CN101457011A - Preparation of composite nano particle modified epoxy resin - Google Patents
Preparation of composite nano particle modified epoxy resin Download PDFInfo
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- CN101457011A CN101457011A CNA2007101249806A CN200710124980A CN101457011A CN 101457011 A CN101457011 A CN 101457011A CN A2007101249806 A CNA2007101249806 A CN A2007101249806A CN 200710124980 A CN200710124980 A CN 200710124980A CN 101457011 A CN101457011 A CN 101457011A
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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
Technical field
A kind of preparation of composite nano particle modified epoxy resin
Background technology
Resins, epoxy is the oligopolymer that contains two above epoxy group(ing) in the molecule, can form three-dimensional netted thermosetting resin with the solidifying agent reaction.Its research starts from early 1930s, and scale operation and application then are after 1948.Resins, epoxy (EP) is the most widely used matrix resin of polymer matrix composite.EP is a kind of thermosetting resin, have excellent cementability, wear resistance, mechanical property, electrical insulation capability, chemical stability, resistant of high or low temperature, and low, the easy machine-shaping of shrinking percentage, stress transmission preferably and advantage such as with low cost, be used widely in fields such as tackiness agent, electronic instrument, light industry, building, machinery, space flight and aviation, coating, bonding and electric insulating material, advanced composite material matrixes.But EP solidifies back cross-linking density height, be tridimensional network, have that internal stress is big, matter is crisp, deficiencies such as resistance to fatigue, thermotolerance, poor impact resistance, and stripping strength, cracking are answered shortcomings such as step-down and humidity resistance be relatively poor, surface energy height has in addition limited its application in some high-tech sector to a great extent.EP has been applied to aspects such as electric packaged material such as structure adhesives, semiconductor sealing material, fiber reinforced material, veneer sheet, Copper Foil, unicircuit in recent years, this just requires the EP material to have better properties, as obdurability, inner low stressization, thermotolerance, water tolerance, chemical proofing etc.Therefore, toughness reinforcing enhancing is one of important subject of people's modification EP always to EP.All there are the relatively poor problem of bonding interface between wild phase and resin matrix in general EP weighting agent and toughner, and it is cost that flexible improves with expendable material intensity, modulus and thermotolerance, and the raising of its physics, mechanics and thermal characteristics is restricted.
Along with the industrial high speed development of modernization, the performance of material has been proposed more and more higher requirement, low-costly realize that the high performance of material is the advanced subject of investigation of materials and application.Realize that epoxy resin high-performanceization generally has two kinds of approach: 1) development of new Resins, epoxy; 2) adopt copolymerization-blending method that existing Resins, epoxy is carried out modification.Development of new Resins, epoxy research cycle is long, cost is higher.That has reported has: add silicone resin and improve its dielectric properties in Resins, epoxy, liquid polymer is epoxy resin toughened, Resins, epoxy and acrylate resin emulsion form half latex type IPN significantly improves its cohesive strength and water tolerance, the toughness reinforcing reinforced epoxy of polycarbonate etc.
In recent years, polymkeric substance-nano composite material became the focus of people's research.Surface effects that nanoparticle is strong and volume effect make polymer materials and the compound back of nano material demonstrate special advantages at aspects such as optics, mechanical properties, for exploitation high-performance multifunctional novel material provides a new approach.Because Resins, epoxy is thermosetting resin, strong, stable height of cohesiveness and shrinking percentage are little, are the widely used a kind of body materials of present matrix material.The surface atom of nanoparticle has nonsaturation, can strengthen particle and combine with the interface of matrix, can carry out combining of physics and chemistry with Resins, epoxy.Epoxy resin nano composites is a valid approach of modified epoxy.Therefore, become important research project by filling-modified preparation epoxy resin-base composite material.
In general sense with particle diameter between 1～100nm, particle with obvious surface effects is called nano particle or nanoparticle, with disperse phase at least the matrix material of the size on the one dimension direction between 1～100nm be called nano composite material.Owing to having great specific surface area and high surfactivity, nanoparticle produced four big effects: small-size effect, surface (volume) effect, quantum size effect and macroscopic quantum effect, thus have peculiar physics and chemical property.Adopting nanoparticle filling-modified is the important means that forms high performance composite, nano composite material has the not available special property of conventional matrix material because of containing nanostructure, so the preparation of nano composition becomes the focus of current research.The birth of nanoparticle is that composite study has increased new content, and nano combined system is different with common polymer inorganic system, and the interface interaction power between nanoparticle and the matrix is very strong, makes nano combined system show excellent mechanical property.In recent years, the purposes that nano material is new constantly is developed, and research work is very active.At present, the research of relevant nano material mainly is the enhancing, toughness reinforcing to polymkeric substance.The modulus of Resins, epoxy is low, and when being used as the matrix of matrix material, mechanical property can not given full play to.
