CN101570590A - Preparation method for organically-modified nano-silica/nylon 66 composite material - Google Patents
Preparation method for organically-modified nano-silica/nylon 66 composite material Download PDFInfo
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- CN101570590A CN101570590A CNA2009100435267A CN200910043526A CN101570590A CN 101570590 A CN101570590 A CN 101570590A CN A2009100435267 A CNA2009100435267 A CN A2009100435267A CN 200910043526 A CN200910043526 A CN 200910043526A CN 101570590 A CN101570590 A CN 101570590A
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Abstract
The invention discloses an organically-modified nano-silica/nylon 66 composite material and a preparation method thereof. The method has the following advantages that: 1) the surface of nano-silica subjected to chemical modification has an epoxy group, an amino-group and other groups, the nano-silica can react with binary acid to form a chemical bond which is subjected to ultrasonic dispersion so as to reduce the agglomeration phenomenon of nano-silica particles, improve the dispersibility of the nano-silica and further obtain the composite material with good dispersibility; and 2) in the preparation process, a GSH-2 type high-pressure autoclave is adopted to prepare the composite material by in-situ polymerization, and the method has certain directive significance on industrialized production of the composite material.
Description
Technical field
The invention belongs to the technical field of high molecule nano composite material, be specifically related to the preparation method of organically-modified nano-silica silicon/nylon 66 composite material.
Background technology
Because surface effects, volume effect, the quantum size effect of nanoparticle, add that density polymer is little, intensity is high, good characteristic such as corrosion-resistant, easy processing, nano material has caused extensive concern at home and abroad in recent years, becomes the emphasis and the focus of Materials science research.Nylon 66 belongs to AABB type nylon, AABB type nylon has the physical strength height, the characteristics that rigidity is big are the principal item of engineering plastics, are usually used in production intensity height, wear-resisting, various trolley parts that self lubricity is good, mechanical part, electronic apparatus wrapping material etc.Shortcomings such as but also there is low temperature in AABB type nylon and the dry state shock strength is poor, water-intake rate is big, notched Izod impact strength is low.Study on the modification at these shortcomings is a lot, adopts nanometer particle-modified AABB type nylon to obtain development at full speed.At present, the preparation method of nano composite material mainly contains sol-gel method, graft process, blending method, situ aggregation method etc., the whole bag of tricks all exists how to avoid being separated in the nano composite material preparation process in various degree, increases the problem of the interface interaction of nanoparticle and body material.Though though the research of research research nano silicon/nylon 66 composite material is more, major part all concentrates on the method that adopts mechanical blending, the dispersiveness of nano silicon in matrix is not good, and improved performance is limited.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of organically-modified nano-silica silicon/nylon 66 composite material.Adopt the in-situ modified nano-silicon dioxide particle of silane coupling agent, make its surface carry epoxy group(ing), amino groups.Adopt situ aggregation method to prepare organically-modified nano-silica silicon/nylon 66 composite material, make the group on the nano-silica surface participate in polyreaction, improve the interface binding power of the dispersiveness of nano silicon in matrix and enhancing nano silicon and nylon matrix, lay the first stone for preparing high performance nano composite material.
The objective of the invention is to realize in the following way: a kind of preparation method of organically-modified nano-silica silicon/nylon 66 composite material:
A, elder generation join 10-60wt% part tetraethoxy in the 30-80wt% anhydrous ethanol solvent, mechanical stirring adds 4-16wt% distilled water again, adds 0.1-3wt% ammoniacal liquor then as catalyzer, at 40-60 ℃ of hydrolysis 6-10h, obtain the suspension of nano silicon, ethanol and ammoniacal liquor;
B, the 0.5-3wt% organic modifiers joined in the suspension of nano silicon, ethanol and ammoniacal liquor of 97-99.5wt%,, obtain the suspension of organically-modified nano-silica silicon, ethanol and ammoniacal liquor at 40-60 ℃ of reaction 6-10h;
C, 33-67wt% distilled water joined in the suspension of organically-modified nano-silica silicon, ethanol and ammoniacal liquor of 33-67wt%, under 50-65 ℃, vacuumize and remove ethanol and ammoniacal liquor, obtain organically-modified nano-silica silicon suspension;
D, organically-modified silica suspension is joined in the nylon salt, add distilled water, be made into the nylon salt aqueous solution of 65-70wt% concentration, in 45-55 ℃ of water ultrasonic 15-20 minute then, obtain organically-modified nano-silica silicon and nylon salt mixed solution;
E, organically-modified nano-silica silicon and nylon salt mixed solution are joined in the polymeric kettle, at 200-230 ℃, 1.6-1.8MPa prepolymerization 1-3h, then at 265-275 ℃,-0.01 to-0.04MPa polymerization 10-30 minute, after water-cooled, pelletizing, drying, promptly get organically-modified nano-silica silicon/nylon 66 composite material.
