1MHz, dielectric loss 0.0024.Water-intake rate 0.38%
Example 12 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3, the 5-bis trifluoromethyl phenyl)-2,2, the 2-Halothane is 100 parts, 40 parts of 4-methyl hexahydrophthalic anhydrides (HMPA), 40 parts of 4-methyl tetrahydro phthalic anhydrides (MeTHPA), 2,4,0.2 part of 6-three (dimethylamine methyl) phenol,, 1,0.1 part of 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), 12 parts of cresylglycidylethers (CGE) are heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 100 ℃ solidified 1 hour, and 150 ℃ solidified 2 hours, 170 ℃ of after fixing 3 hours.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 1.87 * 10
15Ω cm, 25 ℃ of specific inductivity 3.34 when recording 1MHz, dielectric loss 0.0041.Water-intake rate 0.38%
Example 13 gets 4,4 '-two (2,3-epoxypropyl phenyl)-1-(3-trifluoromethyl)-2,2,100 parts of 2-Halothane, 30 parts of HHPAs (HHPA), 50 parts of tetrahydrophthalic anhydride (THPA), 1,0.1 part of 8-binary aza-bicyclo [5.4.0.] hendecene-7 (DBU), 0.2 part of 1-cyanoethyl-2-ethyl-4-methylimidazole, 5 parts of cresylglycidylethers (CGE) and 10 parts of n-butyl glycidyl ethers (BGE), be heated to fusion, stir into homogeneous phase solution, evenly mixed.It is watered cast from diameter 10cm, in the steel die of dark 5mm, 150 ℃ solidified 1 hour, and 200 ℃ solidified 2 hours, 220 ℃ of after fixing 1 hour.Slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin disk.Recording its volume specific resistance is 1.49 * 10
16Ω cm, 25 ℃ of specific inductivity 3.20 when recording 1MHz, dielectric loss 0.0018.Water-intake rate 0.35%.
Claims (5)
1, a kind of method for preparing fluorine-containing epoxy resin and derivative thereof, its synthetic route is:
Main preparation process is:
A) 40-60 part is replaced α, α, α-trifluoromethyl acetophenone and 240-360 part phenol and the lewis acidic mixture heating up of 4-5 part feed HCl gas simultaneously to 80-100 ℃, react 2-4 hour, get fluorine-containing diphenol;
B) with 30-40 part diphenol of step a gained and 600-800 part epoxy chloropropane in the NaOH solution of 60-90 part 40-50%, 50-75 ℃ of reaction 2-4 hour down, epoxidation gets fluorine-containing epoxy and derivative thereof;
C) get the product of 80-100 part step b preparation, mixes, add 10-15 part thinner again and be heated to and dissolve and stir with 20-80 part organic amine curing agent or organic acid anhydride solidifying agent, 0.3-0.5 part curing catalyst;
D) solution-cast that step c is prepared is in mould, and 80-150 ℃ solidified 1-2 hour, and 150-250 ℃ solidified 1-3 hour;
E) slowly cooling under the room temperature is peeled off and is obtained uniform and smooth, the no bubble in surface, flawless cured resin.
2, preparation method according to claim 1 is characterized in that, described Lewis acid comprises aluminum chloride, magnesium chloride or zinc chloride and composition thereof.
3, preparation method according to claim 1, it is characterized in that described organic amine curing agent comprises 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-two (2,2 '-bis trifluoromethyl-4-amido phenoxy group) benzene, 3,3 ', 5,5 '-tetramethyl--4, the mixture of 4 '-diaminodiphenylmethane and any ratio thereof; The organic acid anhydride solidifying agent comprises the mixture of 4-methyl hexahydrophthalic anhydride, 4-methyl tetrahydro phthalic anhydride, HHPA or tetrahydrophthalic anhydride and any ratio thereof.
4, preparation method according to claim 1, it is characterized in that, described curing catalyst comprises: 2,4,6-three (dimethylamine methyl) phenol, 1, the mixture of 8-binary aza-bicyclo [5.4.0.] hendecene-7,2-ethyl-4-methylimidazole, glyoxal ethyline, trolamine or 1-cyanoethyl-2-ethyl-4-methylimidazole and any ratio thereof.
5. preparation method according to claim 1, it is characterized in that described thinner comprises: the mixture of phenyl glycidyl ether, cresylglycidylether, n-butyl glycidyl ether, diglycidylaniline, glycerol triglycidyl ether and any ratio thereof.
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| CN101215367B (en) * | 2007-12-29 | 2010-08-11 | 海洋化工研究院 | Epoxy resin containing perfluoroalkyl side chain and its preparing method and application |
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| CN103360347A (en) * | 2012-04-06 | 2013-10-23 | 中国科学院化学研究所 | Fluorine-containing epoxy resin and preparation method thereof |
| CN103410003B (en) * | 2013-08-13 | 2016-03-23 | 厦门大学 | A kind of fluorine-containing self-lubricating type fabric coating material and preparation method thereof |
| CN103980231B (en) * | 2014-06-04 | 2016-03-30 | 中国科学院上海有机化学研究所 | A kind of synthetic method of pentafluorophenyl group propylene oxide |
| CN106280254A (en) * | 2016-08-15 | 2017-01-04 | 江苏中鹏新材料股份有限公司 | Filler and preparation method thereof and purposes at the bottom of a kind of low-k moulding type epoxy |
| CN108997560A (en) * | 2017-06-07 | 2018-12-14 | 洛阳尖端技术研究院 | A kind of epoxy resin composite material and its preparation method and application |
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| CN113736349B (en) * | 2021-09-14 | 2022-05-17 | 安徽华辉塑业科技股份有限公司 | Corrosion-resistant epoxy resin coating and preparation method thereof |
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| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101215367B (en) * | 2007-12-29 | 2010-08-11 | 海洋化工研究院 | Epoxy resin containing perfluoroalkyl side chain and its preparing method and application |
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Assignee: Beijing SHOUKEHUA Micro-Electronics Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2008.11.7 to 2013.11.6 Contract record no.: 2008990001374 Denomination of invention: Epoxy resin of containing fluorine, ramification, preparation method and application Granted publication date: 20061011 License type: Exclusive license Record date: 2008.12.5 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.7 TO 2013.11.6; CHANGE OF CONTRACT Name of requester: BEIJING SHOUKE MICROELECTRONICS CO., LTD. Effective date: 20081205 |
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