It is a kind of easy of toughness reinforcing enhancing polymeric matrix and efficient ways that inorganic rigid particle is filled, owing to having special structure, nano-silicon dioxide particle shows peculiar physics and chemical property, as mechanics, the optics of excellence, performances such as electromagnetism, absorption.Nano inoganic particle obviously is different from conventional powder filler with its unique surface effects, volume effect and quantum effect.The nano grade inorganic particle is effective to polymer modification, efficient is high, and adds nanoparticle in the Resins, epoxy improving the Resins, epoxy flexible simultaneously, also can improve the mechanical property and the thermotolerance of Resins, epoxy.
Nano silicon in the matrix material had both been inherited the good fillibility of general silica, made matrix material have excellent more performance again, so nanometer SiO
2Can be used to prepare various resins, coating, support of the catalyst etc., is excellent strongthener.In addition, with nano-TiO
2, CaCO
3Be strongthener, the preparation nano composite material, reach enhancing to Resins, epoxy, toughness reinforcing, increase firm effect, to give full play to the mechanical property of Resins, epoxy.By the dispersion of meticulous control nano material in superpolymer and compound, can in the more weak microcell of resin, play reinforcement, filling, increase interface interaction power, reduce the effect of free volume.
Summary of the invention
Crisp in order to improve Resins, epoxy matter, deficiencies such as resistance to fatigue, thermotolerance, poor impact resistance, and stripping strength, cracking are answered shortcomings such as step-down and humidity resistance be relatively poor, the present invention is by selecting three kinds of inorganic nano stopping composition, by the dispersion of meticulous control nano material in superpolymer and compound, can in the more weak microcell of resin, play reinforcement, filling, increase interface interaction power, reduce the effect of free volume.The preparation nano composite material, reach enhancing to Resins, epoxy, toughness reinforcing, increase firm effect, to give full play to the mechanical property of Resins, epoxy
The invention provides the preparation method of the composite nano particle modified epoxy resin that performances such as a kind of intensity, toughness, rigidity all significantly improve.Concrete grammar is: the Resins, epoxy that comprises 100 parts of weight parts, silicon oil modified dose, 10-35 portions triphenylphosphates of 18～78 parts solidifying agent resol, 1.5～4.5 parts curing catalyst, 750～1635 parts composite nano inoganic filler and 3.5～13.5 parts are as fire retardant, and wherein the composite nano inoganic filler is (A) nanometer SiO
2, (B) nanometer CaCO
3, (C) nano-TiO
2Mixture, wherein the A of 15～40nm partly accounts for 40～80% of total amount weight percent; The B of 20～35nm partly accounts for 10～40%; The C of 35～50nm partly accounts for 5～30%.Composition of the present invention has good flowability, and filling has reduced specific absorption simultaneously, is used for encapsulating extensive, super large-scale integration.
Embodiment
Implement will be further understood that the present invention from following illustrative.
Adopt Resins, epoxy, resol, curing catalyst, composite nanoparticle weighting agent, silicon oil modified dose of preparation composite nano particle modified epoxy resin.
Embodiment 1
Proportioning raw materials is: the Resins, epoxy that comprises 100 parts of weight parts, silicon oil modified dose, 10-35 portions triphenylphosphates of 18～78 parts solidifying agent resol, 1.5～4.5 parts curing catalyst, 750～1635 parts composite nano inoganic filler and 3.5～13.5 parts are as fire retardant, and wherein the composite nano inoganic filler is (A) nanometer SiO
2, (B) nanometer CaCO
3, (C) nano-TiO
2Mixture, wherein the A of 15～40nm partly accounts for 40～80% of total amount weight percent; The B of 20～35nm partly accounts for 10～40%; The C of 35～50nm partly accounts for 5～30%.
Embodiment 2
Proportioning raw materials is: the Resins, epoxy that comprises 100 parts of weight parts, silicon oil modified dose, 10-35 portions triphenylphosphates of 18～78 parts solidifying agent resol, 1.5～4.5 parts curing catalyst, 750～1635 parts composite nano inoganic filler and 3.5～13.5 parts are as fire retardant, and wherein the composite nano inoganic filler is (A) nanometer SiO
2, (B) nanometer CaCO
3, (C) nano-TiO
2Mixture, wherein A partly accounts for 60% of total amount weight percent; B partly accounts for 30%; C partly accounts for 10%.