Described organic modifiers is a silane coupling agent.
Described silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyldiethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl three ethoxy silane or N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
The present invention has following beneficial effect, 1) nano-silica surface epoxy group(ing), amino groups on the chemically modified band, can form chemical bond with diprotic acid, diprotic acid reaction, and through ultra-sonic dispersion, therefore reduced the agglomeration of nano-silicon dioxide particle, improve the dispersiveness of nano silicon, and then obtained the matrix material of good dispersion property.2) in the preparation process, adopt GSH-2 type autoclave in-situ polymerization to prepare this matrix material, its suitability for industrialized production is had certain directive significance.
Embodiment
Following embodiment is that the present invention will be further described:
Embodiment 1
The first step: the preparation of organically-modified nano-silica silicon
With the tetraethoxy of 40mL, the 80mL dehydrated alcohol, 12mL distilled water joins in the there-necked flask of 500mL, is warming up to 45 ℃, adds ammoniacal liquor 2.0mL behind the mechanical stirring 10min, hydrolysis 6-8h.Add silane coupling agent γ-An Bingjisanyiyangjiguiwan 1.2mL then, 45 ℃ are continued reaction 8h.Add 100mL distilled water then, vacuumize under 50 ℃ and remove ethanol and ammoniacal liquor, promptly get the suspension of 100mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon, wherein the siliceous amount of γ-An Bingjisanyiyangjiguiwan organically-modified nano-silicaization is 10g.
Second step: the preparation of organically-modified nano-silica silicon/nylon 66 composite material
With above-mentioned system the suspension of 100mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon join in the 990g nylon salt, add distilled water again to 1430g, be made into the nylon salt aqueous solution of 69.2wt% concentration, at 50 ℃ of ultrasonic 15min, then this mixing solutions is joined in the polymerization reaction kettle, at 200-230 ℃, 1.6-1.8Mpa prepolymerization 1-3h, then at 265-275 ℃,-0.01Mpa polymerization 10-30min promptly gets organically-modified nano-silica silicon/nylon 66 composite material
Embodiment 2
The first step: the preparation of organically-modified nano-silica silicon
With the tetraethoxy of 80mL, the 160mL dehydrated alcohol, 24mL distilled water joins in the there-necked flask of 500mL, is warming up to 50 ℃, and mechanical stirring adds ammoniacal liquor 4.0mL behind the 5min, hydrolysis 8h.Add silane coupling agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 2.4mL then, 50 ℃ are continued reaction 8h.Add 200mL distilled water then, vacuumize under 65 ℃ and remove ethanol, promptly get 200mL γ-(2,3-epoxy third oxygen) suspension of propyl trimethoxy silicane organically-modified nano-silica silicon, wherein γ-(2,3-epoxy third oxygen) siliceous amount of propyl trimethoxy silicane organically-modified nano-silicaization is 20g.
Second step: the preparation of organically-modified nano-silica silicon/nylon 66 composite material
With above-mentioned system 200mL γ-(2,3-epoxy third oxygen) suspension of propyl trimethoxy silicane organically-modified nano-silica silicon joins in the 980g nylon salt, add distilled water again to 1430g, be made into the nylon salt aqueous solution of 68.5wt% concentration, at 50 ℃ of ultrasonic 15min, then this mixing solutions is joined in the polymerization reaction kettle, at 200-230 ℃, 1.6-1.8Mpa prepolymerization 1-3h, then at 265-275 ℃,-0.02Mpa polymerization 10-30min promptly gets organically-modified nano-silica silicon/nylon 66 composite material.
Embodiment 3
The first step: the preparation of organically-modified nano-silica silicon
With the tetraethoxy of 120mL, the 240mL dehydrated alcohol, 36mL distilled water joins in the there-necked flask of 1000mL, is warming up to 55 ℃, and mechanical stirring adds ammoniacal liquor 6.0mL behind the 5min, hydrolysis 8h.Add silane coupling agent γ-An Bingjisanyiyangjiguiwan 3.6mL then, 55 ℃ are continued reaction 8h.Add 300mL distilled water then, vacuumize under 65 ℃ and remove ethanol, promptly get the suspension of 300mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon, wherein the siliceous amount of γ-An Bingjisanyiyangjiguiwan organically-modified nano-silicaization is 30g.
