CN101457020B - Nano silicon nitride/epoxy silicone hydride/cyanate ester resin composite material and preparation method thereof - Google Patents
Nano silicon nitride/epoxy silicone hydride/cyanate ester resin composite material and preparation method thereof Download PDFInfo
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- CN101457020B CN101457020B CN2007101992201A CN200710199220A CN101457020B CN 101457020 B CN101457020 B CN 101457020B CN 2007101992201 A CN2007101992201 A CN 2007101992201A CN 200710199220 A CN200710199220 A CN 200710199220A CN 101457020 B CN101457020 B CN 101457020B
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Abstract
The invention relates to a nano-silicon nitride/epoxy silane/cyanate resin composite and the preparation thereof and is characterized in that: 100 portions of cyanate resin and 1 to 20 epoxy silane are reacted and 0.5 to 10 nano-silicon nitride is added to dispersed in a high speed and then the solidification carried out according to a certain solidifying technique, therefore the nano-silicon nitride/epoxy silane/cyanate resin composite is gained. For the epoxy group inside the epoxy silane can react with the cyanate resin and moreover, the molecule has a small weight and the viscosity of the modified resin system is low, which is beneficial for the dispersion of the nano-silicon nitride, and the prepared nano-silicon nitride/epoxy/cyanate resin composite is made to be provided with good mechanical properties, good thermal properties and good dielectricity and can be used as integrated circuit plates or sealing materials in the electronic field.
Description
Technical field
The present invention relates to a kind of nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material and preparation method thereof, is a kind ofly to adopt the rigidity of nano-silicon nitride and the reactive acting in conjunction of epoxy radicals silicone hydride to prepare cyanate ester resin composite material specifically.
Background technology
Cyanate ester resin has the advantage that mechanical property is excellent, thermotolerance is high, water-intake rate is low, the more important thing is that its dielectric properties are excellent, is electronic package material resin matrix of new generation.But the same with other thermosetting resin, this resin is the crisp weakness of existence also.At present a lot of about the toughening modifying method of cyanate, mainly contain with the thermosetting resin copolymerization, with the thermoplastics blend, with elastomer blended etc.But these methods respectively have its shortcoming in toughness reinforcing.Wherein, the toughening effect of thermosetting resin modification is not remarkable, the thermotolerance of thermoplastics and elastomer-modified meeting sacrifice system.Organic-inorganic nanocomposite not only can have the characteristics and the character of inorganic materials; Thermotolerance, high-temperature stability, low thermal coefficient of expansion like inorganic materials; And can be with toughness, ductility and the workability of organic polymer; Therefore, nanometer particle-modified cyanate ester resin becomes the focus of Materials science research.But because cyanate ester resin and inorganic nano-particle are the easy agglomeration of inconsistent and nanoparticle, be unfavorable for the dispersion of inorganic particulate in resin matrix on thermodynamics, be undoubtedly a very adverse factors for preparation cyanate nano composite material.Therefore, prepare cyanate nano composite material, improve the dispersiveness of inorganic nano-particle in matrix and seem particularly important with superperformance.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes a kind of nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material and preparation method thereof, and a kind of H.T., HS and the thermotolerance of excellence and cyanate ester resin composite material of dielectric properties and preparation method thereof can be provided.
Technical scheme
Technical characterictic of the present invention is to fill a prescription to form and counts by quality: 100 parts of cyanate ester resins, 1～20 part of epoxy radicals silicone hydride, 0.5～10 part of nano-silicon nitride.
Described epoxy radicals silicone hydride is γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane.
The particle diameter of described nano-silicon nitride particle is 10～100nm, and handle through coupling agent γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane on the surface.
A kind of preparation method who prepares nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material is characterized in that preparation process is following:
(1), adds the epoxy radicals silicone hydride heated and stirred, reaction 10～50min with behind the cyanate ester resin heating and melting;
(2) in performed polymer, add nano-silicon nitride through coupling agent treatment, utilize the high speed homogenization stirrer to be uniformly dispersed after, pour in the good mould of preheating;
(3) vacuumize remove bubble after, put into baking oven and be cured, curing process is three sections continuous solidification methods: 140～160 ℃ solidified 1～4 hour down, 170～180 ℃ solidified 1～4 hour down, 190～200 ℃ solidified 1～4 hour down;
(4) at last 220～240 ℃ of following aftertreatments 2～6 hours, promptly get nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material.
