CN101457011A - Preparation of composite nano particle modified epoxy resin - Google Patents

Abstract

The invention relates to the preparation of composite nano-particle modified epoxy resin, which comprises 100 weight proportion of epoxy resin, 18-78 weight proportion of curing agent phenolic aldehyde resin, 1.5-4.5 weight proportion of curing accelerator, 750-1635 weight proportion of composite inorganic nano-filler, 3.5-13.5 weight proportion of silicon oil modifier, and 10-35 proportion of triphenyl phosphate which is used for a flame retardant, wherein, the composite inorganic nano-filler refers to the mixture of (A) Nano-SiO2, (B) Nano-CaCO3 and (C) Nano-TiO2, wherein, 15-40nm A shares 40-80 percent of a total weight percentage, 20-35nm B shares 10-40 percent and 35-50nm C shares 5-30 percent.

Description

Preparation of a composite nanoparticle modified epoxy resin

technical field

Preparation of a composite nanoparticle modified epoxy resin

Background technique

Epoxy resin is an oligomer containing more than two epoxy groups in one molecule, which can react with a curing agent to form a three-dimensional network thermosetting plastic. Its research began in the early 1930s, while large-scale production and application was after 1948. Epoxy resin (EP) is the most widely used matrix resin for polymer matrix composites. EP is a thermosetting resin with excellent adhesion, wear resistance, mechanical properties, electrical insulation properties, chemical stability, high and low temperature resistance, low shrinkage, easy processing and molding, better stress transmission and cost Low cost and other advantages, it is widely used in adhesives, electronic instruments, light industry, construction, machinery, aerospace, coatings, bonding, electronic and electrical insulation materials, advanced composite material substrates and other fields. However, after EP is cured, the crosslinking density is high, and it has a three-dimensional network structure. It has large internal stress, brittle texture, poor fatigue resistance, heat resistance, and impact resistance, as well as low peel strength, low cracking strain, and poor heat and humidity resistance. And other shortcomings, coupled with high surface energy, to a large extent limit its application in some high-tech fields. In recent years, EP has been applied to structural bonding materials, semiconductor packaging materials, fiber reinforced materials, laminates, copper foil, integrated circuits and other electronic and electrical packaging materials, which requires EP materials to have better properties, such as strength, toughness, Internal stress reduction, heat resistance, water resistance, chemical resistance, etc. Therefore, the toughening and strengthening of EP has always been one of the important research topics for people to modify EP. General EP fillers and tougheners have the problem of poor interface adhesion between the reinforcing phase and the resin matrix. The improvement of toughness is at the expense of material strength, modulus and heat resistance, making it physically, The improvement of mechanical and thermal properties is limited.

With the rapid development of modern industry, higher and higher requirements are put forward for the performance of materials. Realizing the high performance of materials at low cost is the frontier topic of material research and application. There are generally two ways to realize the high performance of epoxy resin: 1) develop new epoxy resin; 2) modify existing epoxy resin by copolymerization-blending method. The development of new epoxy resin has a long research period and high cost. It has been reported that adding silicone resin to epoxy resin improves its dielectric properties, liquid polymer toughens epoxy resin, epoxy resin and acrylate resin emulsion form semi-latex IPN to make its bond strength and water resistance Substantially improved, polycarbonate toughened and reinforced epoxy resin.

In recent years, polymer-nanocomposites have become a research hotspot. The strong surface effect and volume effect of nanoparticles make the combination of polymer materials and nanomaterials show unique advantages in optical and mechanical properties, which provides a new way for the development of high-performance multifunctional new materials. Since epoxy resin is a thermosetting resin with strong adhesion, high stability and low shrinkage, it is currently a widely used matrix material for composite materials. The surface atoms of nanoparticles have unsaturation, which can enhance the interfacial bonding between particles and matrix, and can be physically and chemically combined with epoxy resin. Epoxy resin nanocomposites are an effective way to modify epoxy resins. Therefore, the preparation of epoxy resin-based composites by filling modification has become an important research topic.

