CN101186796A - A kind of preparation method of epoxy resin adhesive - Google Patents

Abstract

The invention discloses a preparation method of epoxy resin adhesive. Using epoxy-based phenyl silicone oil as a toughening modifier for epoxy resin adhesives, by introducing phenyl groups into the molecular structure of epoxy-based silicone oil, the compatibility of silicone resin and epoxy resin mixing is improved, and at the same time Due to the joint action of the flexible Si-O-Si chain and the rigid phenyl group, the impact toughness and bending strength of the cured product can be improved at the same time, it has the effect of toughening and strengthening, and has excellent heat resistance and electrical insulation properties Its initial thermal decomposition temperature is greater than 400°C, its volume resistivity is greater than 10 ¹⁷ Ω.cm at room temperature, and its dielectric loss is less than 2% at room temperature and 155°C, and it is especially suitable for the casting and packaging of electronic materials and the manufacture of electrical insulating materials.

Description

A kind of preparation method of epoxy resin adhesive

technical field

The invention relates to a preparation method of an adhesive, in particular to a preparation method of an epoxy resin adhesive.

Background technique

Epoxy resin has the advantages of excellent mechanical properties, electrical properties, chemical resistance, bonding properties, etc., and is widely used in coatings, adhesives, electrical and electronic material insulation, and the matrix of advanced composite materials. Insulation materials are developing towards high performance, which requires materials to have higher performance, such as high toughness, low internal stress, heat resistance, moisture resistance, etc., while epoxy resin cured products are mostly brittle and have low heat resistance. Easy to absorb moisture and so on.

At present, the methods of epoxy resin toughening mainly include: rubber elastomer toughening, thermoplastic resin toughening, thermotropic liquid crystal toughening, interpenetrating network toughening, silicone toughening, etc., each method has its own advantages and disadvantages. Among them, silicone polymers have the advantages of low surface energy, heat resistance, oxygen aging resistance, good hydrophobicity, and excellent insulation properties due to the large amount of flexible Si-O-Si chains in their molecular structure, which can make up for the lack of epoxy resins. It can meet the needs of the development of high-performance composite materials, but the compatibility between the two is poor. Functional polysiloxane-modified epoxy resins, especially epoxy-containing polyoxanes, have attracted much attention due to their good compatibility with epoxy resins, such as patents CN 1747985A, CN1189847A, CN1932149A, CN1875071A, However, most of the epoxy-based polysiloxanes used are low-polymerization molecules, and there are still problems such as poor compatibility between high-molecular-weight epoxy silicone oil and epoxy resin. Even after pre-reaction and curing, phase separation still occurs, resulting in Decreased heat resistance and mechanical properties. Patent CN1796455A discloses a method for modifying epoxy resin composite materials with epoxy-based silicone oil, mainly through the pre-reaction of epoxy-based silicone oil and amine curing agent, and then mixing with epoxy resin, but the amount of addition is increased to a certain proportion After that, the performance will drop sharply, seriously affecting the operability of the application process.

Invention content:

The purpose of the present invention is to improve the shortcomings of poor compatibility, decreased flexural strength and poor electrical properties during toughening of epoxy-based silicone oil modified epoxy resin adhesives, to achieve good compatibility, and to achieve good compatibility while toughening. Reduced flexural strength, heat resistance and insulation properties.

A kind of preparation method of epoxy resin adhesive of the present invention is as follows, and following all represents with weight part:

Melt 100 parts of epoxy resin at 80-100°C, stir evenly, and vacuum debubble for 0.5-1.0 hours, raise the temperature to 100-160°C, add 0.01-10 parts of curing accelerator, stir until the curing accelerator melts evenly, and cool down to Add 0-100 parts of filler at 80-100°C, disperse evenly, then add 0.1-200 parts of epoxy phenyl silicone oil, 10-150 parts of curing agent, and stir evenly to obtain an epoxy resin adhesive.

The epoxy resin used in the present invention is the mixture of bisphenol A epoxy resin and linear phenol formaldehyde epoxy resin, and the weight ratio is 1: 2-3: 1; Bisphenol A epoxy resin, cycloaliphatic epoxy resin and linear The mixture of phenol formaldehyde epoxy resin, the weight ratio is 1:1:4-2:1:1; The mixture of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin and linear phenol formaldehyde epoxy resin, the weight ratio is 1:1:4-2:1:1; a mixture of hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin and linear phenol formaldehyde epoxy resin in a weight ratio of 1:1:2-2:1:1 ; A mixture of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin and linear phenol formaldehyde epoxy resin in a weight ratio of 1:1:1:6-3:3:1:1 Wherein the epoxy equivalent of bisphenol A epoxy resin is 150-2000g/mol, the epoxy equivalent of linear phenol formaldehyde epoxy resin is 180-250g/mol, the epoxy equivalent of hydrogenated bisphenol A epoxy resin is 200- 1100g/mol, the epoxy equivalent of linear phenol formaldehyde epoxy resin is 180-250g/mol, and the alicyclic epoxy resin is 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxy ring Hexane methyl ester with an epoxy equivalent of 131-143 g/mol or 3,4-epoxy-6-methylcyclohexanecarboxylate-3',4'-epoxy-6-methylcyclohexane Methyl ester, its epoxy equivalent is 152-156g/mol.

