CN1312189C - Epoxy resin with three functional groups and its derivatives, their preparation method and use - Google Patents

Abstract

The invention relates to a preparation and curing method of trifunctional epoxy and derivatives thereof. Reaction of 4-hydroxyaromatic ketone or aldehyde compound with phenol under acid catalysis to generate substituted triphenol compound, reaction of triphenol compound with epichlorohydrin under base catalysis to obtain trifunctional epoxide and its derivatives; the trifunctional Epoxy compounds are cured with organic acid anhydrides or amines to obtain epoxy resins. The cured epoxy resin has a higher glass transition temperature, lower CTE, lower dielectric constant and dielectric loss. It has important application value in high-tech fields such as microelectronic packaging.

Description

A kind of trifunctional epoxy resin and its derivatives and preparation method and application

technical field

The invention relates to a trifunctional epoxy resin and its derivatives.

The present invention also relates to a preparation method of the above-mentioned epoxy resin.

The present invention also relates to the use of the above-mentioned epoxy resins.

Background technique

Epoxy resin has excellent thermal stability, chemical stability, excellent dielectric properties and low moisture absorption, and has been widely used in the microelectronics industry. With the rapid development of integrated circuits in the direction of small, light and thin, the form of microelectronic packaging has also changed from traditional dual in-line (DIP) and quad flat (QFP) to flip-chip ball grid array (FC) -PBGA), Chip Scale Package (CSP) and Multi-Chip Module (MCM). Advanced microelectronic packaging technology has higher and higher performance requirements for epoxy resin, mainly including: 1) high heat resistance and stability, low coefficient of thermal expansion (CTE); 2) high mechanical strength, low modulus; 3 ) Low dielectric constant and dielectric loss, and 4) low water absorption, etc. The thermal stress of the packaging material has a greater impact on the reliability of the packaging. For example, when the CTE of the epoxy material and the CTE of the silicon substrate are greatly different, cracks are likely to occur when heated. Therefore, people have carried out systematic research work on increasing the glass transition temperature of epoxy resin and reducing the CTE of epoxy resin. US Patent 6139978 discloses the application of a multi-functional epoxy in BGA packaging; Oh et al. Synthesis and characterization of oxygen resins. The research results show that the thermal stability of the material can be improved and the CTE of the material can be reduced by using multifunctional epoxy to increase the crosslinking density of the epoxy resin.

Contents of the invention

The purpose of the present invention is to disclose a kind of trifunctional epoxy resin and its derivatives.

Another object of the present invention is to disclose the preparation method of the above-mentioned epoxy resin.

The trifunctional epoxy resin and its derivatives disclosed by the present invention have definite molecular weight, and its epoxy value is consistent with the theoretical value; the cured resin formed by the curing reaction of the epoxy compound and its derivatives with curing agents such as acid anhydride or organic amine It has a higher glass transition temperature, lower CTE, lower dielectric constant and dielectric loss. Therefore, it has important application value in high-tech fields such as microelectronic packaging.

The trifunctional epoxy resin of the present invention has the chemical structure shown below:

Trifunctional epoxy resin of the present invention is characterized in that its preparation process is carried out by following chemical synthesis route:

The specific process is:

1) By weight, 40-50 parts of 4-hydroxyaromatic ketone or aldehyde compound, 4-40 parts of Lewis acid, 240-300 parts of phenol, react at 80-100 °C in HCl atmosphere for 2-4 hours , remove phenol, and recrystallize the product with ethanol to obtain triphenol compound;

2) In parts by weight, 40-50 parts of triphenol compounds, 1000-1000 parts of epichlorohydrin, and 80-100 parts of alkali are reacted at 45-70 ° C for 2-4 hours, and the product is made of methyl isobutyl Base ketone extraction, remove the organic phase, get trifunctional epoxy and its derivatives;

3) Mix the trifunctional epoxy compound and its derivatives, the curing agent, the curing accelerator, and the diluent uniformly in a ratio of 80-100:25-85:0.3-0.5:0-10 in parts by weight;

4) Pour the above mixture into a mold and heat to cure. The curing conditions are: 80-150°C for 1-2 hours, 150-160°C for 2-10 hours;

5) Slowly cool the cured product to room temperature, and peel off to obtain a cured resin with a uniform and smooth surface, no bubbles, and no defects.

