CN1268682C - Nano composite material of polystyrene-maleic anhydride/kaoline - Google Patents
Nano composite material of polystyrene-maleic anhydride/kaoline Download PDFInfo
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- CN1268682C CN1268682C CN 200410026502 CN200410026502A CN1268682C CN 1268682 C CN1268682 C CN 1268682C CN 200410026502 CN200410026502 CN 200410026502 CN 200410026502 A CN200410026502 A CN 200410026502A CN 1268682 C CN1268682 C CN 1268682C
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- maleic anhydride
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Abstract
The present invention relates to a polystyrene-maleic anhydride/kaoline nanometer composite material and a preparation method thereof. The nanometer composite material is prepared from nanometer kaoline inorganic phases dispersed in a continuous phase of a polystyrene-maleic anhydride high polymer, wherein the weight content of the inorganic phases accounts for 1 to 30 % of the weight of the high polymer. The preparation steps of the nanometer composite material comprise: firstly, 100 portions of maleic anhydride and 1.0 to 30 portions of kaoline modified by organic intercalation are dispersed in 100 to 500 portions of solvent and then added into 100 to 140 portions of styrene monomer containing a free radical initiator, and the temperature is raised to initiate a reaction at the temperature of 60 to 110DEG C for 2 to 4 hours; secondly, the reaction product is poured into a precipitating agent, precipitated, washed and dried to obtain the product. Compared with an uncompounded high polymer, the composite material has the advantages of outstanding high temperature resisting performance and favorable application prospects.
Description
Technical field
The present invention relates to high polymer/inorganic thing nano composite material and preparation method thereof, especially polystyrene-maleic anhydride (SMA)/kaolin nano composite material and preparation method thereof.
Technical background
The inorganic materials that is external phase (matrix) with the superpolymer, has a nanostructure distributes wherein by specific rule with nano-scale, unique effect with low add-on performance nano material, cause performance of composites to be improved largely or give the novel high polymer matrix material of its peculiar function, be referred to as polymer/inorganic thing nano composite material.
Polymer/inorganic thing nano composite material is one of effective way of improving traditional material performance and exploitation novel material.The polymer/inorganic nanometer matrix material is with its high heat resistance, high strength, high gas-obstructing character and low special performances such as the coefficient of expansion, be expected to be used widely at aspects such as aviation, automobile, household electrical appliances, electronics, building, food product pack, this will provide the novel material of excellent performance for economic construction.
Realize great-leap-forward development in order to ensure economy, in new round competition, keep good momentum, support as the electronic information of giving priority to, biotechnology and novel material, the development nanotechnology, promote conventional industries, develop novel high-tech industry, listed the overall plan of state key development in.The raw mineral materials kaolin that reserves are enriched in employing is base material, Technology requirement according to final use properties and processing process, by online treatment or to the aftertreatment of existing commercial product targetedly in its production process, the polymkeric substance of processability excellence/kaolin nano composite material is to promote the macromolecular material industrial upgrading.Along with the China's entry into the WTO and the arriving in kownledge economy age, strengthen nanotechnology and have application in the conventional industries of advantage, can well drive the transformation of conventional industries and the upgrading of product at high molecule plastic and rubber, functional paint, building materials, weaving, fine chemistry industry and light industry etc.
The approach for preparing such matrix material has substantially:
(1) original position forms nano unit in the polymeric matrix, and in matrix uniform distribution or press the polymkeric substance condensed state structure and assemble;
(2) nano unit exists down, and monomer or performed polymer in-situ polymerization generate polymeric matrix, and constitutes the assembling thing by its specific interaction;
(3) nano unit and polymkeric substance generate simultaneously;
(4) synthetic or by natural product and intercalation thereof, peel off disperse and nano unit and the direct blend of polymkeric substance (the common grinding in preparing as coating, the fusion coextrusion in the plastic working) etc.Wherein polymeric matrix comprises thermoplasticity and thermoset two big classes.
What adopt mostly at present is the 4th kind of method, and the present invention's employing is second method.
Kaolinic chemical formula is Al
4(Si
4O
10) (OH)
8, be a kind of 1: 1 type layered silicate, each crystal layer unit is formed by common oxygen is interconnection by one deck silicon-oxy tetrahedron and layer of aluminum oxygen octahedra.Kaolin is different with polynite, interlayer does not contain exchangable ion, and linked together tightly by hydrogen bond between the crystal layer, the intercalation effect of guest molecule is difficulty relatively, have only minority polar small molecules such as dimethyl sulfoxide (DMSO) (DMSO), methane amide (FA), dimethyl formamide (DMF) etc. can directly insert the kaolin interlayer, other organic molecules then form intercalated compound by mode and the kaolin that replaces.