Beneficial effect
The present invention is with respect to prior art, and its advantage is:
(1) the present invention adopts nano-silicon nitride and epoxy radicals silicone hydride to come modified cyanic acid ester resin simultaneously, belongs to a kind of novel trielement composite material.
(2) the present invention utilizes molecular weight little epoxy radicals silicone hydride that contains reactive group and cyanate ester monomer to react as resin matrix.The viscosity of this performed polymer is very low, and in awide temperature range, remains unchanged, and helps the dispersion of nanoparticle in resin matrix.
(3) nano-silicon nitride used in the present invention is handled through containing epoxy silane coupling.The epoxy group(ing) of this coupling agent end position can be reacted with cyanate ester monomer, increased the consistency between inorganic nano-particle and the matrix resin, has improved two alternate interfaces bonding degree
(4) nano-silicon nitride/epoxy radicals silicone hydride of the present invention/cyanate ester resin composite material has excellent mechanical property, thermal property, dielectric properties, can be used as the surface-mounted integrated circuit or the packaged material of electronic applications.
(5) preparation method of nano-silicon nitride/epoxy radicals silicone hydride of the present invention/cyanate ester resin composite material has characteristics such as operating procedure is simple, pollution-free, is the wide method for preparing organic-inorganic nanocomposite of a kind of suitability.
Embodiment
Combine embodiment that the present invention is further described at present:
Nano-silicon nitride has particular structural and shows peculiar physics and chemical property, like the thermal conductivity and the electromagnetic property of excellence, in polymer modification, is used widely.And organosilane is owing to have characteristics such as active height, good heat resistance; Aspect modified epoxy, also demonstrate the characteristic of many excellences; And organosilane usually as the coupling agent that connects between mineral filler and the organic resin, plays a kind of bridging action between inorganic phase and organic phase.
The method for preparing organic-inorganic nanocomposite is a lot, and sol-gel method, solution blended process, melt-blending process, in-situ inserted method etc. are arranged.Because organic constituent and the uncompatibility of inorganic component on thermodynamics and the easy agglomeration of nanoparticle are unfavorable for the dispersion of inorganic particulate in organic matrix.Therefore, prepare the organic-inorganic nanocomposite with superperformance, key is control inorganic particulate dispersed in organic matrix and improves two alternate consistencies.
The present invention adopts a kind of epoxy radicals silicone hydride and cyanate ester resin reaction as the modified resin matrix.This performed polymer viscosity is low; And in awide temperature range, remain unchanged; Help the dispersion of inorganic nano-particle silicon nitride, and the surface of nano-silicon nitride has increased the consistency between inorganic nano-particle and the organic resin through containing the processing of active epoxy base coupling agent.
Embodiment 1:
At first with behind 100 parts of cyanate ester resin heating and meltings; Add 6 parts of epoxy radicals silicone hydride heated and stirred, behind reaction 10～50min, add 1.0 parts of nano-silicon nitrides of handling through coupling agent KH-560 again; After utilizing the high speed homogenization stirrer to be uniformly dispersed; Pour in the good mould of preheating, vacuumize remove bubble after, put into baking oven and be cured.Curing process is three sections continuous solidification methods: 140～160 ℃ solidified 1～4 hour down, and 170～180 ℃ solidified 1～4 hour down, and 190～200 ℃ solidified 1～4 hour down.220～240 ℃ of following aftertreatments 2～6 hours, promptly get nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material at last.
Embodiment 2:
At first with behind 100 parts of cyanate ester resin heating and meltings; Add 6 parts of epoxy radicals silicone hydride heated and stirred, behind reaction 10～50min, add 2.0 parts of nano-silicon nitrides of handling through coupling agent KH-560 again; After utilizing the high speed homogenization stirrer to be uniformly dispersed; Pour in the good mould of preheating, vacuumize remove bubble after, put into baking oven and be cured.Curing process is three sections continuous solidification methods: 140～160 ℃ solidified 1～4 hour down, and 170～180 ℃ solidified 1～4 hour down, and 190～200 ℃ solidified 1～4 hour down.220～240 ℃ of following aftertreatments 2～6 hours, promptly get nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material at last.