The Lewis acid used in the preparation process of the present invention includes: anhydrous aluminum trichloride, anhydrous magnesium chloride, anhydrous zinc chloride and the like.

The curing agent used in the preparation process of the present invention includes organic amine curing agent and organic acid anhydride curing agent. Organic amine curing agents include 4,4'-diaminodiphenyl ether (ODA), 4,4'-diaminodiphenylmethane (DDM), 4,4'-diaminodiphenylsulfone (DDS), 4,4 '-Bis(2,2'-bistrifluoromethyl-4-aminophenoxy)benzene (6FAPB), 3,3',5,5'-tetramethyl-4,4'-diaminobis Benzene (TMDA) and mixtures thereof in any proportion. Organic acid anhydride curing agents include 4-methylhexahydrophthalic anhydride (HMPA), 4-methyltetrahydrophthalic anhydride (MeTHPA), hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride (THPA) and mixtures thereof in any proportion.

The curing accelerator used in the preparation process of the present invention includes: 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), 1,8-binary aza-bicyclo[5.4.0.] Undecene-7 (DBU), 2-ethyl-4-methylimidazole, 2-methylimidazole, triethanolamine, 1-cyanoethyl-2-ethyl-4-methylimidazole and any proportion thereof mixture.

The diluent used in the preparation process of the present invention includes: phenyl glycidyl ether (PGE), cresol glycidyl ether (CGE), n-butyl glycidyl ether (BGE), diglycidyl aniline (DGA), propylene glycol Triol triglycidyl ether (GGE) and mixtures thereof in any proportion.

The trifunctional epoxy resin and its derivatives disclosed by the present invention have excellent thermal stability, low thermal expansion coefficient, low dielectric constant and dielectric loss, etc.; these excellent comprehensive properties make it widely used in microelectronics It has potential important application value in packaging. Typical applications include solid epoxy molding compound, liquid epoxy encapsulating compound, epoxy conductive silver paste, thermal conductive paste, underfill for flip chip, etc.

Detailed ways

The following examples 1-3 are the preparation methods of trifunctional epoxy compounds and derivatives thereof; Examples 4-9 are the curing process of trifunctional epoxy compounds and derivatives thereof.

Example 1:

The preparation of 1,1,1-tris(4-hydroxyphenyl)methane: in the there-necked flask equipped with electromagnetic stirring, condenser tube and nitrogen inlet and outlet, add 40 parts of 4-hydroxybenzaldehyde, 240 parts of phenol and chlorinated 4 parts of aluminum, the reaction mixture was heated to 100°C, and HCl gas was introduced at the same time, and the reaction was carried out for 2-3 hours to obtain a reddish-brown liquid. -Hydroxyphenyl)methane solid.

The preparation of 1,1,1-tris(2,3-epoxypropylphenyl)methane: 50 parts of 1,1,1-tris(4-hydroxyphenyl)methane and 1000 parts of epichlorohydrin, 100 parts A portion of 48% NaOH solution was added into a three-necked flask, and reacted at 65° C. for three hours. The product was extracted with methyl isobutyl ketone and washed with water. All the solvent was evaporated from the organic phase to obtain a white 1,1,1-tris(2,3-epoxypropylphenyl)methane solid.

Example 2:

The preparation of 1,1,1-tris(4-hydroxyphenyl)ethane: in the there-necked flask equipped with electromagnetic stirring, condenser tube and nitrogen inlet and outlet, add 50 parts of 4-hydroxyacetophenone, 300 parts of phenol and 5 parts of zinc chloride, the reaction mixture was heated to 100°C, and HCl gas was introduced at the same time, and the reaction was carried out for 2-3 hours to obtain a reddish-brown liquid. The phenol was evaporated under reduced pressure, and the product was recrystallized with ethanol to obtain white 1,1,1-tri (4-Hydroxyphenyl)ethane solid.

Preparation of 1,1,1-tris(2,3-epoxypropylphenyl)ethane: 40 parts of 1,1,1-tris(4-hydroxyphenyl)ethane and 800 parts of epichlorohydrin , 80 parts of 48% NaOH solution were added into a three-necked flask, and reacted at 65° C. for three hours. The product was extracted with methyl isobutyl ketone and washed with water. All the solvent was evaporated from the organic phase to obtain a white solid of 1,1,1-tris(2,3-epoxypropylphenyl)ethane.