The structural formula of the epoxy group phenyl silicone oil that the present invention uses is:

or

Where m=1-100, n=1-100.

The curing agent used in the present invention is maleic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, diaminodiphenylmethane or diaminodiphenylsulfone .

The curing accelerator used in the present invention is aluminum acetylacetonate, copper acetylacetonate, neodymium acetylacetonate, 2,4,6-tris(dimethylaminomethyl)phenol or benzyldimethylamine.

The filler used in the present invention is SiO ₂ , Al ₂ O ₃ or TiO ₂ , and the particle size is 1nm-100mm.

A kind of preparation method of epoxy resin adhesive of the present invention, utilize epoxy group phenyl silicone oil as the toughening modifier of epoxy resin adhesive, by introducing phenyl group in the molecular structure of epoxy group silicone oil, improve organic silicon Compatibility between resin and epoxy resin, and due to the joint action of flexible Si-O-Si chain and rigid phenyl group, it can improve the impact toughness and bending strength of the cured product at the same time, and has the effect of toughening and strengthening. And it has excellent heat resistance and electrical insulation performance, its initial thermal decomposition temperature is greater than 400°C (TGA measurement, heating rate in N ₂ is 20°C/min), the volume resistivity is greater than 10 ¹⁷ Ω.cm at room temperature, room temperature and The dielectric loss is less than 2% at 155°C, and it is especially suitable for the casting and packaging of electronic materials and the manufacture of electrical insulation materials.

Detailed ways:

The following implementation is a further description of the present invention, but does not limit the scope of the present invention. ,

In the following examples, impact strength, flexural strength, volume resistivity and dielectric loss are tested according to GB/T2571-1995, GB/T 2570-1995, GB/T 1410-2006 and GB/T 1409-1988 respectively, TGA thermal weight loss The test was carried out under the condition that the heating rate was 20°C/min in _N2 .

Example 1:

25g bisphenol A epoxy resin (brand DER331, DOW Chemicals, epoxy equivalent is 182-192g/mol), 25g bisphenol A epoxy resin (brand 1050, Wuxi Diaisheng, epoxy equivalent 450-500 is g Melt with 50g of linear phenol-formaldehyde epoxy resin (grade F-44, Shanghai Zhengrui, epoxy equivalent is 205-213g/mol) at 80-100°C, stir well and vacuum debubble for 0.5-1.0 hours , heat up to 140°C and add 0.3g aluminum acetylacetonate, stir until the aluminum acetylacetonate is evenly melted, then cool down to 100°C and add 30g methylhexahydrophthalic anhydride and 10g epoxy phenyl silicone oil (structural formula is a, m =20-25, n=23-26), stirred evenly to obtain 140g epoxy resin adhesive. The mixture was transparent before and after mixing and curing, and no phase separation occurred. Impact strength 15KJ/m ² , 40% higher than pure epoxy system; bending strength 107MPa, 7% higher than pure epoxy system; volume resistivity 4×10 ¹⁷ Ω.cm at room temperature, dielectric loss 0.3%; at 155°C Dielectric loss 1.1%; TGA initial thermal decomposition temperature 430°C (N ₂ , heating rate 20°C/min).

Example 2:

50g bisphenol A epoxy resin (brand name DER331, DOW Chemicals, epoxy equivalent 182-192 is g/mol), 25g alicyclic epoxy resin (brand name ERL4221, Union Carbide, epoxy equivalent is 131-143g/mol) mol); and 25g of linear phenol-formaldehyde epoxy resin (brand F-44, Shanghai Zhengrui, epoxy equivalent is 205-213g/mol) melted at 80-100°C, stirred evenly and vacuum degassed for 0.5-1.0 hours, Heat up to about 140°C and add 0.25g of aluminum acetylacetonate, stir until the aluminum acetylacetonate is evenly melted, then cool down to 100°C and add 35g of methylhexahydrophthalic anhydride and 10g of epoxy phenyl silicone oil (structural formula such as b, m =21-25, n=24-28), to obtain 145g of epoxy resin adhesive. The mixture was transparent before and after mixing and curing, and no phase separation occurred. Impact strength 13KJ/m ² , 34% higher than pure epoxy system; bending strength 114MPa, 10% higher than pure epoxy system; volume resistivity at room temperature 6×10 ¹⁷ Ω.cm, dielectric loss 0.25%; at 155°C Dielectric loss 1.5%; TGA initial thermal decomposition temperature 507°C (N ₂ , heating rate 20°C/min).