Generally speaking, particles with a particle size between 1 and 100 nm and obvious surface effects are called nanoparticles or nanoparticles, and composite materials with a dispersed phase at least in one dimension between 1 and 100 nm are called nanoparticles. for nanocomposites. Due to the large specific surface area and high surface activity of nanoparticles, there are four major effects: small size effect, surface (volume) effect, quantum size effect and macroscopic quantum effect, which have peculiar physical and chemical properties. The use of nanoparticle filling modification is an important means to form high-performance composite materials. Nanocomposite materials have special properties that conventional composite materials do not have because of their nanostructures. Therefore, the preparation of nanoparticle composite materials has become a current research hotspot. The birth of nanoparticles has added new content to the research of composite materials. The nanocomposite system is different from the usual polymer inorganic system. The interfacial force between the nanoparticles and the matrix is very strong, so that the nanocomposite system exhibits excellent mechanical properties. . In recent years, new uses of nanomaterials have been continuously developed, and the research work is very active. At present, the research on nanomaterials mainly focuses on the reinforcement and toughening of polymers. The modulus of epoxy resin is low, and when it is used as the matrix of composite materials, the mechanical properties cannot be fully exerted.

Inorganic rigid particle filling is a simple and effective method to toughen and strengthen polymer matrix. Due to the special structure of nano-silica particles, it exhibits peculiar physical and chemical properties, such as excellent mechanical, optical, electromagnetic Chemical, adsorption and other properties. Nano-inorganic particles are obviously different from conventional powder fillers by their unique surface effect, volume effect and quantum effect. Nano-scale inorganic particles have good effect and high efficiency on polymer modification, and the addition of nanoparticles to epoxy resin can not only improve the toughness of epoxy resin, but also improve the mechanical properties and heat resistance of epoxy resin.

The nano-silica in the composite material not only inherits the excellent filling properties of ordinary silica, but also makes the composite material have more excellent properties. Therefore, nano- _SiO2 can be used to prepare various resins, coatings, catalyst carriers, etc., and is an excellent Reinforcement material. In addition, nano-TiO ₂ and CaCO ₃ are used as reinforcing materials to prepare nano-composite materials to achieve the effect of strengthening, toughening and rigidizing epoxy resin, so as to give full play to the mechanical properties of epoxy resin. By finely controlling the dispersion and compounding of nanomaterials in polymers, it can reinforce and fill the weaker micro-regions of the resin, increase the interface force and reduce the free volume.

Contents of the invention

In order to improve the shortcomings of epoxy resin such as brittleness, poor fatigue resistance, heat resistance, and impact resistance, as well as the shortcomings of peel strength, low cracking strain, and poor heat and humidity resistance, the present invention selects three kinds of inorganic nano fillers, through Finely controlling the dispersion and compounding of nanomaterials in polymers can reinforce and fill weaker resin micro-regions, increase interfacial force, and reduce free volume. Prepare nano-composite materials to achieve the effect of strengthening, toughening and stiffening epoxy resin, so as to give full play to the mechanical properties of epoxy resin

The invention provides a method for preparing composite nanoparticle-modified epoxy resin with significantly improved strength, toughness, rigidity and other properties. The specific method is: comprising 100 parts by weight of epoxy resin, 18-78 parts of curing agent phenolic resin, 1.5-4.5 parts of curing accelerator, 750-1635 parts of composite inorganic nano filler and 3.5-13.5 parts of silicone oil modified 10-35 parts of triphenyl phosphate as a flame retardant, wherein the composite inorganic nano filler is a mixture of (A) nano-SiO ₂ , (B) nano-CaCO ₃ , (C) nano-TiO ₂ , of which 15-40nm Part A accounts for 40-80% of the total weight percentage; Part B of 20-35nm accounts for 10-40%; Part C of 35-50nm accounts for 5-30%. The composition of the invention has excellent fluidity and filling property, and reduces absorption rate at the same time, and is used for encapsulating large-scale and ultra-large-scale integrated circuits.