Example 3:

The preparation of 1,1,1-tris(4-hydroxyphenyl)-2,2,2-trifluoroethane: in the there-necked flask equipped with electromagnetic stirring, condenser and nitrogen inlet and outlet, add 4-hydroxy- α, α, 40 parts of α-trifluoromethyl acetophenone, 240 parts of phenol, 4 parts of zinc chloride, the reaction mixture was heated to 100 ° C, and HCl gas was introduced at the same time, and the reaction was carried out for 3-4 hours to obtain a reddish-brown liquid. The phenol was distilled off under reduced pressure, and the product was recrystallized from ethanol to obtain a white 1,1,1-tris(4-hydroxyphenyl)-2,2,2-trifluoroethane solid.

The preparation of 1,1,1-tris(2,3-epoxypropylphenyl)-2,2,2-trifluoroethane: 50 parts of 1,1,1-tris(4-hydroxyphenyl) -2,2,2-Trifluoroethane, 1000 parts of epichlorohydrin, and 100 parts of 48% NaOH solution were added to a three-necked flask, and reacted at 65°C for three hours, the product was extracted with methyl isobutyl ketone, and water washing. All the solvent was evaporated from the organic phase to obtain a white solid of 1,1,1-tris(2,3-epoxypropylphenyl)-2,2,2-trifluoroethane.

Example 4:

Take 90 parts of 1,1,1-tris(2,3-epoxypropylphenyl)methane epoxy resin, 30 parts of 4,4'-diaminodiphenyl ether (ODA), 2,4,6-tri (Dimethylaminomethyl)phenol 0.5 part, 10 parts phenyl glycidyl ether (PGE), heated to melt, stirred into a homogeneous solution, and mixed evenly. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 150° C. for 1 hour, 200° C. for 2 hours, and post-cured at 220° C. for 2 hours. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured volume resistivity was 1.08×10 ¹⁶ Ω·cm, the dielectric constant was 3.51 at 1 MHz at 25°C, and the dielectric loss was 0.0082 (Q table method, the same below). Water absorption rate 0.56% (measured after soaking at room temperature for 24 hours, the same below)

Example 5:

Take 100 parts of 1,1,1-tris(2,3-epoxypropylphenyl)ethane, 35 parts of 4,4'-diaminodiphenyl ether (DDE), 2,4,6-tris(di 0.5 parts of methylaminomethyl) phenol, 10 parts of cresol glycidyl ether (CGE), heated to melt, stirred into a homogeneous solution, and mixed evenly. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 150° C. for 1 hour, 200° C. for 2 hours, and post-cured at 220° C. for 2 hours. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured glass transition temperature is 223 degrees, the volume resistivity is 2.02×10 ¹⁶ Ω·cm, the dielectric constant is 3.62 at 1 MHz at 25°C, and the dielectric loss is 0.0097. The water absorption rate is 0.91%.

Example 6:

Take 80 parts of 1,1,1-tris(4-hydroxyphenyl)-2,2,2-trifluoroethane, 25 parts of 4,4'-diaminodiphenylsulfone (DDS), 1,8-di 0.3 parts of aza-bicyclo[5.4.0.]undecene-7 (DBU), 10 parts of n-butyl glycidyl ether (BGE), heated to melt, stirred to form a homogeneous solution, and mixed evenly. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 150° C. for 1 hour, 220° C. for 2 hours, and post-cured at 240° C. for 1 hour. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured glass transition temperature is 250°C, the volume resistivity is 9.87×10 ¹⁵ Ω·cm, the dielectric constant is 3.41 at 1 MHz at 25°C, and the dielectric loss is 0.0037. Water absorption 0.45%

Example 7:

Take 100 parts of 1,1,1-tris(2,3-epoxypropylphenyl)ethane, 85 parts of 4-methylhexahydrophthalic anhydride (HMPA), 1-cyanoethyl-2-ethyl-4 - 0.3 parts of methylimidazole, heated and stirred evenly. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 80° C. for 1 hour, 150° C. for 2 hours, and post-cured at 170° C. for 1 hour. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured glass transition temperature is 205°C, the volume resistivity is 8.53×10 ¹⁶ Ω·cm, the dielectric constant is 3.30 at 1 MHz at 25°C, and the dielectric loss is 0.0023. Water absorption 0.39%