Embodiment 3:
At first with behind 100 parts of cyanate ester resin heating and meltings; Add 6 parts of epoxy radicals silicone hydride heated and stirred, behind reaction 10～50min, add 3.0 parts of nano-silicon nitrides of handling through coupling agent KH-560 again; After utilizing the high speed homogenization stirrer to be uniformly dispersed; Pour in the good mould of preheating, vacuumize remove bubble after, put into baking oven and be cured.Curing process is three sections continuous solidification methods: 140～160 ℃ solidified 1～4 hour down, and 170～180 ℃ solidified 1～4 hour down, and 190～200 ℃ solidified 1～4 hour down.220～240 ℃ of following aftertreatments 2～6 hours, promptly get nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material at last.
The performance index of nano-silicon nitride/epoxy radicals silicone hydride of the present invention/cyanate ester resin composite material are following:
Flexural strength:＞125Mpa; Shock strength:＞13.0kJ/m
2
Specific inductivity:＜3.15; Tangent of the dielectric loss angle Tan δ:＜0.014;
Second-order transition temperature:＞260 ℃; Initial heat decomposition temperature ℃:＞410 ℃;
The corresponding temperature of maximum rate of weight loss:＞435 ℃.
Claims (4)
1. nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material is characterized in that filling a prescription forming and counts by quality: 100 parts of cyanate ester resins, 1～20 part of epoxy radicals silicone hydride, 0.5～10 part of nano-silicon nitride.
2. nano-silicon nitride/epoxy radicals silicone hydride according to claim 1/cyanate ester resin composite material is characterized in that: described epoxy radicals silicone hydride is γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane.
3. nano-silicon nitride/epoxy radicals silicone hydride according to claim 1/cyanate ester resin composite material; It is characterized in that: the particle diameter of described nano-silicon nitride particle is 10～100nm; Handle through coupling agent γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane on the surface.
4. preparation method who prepares described any the nano-silicon nitride/epoxy radicals silicone hydride of claim 1～3/cyanate ester resin composite material is characterized in that preparation process is following:
(1), adds the epoxy radicals silicone hydride heated and stirred, reaction 10～50min with behind the cyanate ester resin heating and melting;
(2) in performed polymer, add nano-silicon nitride through coupling agent treatment, utilize the high speed homogenization stirrer to be uniformly dispersed after, pour in the good mould of preheating;
(3) vacuumize remove bubble after, put into baking oven and be cured, curing process is three sections continuous solidification methods: 140～160 ℃ solidified 1～4 hour down, 170～180 ℃ solidified 1～4 hour down, 190～200 ℃ solidified 1～4 hour down;
(4) at last 220～240 ℃ of following aftertreatments 2～6 hours, promptly get nano-silicon nitride/epoxy radicals silicone hydride/cyanate ester resin composite material.
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| CN2007101992201A CN101457020B (en) | 2007-12-14 | 2007-12-14 | Nano silicon nitride/epoxy silicone hydride/cyanate ester resin composite material and preparation method thereof |
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| CN2007101992201A CN101457020B (en) | 2007-12-14 | 2007-12-14 | Nano silicon nitride/epoxy silicone hydride/cyanate ester resin composite material and preparation method thereof |
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| CN101457020B true CN101457020B (en) | 2012-05-09 |
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| CN106221213B (en) * | 2016-07-29 | 2018-08-31 | 苏州巨峰电气绝缘系统股份有限公司 | A kind of nuclear power driving mechanism high-temperature insulation structural member and preparation method thereof |
| CN106543774A (en) * | 2016-10-26 | 2017-03-29 | 安徽理工大学 | A kind of Nano powder of silicon nitride method for organic modification of surface |
| CN106589928A (en) * | 2016-11-16 | 2017-04-26 | 马鞍山市华能电力线路器材有限责任公司 | Novel wearable flame-retardant nylon composite material for electric power fittings and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020105093A1 (en) * | 2001-02-07 | 2002-08-08 | International Business Machines Corporation | Encapsulant composition and electronic package utilizing same |
| JP2005223096A (en) * | 2004-02-04 | 2005-08-18 | Matsushita Electric Ind Co Ltd | Module incorporating circuit component and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020105093A1 (en) * | 2001-02-07 | 2002-08-08 | International Business Machines Corporation | Encapsulant composition and electronic package utilizing same |
| JP2005223096A (en) * | 2004-02-04 | 2005-08-18 | Matsushita Electric Ind Co Ltd | Module incorporating circuit component and manufacturing method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 唐玉生.晶须改性氰酸酯树脂及其复合材料研究.《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》.2005,(第4期),1,16-28. * |
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