Example 3:

With 25g bisphenol A epoxy resin (brand DER331, DOW Chemicals, epoxy equivalent is 182-192g/mol), 25g bisphenol A epoxy resin (brand 1050, Wuxi Di Aisheng, epoxy equivalent is 450- 500g/mol); and 50g of linear phenol-formaldehyde epoxy resin (grade F-44, Shanghai Zhengrui, epoxy equivalent of 205-213g/mol) melted at 80-100°C, stirred evenly and vacuum degassed 0.5-1.0 After hours, heat up to about 140°C and add 0.3g of aluminum acetylacetonate, stir until the aluminum acetylacetonate is evenly melted, then cool down to about 100°C and add 5g of SiO ₂ with a particle size of about 15nm, and add 32g of methylhexahydrophthalate after dispersing evenly Diformic anhydride and 10 g of epoxy phenyl silicone oil (structural formula such as a, m=30-33, n=35-37) to obtain 147 g of epoxy resin adhesive. The mixture was transparent before and after mixing and curing, and no phase separation occurred. Impact strength 18KJ/m ² , 46% higher than pure epoxy system; bending strength 126MPa, 17% higher than pure epoxy system; volume resistivity at room temperature 8×10 ¹⁷ Ω.cm, dielectric loss 0.28%; at 155°C Dielectric loss 1.9%; TGA initial thermal decomposition temperature 475°C (N ₂ , heating rate 20°C/min).

Claims (6)

1. the preparation method of an epoxyn is characterized in that its preparation method is as follows, below is weight part and represents:

With 100 parts of Resins, epoxy 80-100 ℃ of following fusion, the final vacuum de-bubbled that stirs 0.5-1.0 hour, be warming up to 100-160 ℃ and add curing catalyst 0.01-10 part, be stirred to the curing catalyst fusion evenly, be cooled to and add 0-100 part filler below 100 ℃, add 0.1-200 part epoxy and phenyl silicone oil, 10-150 part solidifying agent after being uniformly dispersed again, stirring obtains a kind of epoxyn.

2. the preparation method of a kind of epoxyn according to claim 1 is characterized in that Resins, epoxy is the mixture of bisphenol A epoxide resin and linear phenol formaldehyde (PF) Resins, epoxy, and weight ratio is 1: 2-3: 1; The mixture of bisphenol A epoxide resin, cycloaliphatic epoxy resin and linear phenol formaldehyde (PF) Resins, epoxy, weight ratio are 1: 1: 4-2: 1: 1; The mixture of bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin and linear phenol formaldehyde (PF) Resins, epoxy, weight ratio are 1: 1: 4-2: 1: 1; The mixture of hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin and linear phenol formaldehyde (PF) Resins, epoxy, weight ratio are 1: 1: 2-2: 1: 1; The mixture of bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin and linear phenol formaldehyde (PF) Resins, epoxy, weight ratio are 1: 1: 1: 6-3: 3: 1: 1; Wherein the epoxy equivalent (weight) of bisphenol A epoxide resin is 150-2000g/mol, and the epoxy equivalent (weight) of linear phenol formaldehyde (PF) Resins, epoxy is 180-250g/mol; The epoxy equivalent (weight) of hydrogenated bisphenol A epoxy resin is 200-1100g/mol; Cycloaliphatic epoxy resin is 3,4-epoxy-cyclohexane formic acid-3 ', 4 '-epoxy-cyclohexane methyl esters, epoxy equivalent (weight) is 131-143g/mol or 3,4-epoxy group(ing)-6-methylcyclohexane formic acid-3 ', 4 '-epoxy group(ing)-6-methylcyclohexane methyl esters, epoxy equivalent (weight) is 152-156g/mol.

3. the preparation method of a kind of epoxyn according to claim 1 is characterized in that the structural formula of epoxy and phenyl silicone oil is:

Or

M=1-100 wherein, n=1-100.

4. the preparation method of a kind of epoxyn according to claim 1 is characterized in that solidifying agent is MALEIC ANHYDRIDE, methylhexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl carbic anhydride, diaminodiphenyl-methane or diamino diphenyl sulfone.

5. the preparation method of a kind of epoxyn according to claim 1 is characterized in that promotor is aluminium acetylacetonate, acetylacetone copper, methyl ethyl diketone neodymium, 2,4,6-three (dimethylamino methyl) phenol or Bian Ji dimethylamine.

6. the preparation method of a kind of epoxyn according to claim 1 is characterized in that filler is SiO ₂, Al ₂O ₃Or TiO ₂, its particle diameter is 1nm-100mm.