Example 8:

Take 100 parts of 1,1,1-tris(4-hydroxyphenyl)-2,2,2-trifluoroethane, 4,4'-bis(2,2'-bistrifluoromethyl-4-amine 35 parts of phenyloxy)benzene (6FAPB), 0.3 parts of 1,8-binary aza-bicyclo[5.4.0.]undecene-7(DBU), heated to melt, stirred into a homogeneous solution, mixed uniform. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 150° C. for 1 hour, at 200° C. for 2 hours, and post-cured at 250° C. for 1 hour. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured glass transition temperature is 235°C, the volume resistivity is 7.93×10 ¹⁶ Ω·cm, the dielectric constant is 3.28 at 1 MHz at 25°C, and the dielectric loss is 0.0021. Water absorption 0.35%

Example 9:

Take 90 parts of 1,1,1-tris(4-hydroxyphenyl)-2,2,2-trifluoroethane, 3,3',5,5'-tetramethyl-4,4'-diamino 30 parts of diphenylmethane (TMDA), 0.3 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 10 parts of n-butyl glycidyl ether (BGE), heated to melt, stirred into a homogeneous solution, Mix well. It was cast in a steel mold with a diameter of 10 cm and a depth of 5 mm, cured at 150° C. for 1 hour, at 200° C. for 2 hours, and post-cured at 250° C. for 1 hour. Cool slowly at room temperature, and peel off to obtain a cured resin disc with a uniform and smooth surface, no bubbles, and no defects. The measured glass transition temperature is 255°C, the volume resistivity is 5.59×10 ¹⁶ Ω·cm, the dielectric constant is 3.41 at 1 MHz at 25°C, and the dielectric loss is 0.0034. Water absorption 0.38%

Claims (7)

1, a kind of trifunctional Resins, epoxy and derivative thereof, chemical structure is as follows:

R＝CF ₃

2, a kind of method for preparing described trifunctional Resins, epoxy of claim 1 and derivative thereof, its synthetic route is:

R＝CF ₃

Main preparation process is:

A) by weight, the 4-hydroxyl aromatic ketone or the aldehyde cpd of 40-50 part, the Lewis acid of 4-40 part, the phenol of 240-300 part, in 80-100 ℃, reaction is 2-4 hour in the HCl atmosphere, removes phenol, gets three phenolic compound;

B) by weight, three phenolic compound of 40-50 part, the epoxy chloropropane of 1000-1000 part, the alkali of 80-100 part, in 45-70 ℃ of reaction 2-4 hour, product extracted with methyl iso-butyl ketone (MIBK), removes organic phase, got trifunctional epoxy and derivative thereof;

C) with trifunctional epoxy compounds and derivative thereof, solidifying agent, curing catalyst, thinner 80-100: 25-85: 0.3-0.5 by weight: 0-10 ratio uniform mixing;

D) said mixture is poured in the mould be heating and curing, condition of cure is: 80-150 ℃ solidified 1-2 hour, 150-160 ℃ after fixing 2-10 hour;

E) cured article is slowly cooled to room temperature, peel off and obtain cured resin;

3. preparation method as claimed in claim 2 is characterized in that Lewis acid described in the step a comprises aluminum chloride, magnesium chloride or zinc chloride and composition thereof.

4. preparation method as claimed in claim 2 is characterized in that, solidifying agent described in the step c comprises organic amine curing agent and organic acid anhydride solidifying agent, 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.

5. preparation method as claimed in claim 2, it is characterized in that, curing catalyst comprises described in the step c: 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.

6. preparation method as claimed in claim 2, it is characterized in that thinner comprises described in the step c: the mixture of phenyl glycidyl ether, cresylglycidylether, n-butyl glycidyl ether, diglycidylaniline, glycerol triglycidyl ether and any ratio thereof.

7, in microelectronics Packaging, be used as the end filler that solids epoxy plastic cement, liquid epoxy are sealed material, epoxy conductive silver slurry, heat conduction slurry and upside-down mounting welding core as the described trifunctional Resins, epoxy of above-mentioned each claim and derivative thereof.