Embodiment 3
A kind of preparation of nanometer modified epoxy resin, the Resins, epoxy that comprises 100 parts of weight parts, silicon oil modified dose, 10-35 portions triphenylphosphates of 18～78 parts solidifying agent resol, 1.5～4.5 parts curing catalyst, 750～1635 parts composite nano inoganic filler and 3.5～13.5 parts are as fire retardant, and wherein the composite nano inoganic filler is (A) nanometer SiO
2, (B) nanometer CaCO
3, (C) nano-TiO
2Mixture, wherein A partly accounts for 80% of total amount weight percent; B partly accounts for 15%; C partly accounts for 5%.
Composite nano modified Resins, epoxy basic mechanical design feature index of the present invention:
125 ℃-138 ℃ of second-order transition temperature Tg
Flexural strength 118-135Mpa
Modulus in flexure 12.5-13.2Gpa
Tensile strength 31-63Mpa
Shock strength 18-44kJ/m
2
The composite nano particle modified epoxy resin of the present invention's preparation is applicable to that encapsulation is extensive, super large-scale integration.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101249806A CN101457011A (en) | 2007-12-12 | 2007-12-12 | Preparation of composite nano particle modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101249806A CN101457011A (en) | 2007-12-12 | 2007-12-12 | Preparation of composite nano particle modified epoxy resin |
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| Publication Number | Publication Date |
|---|---|
| CN101457011A true CN101457011A (en) | 2009-06-17 |
Family
ID=40768145
Family Applications (1)
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|---|---|---|---|
| CNA2007101249806A Pending CN101457011A (en) | 2007-12-12 | 2007-12-12 | Preparation of composite nano particle modified epoxy resin |
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|---|---|
| CN (1) | CN101457011A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532803A (en) * | 2010-12-15 | 2012-07-04 | 颜欢 | Nanoparticle modified epoxy resin |
| CN101935491B (en) * | 2009-06-29 | 2013-07-03 | 苏州Ppg包装涂料有限公司 | Metal packaging coating for foods |
| CN103289522A (en) * | 2013-04-23 | 2013-09-11 | 安徽圣德建材科技有限公司 | Impact-resistant powder paint and preparation method thereof |
| CN103937162A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Low-temperature resin composition and preparation method thereof |
| CN107163285A (en) * | 2017-05-25 | 2017-09-15 | 句容亿格纳米材料厂 | A kind of preparation and application for the improved composite Nano high polymer material of product of rubber and plastic mechanical property |
| CN113045858A (en) * | 2021-03-09 | 2021-06-29 | 云南电网有限责任公司临沧供电局 | Tracking-resistant epoxy resin nano composite material and preparation method thereof |
| CN115449260A (en) * | 2022-10-08 | 2022-12-09 | 杭州临安柏盛印刷技术有限公司 | Preparation method of water-based ink and printing process thereof |
-
2007
- 2007-12-12 CN CNA2007101249806A patent/CN101457011A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935491B (en) * | 2009-06-29 | 2013-07-03 | 苏州Ppg包装涂料有限公司 | Metal packaging coating for foods |
| CN102532803A (en) * | 2010-12-15 | 2012-07-04 | 颜欢 | Nanoparticle modified epoxy resin |
| CN103289522A (en) * | 2013-04-23 | 2013-09-11 | 安徽圣德建材科技有限公司 | Impact-resistant powder paint and preparation method thereof |
| CN103289522B (en) * | 2013-04-23 | 2016-08-03 | 安徽圣德建材科技有限公司 | A kind of impact-resistant powdery paints and preparation method thereof |
| CN103937162A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Low-temperature resin composition and preparation method thereof |
| CN103937162B (en) * | 2014-04-11 | 2016-08-17 | 四川东材科技集团股份有限公司 | Low-temperature resins compositions and preparation method thereof |
| CN107163285A (en) * | 2017-05-25 | 2017-09-15 | 句容亿格纳米材料厂 | A kind of preparation and application for the improved composite Nano high polymer material of product of rubber and plastic mechanical property |
| CN113045858A (en) * | 2021-03-09 | 2021-06-29 | 云南电网有限责任公司临沧供电局 | Tracking-resistant epoxy resin nano composite material and preparation method thereof |
| CN115449260A (en) * | 2022-10-08 | 2022-12-09 | 杭州临安柏盛印刷技术有限公司 | Preparation method of water-based ink and printing process thereof |
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Open date: 20090617 |