Second step: the preparation of organically-modified nano-silica silicon/nylon 66 composite material
The suspension of the 300mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon of above-mentioned system is joined in the 960g nylon salt, add distilled water again to 1430g, be made into the nylon salt aqueous solution of 67.1wt% concentration, at 50 ℃ of ultrasonic 15min, then this mixing solutions is joined in the polymerization reaction kettle, at 200-230 ℃, 1.6-1.8Mpa prepolymerization 1-3h, then at 265-275 ℃,-0.03Mpa polymerization 10-30min promptly gets organically-modified nano-silica silicon/nylon 66 composite material.
Embodiment 4
The first step: the preparation of organically-modified nano-silica silicon
With the tetraethoxy of 160mL, the 320mL dehydrated alcohol, 48mL distilled water joins in the there-necked flask of 1000mL, is warming up to 50 ℃, and mechanical stirring adds ammoniacal liquor 8.0mL behind the 5min, hydrolysis 8h.Add silane coupling agent γ-An Bingjisanyiyangjiguiwan 4.8mL then, 50 ℃ are continued reaction 8h.Add 400mL distilled water then, vacuumize under 65 ℃ and remove ethanol, promptly get the suspension of 400mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon, wherein the siliceous amount of γ-An Bingjisanyiyangjiguiwan organically-modified nano-silicaization is 40g.
Second step: the preparation of organically-modified nano-silica silicon/nylon 66 composite material
The suspension of the 400mL γ-An Bingjisanyiyangjiguiwan organically-modified nano-silica silicon of above-mentioned system is joined in the 940g nylon salt, add distilled water again to 1430g, be made into the nylon salt aqueous solution of 65.7wt% concentration, at 50 ℃ of ultrasonic 15min, then this mixing solutions is joined in the polymerization reaction kettle, at 200-230 ℃, 1.6-1.8Mpa prepolymerization 1-3h, then at 265-275 ℃,-0.04Mpa polymerization 10-30min promptly gets organically-modified nano-silica silicon/nylon 66 composite material.
Claims (3)
1, a kind of preparation method of organically-modified nano-silica silicon/nylon 66 composite material:
A, elder generation join 10-60wt% part tetraethoxy in the 30-80wt% anhydrous ethanol solvent, mechanical stirring adds 4-16wt% distilled water again, adds 0.1-3wt% ammoniacal liquor then as catalyzer, at 40-60 ℃ of hydrolysis 6-10h, obtain the suspension of nano silicon, ethanol and ammoniacal liquor;
B, the 0.5-3wt% organic modifiers joined in the suspension of nano silicon, ethanol and ammoniacal liquor of 97-99.5wt%,, obtain the suspension of organically-modified nano-silica silicon, ethanol and ammoniacal liquor at 40-60 ℃ of reaction 6-10h;
C, 33-67wt% distilled water joined in the suspension of organically-modified nano-silica silicon, ethanol and ammoniacal liquor of 33-67wt%, under 50-65 ℃, vacuumize and remove ethanol and ammoniacal liquor, obtain organically-modified nano-silica silicon suspension;
D, organically-modified silica suspension is joined in the nylon salt, add distilled water, be made into the nylon salt aqueous solution of 65-70wt% concentration, in 45-55 ℃ of water ultrasonic 15-20 minute then, obtain organically-modified nano-silica silicon and nylon salt mixed solution;
E, organically-modified nano-silica silicon and nylon salt mixed solution are joined in the polymeric kettle, at 200-230 ℃, 1.6-1.8MPa prepolymerization 1-3h, then at 265-275 ℃,-0.01 to-0.04MPa polymerization 10-30 minute, after water-cooled, pelletizing, drying, promptly get organically-modified nano-silica silicon/nylon 66 composite material.
2, the preparation method of organically-modified nano-silica silicon/nylon 66 composite material according to claim 1 is characterized in that: described organic modifiers is a silane coupling agent.
3, the preparation method of organically-modified nano-silica silicon/nylon 66 composite material according to claim 2, it is characterized in that: described silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyldiethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl three ethoxy silane or N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
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Assignee: Zhuzhou Jingyu Industrial Co.,Ltd. Assignor: Xiangtan University Contract record no.: 2011430000251 Denomination of invention: Preparation method for organically-modified nano-silica/nylon 66 composite material Granted publication date: 20110413 License type: Exclusive License Open date: 20091104 Record date: 20111024 |
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