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CN1279078C - Epoxy resin of containing fluorine, ramification, preparation method and application - Google Patents

Epoxy resin of containing fluorine, ramification, preparation method and application Download PDF

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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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epoxy resin
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fluorine
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CN1626563A (en
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杨士勇
葛子义
范琳
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Institute of Chemistry CAS
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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

A kind of fluorine-containing epoxy resin and derivative and preparation method and application
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:
Figure C20031011941100051
Preparation process of the present invention is undertaken by following chemical synthesis route
Figure C20031011941100052
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、一种制备含氟环氧树脂及其衍生物的方法，其合成路线为：1. A method for preparing fluorine-containing epoxy resin and derivatives thereof, the synthetic route of which is: 主要制备步骤为：The main preparation steps are: a)将40-60份取代α，α，α-三氟甲基苯乙酮与240-360份苯酚和4-5份路易斯酸的混合物加热至80-100℃，同时通入HCl气体，反应2-4小时，得含氟二酚；a) Heating the mixture of 40-60 parts of substituted α, α, α-trifluoromethyl acetophenone, 240-360 parts of phenol and 4-5 parts of Lewis acid to 80-100° C., while feeding HCl gas to react 2-4 hours, get fluorine-containing diphenol; b)将步骤a所得的30-40份二酚与600-800份环氧氯丙烷于60-90份40-50％的NaOH溶液中，50-75℃下反应2-4小时，环氧化得含氟环氧及其衍生物；b) 30-40 parts of diphenol obtained in step a and 600-800 parts of epichlorohydrin are reacted in 60-90 parts of 40-50% NaOH solution at 50-75° C. for 2-4 hours, and epoxidized Obtain fluorine-containing epoxy and its derivatives; c)取80-100份步骤b制备的产物，与20-80份有机胺固化剂或有机酸酐固化剂、0.3-0.5份固化促进剂混合，再加入10-15份稀释剂加热至溶解并搅拌均匀；c) Take 80-100 parts of the product prepared in step b, mix with 20-80 parts of organic amine curing agent or organic acid anhydride curing agent, 0.3-0.5 part of curing accelerator, add 10-15 parts of diluent, heat until dissolved and stir Uniform; d)将步骤c制备的溶液浇铸于模具中，80-150℃固化1-2小时，150-250℃固化1-3小时；d) casting the solution prepared in step c into a mold, curing at 80-150°C for 1-2 hours, and curing at 150-250°C for 1-3 hours; e)室温下缓慢冷却，剥离得到表面均匀光滑、无气泡、无缺陷的固化树脂。e) slowly cooling at room temperature, and peeling off to obtain a cured resin with a uniform and smooth surface, no bubbles, and no defects. 2、根据权利要求1所述的制备方法，其特征在于，所述路易斯酸包括三氯化铝、氯化镁或氯化锌及其混合物。2. The preparation method according to claim 1, characterized in that the Lewis acid comprises aluminum trichloride, magnesium chloride or zinc chloride and mixtures thereof. 3、根据权利要求1所述的制备方法，其特征在于，所述有机胺固化剂包括4，4’-二氨基二苯醚、4，4’-二氨基二苯甲烷、4，4’-二氨基二苯砜、4，4’-双(2，2’-双三氟甲基-4-胺基苯氧基)苯、3，3’，5，5’-四甲基-4，4’-二氨基二苯甲烷及其任何比例的混合物；有机酸酐固化剂包括4-甲基六氢苯酐、4-甲基四氢苯酐、六氢苯酐或四氢苯酐及其任何比例的混合物。3. The preparation method according to claim 1, wherein the organic amine curing agent includes 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylsulfone, 4,4'-bis(2,2'-bistrifluoromethyl-4-aminophenoxy)benzene, 3,3',5,5'-tetramethyl-4, 4'-diaminodiphenylmethane and its mixture in any proportion; the organic acid anhydride curing agent includes 4-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or tetrahydrophthalic anhydride and its mixture in any proportion. 4、根据权利要求1所述的制备方法，其特征在于，所述固化促进剂包括：2，4，6-三(二甲胺甲基)苯酚、1，8-二元氮杂-双环[5.4.0.]十一烯-7、2-乙基-4-甲基咪唑、2-甲基咪唑、三乙醇胺或1-氰乙基-2-乙基-4-甲基咪唑及其任何比例的混合物。4. The preparation method according to claim 1, wherein the curing accelerator comprises: 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-binary aza-bicyclo[ 5.4.0.] Undecene-7, 2-ethyl-4-methylimidazole, 2-methylimidazole, triethanolamine or 1-cyanoethyl-2-ethyl-4-methylimidazole and any Proportional mixture. 5.根据权利要求1所述的制备方法，其特征在于，所述稀释剂包括：苯基缩水甘油醚、甲酚缩水甘油醚、正丁基缩水甘油醚、二缩水甘油基苯胺、丙三醇三缩水甘油醚及其任何比例的混合物。5. preparation method according to claim 1, is characterized in that, described diluent comprises: phenyl glycidyl ether, cresol glycidyl ether, n-butyl glycidyl ether, diglycidyl aniline, glycerol Triglycidyl ether and mixtures thereof in any proportion.
CNB2003101194114A 2003-12-10 2003-12-10 Epoxy resin of containing fluorine, ramification, preparation method and application Expired - Fee Related CN1279078C (en)

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