Detailed ways

The invention will be further understood from the following illustrative practice.

The composite nanoparticle modified epoxy resin was prepared by using epoxy resin, phenolic resin, curing accelerator, composite nanoparticle filler and silicone oil modifier.

Example 1

The ratio of raw materials is: including 100 parts by weight of epoxy resin, 18-78 parts of curing agent phenolic resin, 1.5-4.5 parts of curing accelerator, 750-1635 parts of composite inorganic nano-filler and 3.5-13.5 parts of silicone oil Modifier, 10-35 parts of triphenyl phosphate as a flame retardant, wherein the composite inorganic nano filler is a mixture of (A) nano-SiO ₂ , (B) nano-CaCO ₃ , (C) nano-TiO ₂ , wherein 15-40nm Part A of the product accounts for 40-80% by weight of the total amount; part B of 20-35nm accounts for 10-40%; part C of 35-50nm accounts for 5-30%.

Example 2

The ratio of raw materials is: including 100 parts by weight of epoxy resin, 18-78 parts of curing agent phenolic resin, 1.5-4.5 parts of curing accelerator, 750-1635 parts of composite inorganic nano-filler and 3.5-13.5 parts of silicone oil Modifier, 10-35 parts of triphenyl phosphate as a flame retardant, wherein the composite inorganic nano filler is a mixture of (A) nano-SiO ₂ , (B) nano-CaCO ₃ , (C) nano-TiO ₂ , wherein part A accounts for 60% of the total weight percentage; Part B accounts for 30%; Part C accounts for 10%.

Example 3

A preparation of nano-modified epoxy resin, comprising 100 parts by weight of epoxy resin, 18-78 parts of curing agent phenolic resin, 1.5-4.5 parts of curing accelerator, 750-1635 parts of composite inorganic nano filler and 3.5-13.5 parts of silicone oil modifier, 10-35 parts of triphenyl phosphate as flame retardant, wherein the composite inorganic nano filler is (A) nano-SiO ₂ , (B) nano-CaCO ₃ , (C) nano-TiO ₂ The mixture, wherein part A accounts for 80% by weight of the total amount; part B accounts for 15%; and part C accounts for 5%.

Composite nano-modified epoxy resin main technical performance index of the present invention:

Glass transition temperature Tg 125°C—138°C

Bending strength 118—135Mpa

Flexural modulus 12.5—13.2Gpa

Tensile strength 31—63Mpa

Impact strength 18—44kJ/m ²

The composite nano particle modified epoxy resin prepared by the invention is suitable for encapsulating large-scale and ultra-large-scale integrated circuits.

Claims (6)

1, a kind of preparation of composite nano particle modified epoxy resin is characterized in that: Resins, epoxy, solidifying agent resol, curing catalyst, composite nano inoganic filler and silicon oil modified dose have prepared a kind of composite nano particle modified epoxy resin.

2, according to the described preparation method of claim 1, it is characterized in that: the composite nano inoganic filler is nanometer SiO ₂, nanometer CaCO ₃, nano-TiO ₂Mixture.

3, according to the described preparation method of claim 2, it is characterized in that: at following surface treated nanometer Si0 of high-speed stirring state ₂, nanometer CaCO ₃, nano-TiO ₂Join in the acetone, used ultrasonication then tens 50 minutes.

4, according to the described preparation method of claim 3, it is characterized in that: under the high-speed stirring state, above-mentioned solution and Resins, epoxy are mixed, deviate from solvent, be warming up to 130 ℃, use ultrasonication 1h.

5, according to the described preparation method of claim 4, it is characterized in that: on the high speed homogenization dispersion machine, disperse 20min.

6, according to the described preparation method of claim 5, it is characterized in that: cooling back adds an amount of solidifying agent, mixes, pour into after finding time to outgas to scribble in the good steel die of releasing agent and preheating, and behind the temperature programming completion of cure, cooling and demolding.