Selected for use the stronger maleic anhydride of polarity to insert thing among the present invention and replaced DMSO as quadratic-layer, FA or DMF, and carry out in-situ polymerization with vinylbenzene, clay mineral is peeled off, form the base material the inside of lamella uniform distribution and superpolymer, reach the purpose of improving the superpolymer physical and mechanical properties.Simultaneously, it also has undersaturated pair of key and reactive functionality, can carry out further modification.
Summary of the invention
The object of the invention is to provide a kind of high transparent, high temperature-resistant polymer/inorganics nano composite material, and the single relatively superpolymer of this material has higher second-order transition temperature.
Another object of the present invention provides the preparation method of this matrix material, under gentle relatively reaction conditions, and the synthetic coating that contains with the transparent SMA/ kaolin of molecular level compound nano composite material.
Height provided by the invention is transparent, heat resistant polymer/inorganics nano composite material is polystyrene-maleic anhydride/kaolin nano composite material, the inorganic phase of nano kaoline that is scattered here and there in polystyrene-maleic anhydride superpolymer external phase, wherein the weight content of inorganic phase is the 1-30% of superpolymer weight.
Wherein this polystyrene-maleic anhydride superpolymer is a random copolymers, and molecular weight is generally 10,000～30,000.Generally between 10～200nm, weight content is preferably the 1-15% of superpolymer weight to the size of inorganic phase in the matrix material.
The preparation method who contains this matrix material carries out reaction in and dispersion by polymer monomer in layered silicate, compound with the assembling, it is synthetic that to have a molecular level compound height transparent, high temperature-resistant polymer/inorganic nano composite material, its step comprises: the kaolin through the organic intercalation modification of 100 parts maleic anhydrides and 1.0～30 parts is scattered in 100～500 parts the solvent, high-speed stirring, form stabilized uniform suspension system, join in 100～140 parts of styrene monomers that contain 0.01～4 part of radical initiator thereafter, high-speed stirring, and elevated temperature to 60～80 ℃ quick initiation reaction, between 60～110 ℃, stirring reaction 2～4 hours, then polymers soln is poured in 1000～5000 parts the precipitation agent, make its precipitation, and filtration washing, drying obtains the white powder product; Above umber all by weight.
Wherein used kaolin is through the organic intercalation modification, and this organic intercalation agent can be dimethyl sulfoxide (DMSO) (DMSO), methane amide (FA), dimethyl formamide (DMF) etc.Used modified kaolin preferably is crushed to suitable particle diameter, available pulverizer, and ball mill, vibration mill etc. are crushed to required grain size, generally about 1～30 μ m.
The weight ratio of used modified kaolin and vinylbenzene and maleic anhydride is 1～30: 100～140: 100, when modified kaolin content is lower than 1 part, second-order transition temperature does not have too big variation, after content surpasses 30 parts, Drawing abillity is affected, therefore, the consumption umber of preferred modified kaolin is 1～15.
Used radical initiator is a Potassium Persulphate, peroxide type initiator or oxidation-reduction type initiators such as ammonium persulphate or benzoyl peroxide.
Used solvent is a benzene, toluene, acetone or N,N-DIMETHYLACETAMIDE, dimethyl formamide etc. and superpolymer consistency preferred organic solvents, preferred benzene, toluene, acetone.
Precipitation agent is pure type organics such as methyl alcohol, ethanol, tetracol phenixin.。
Kaolin used among the present invention is through the organic intercalation modification, and this organic intercalation solvent can be DMSO, FA, DMF etc.Therefore modified kaolin and organic solvent have good consistency in the present invention, simultaneously it and maleic anhydride can form stronger hydrogen bond action, in the process of reaction, replace organic solvent, then carry out in-situ polymerization with vinylbenzene, make kaolin exfoliated, and be dispersed in the polymer matrix.This polymerization adopts the method for solution polymerization to carry out, and reaction type belongs to radical polymerization.In this polystyrene-maleic anhydride/kaolin nano composite material, kaolin is distributed in the superpolymer with nano-scale, and presents exfoliated.The product that obtains is dissolved in the solvent, and the system film can obtain transparent coffee-like film.
Can operate according to the following steps during concrete the preparation:
(a) kaolin through the organic intercalation modification of getting 100～140 parts of maleic anhydrides and 1.0～30 parts is scattered in 100～500 parts the solvent, and high-speed stirring forms stabilized uniform suspension system;
(b) be to be added with below 50 ℃ in 100 parts of styrene monomers of 0.01～4 part of radical initiator at temperature control, slowly drip suspension system through the preparation of (a) step, and high-speed stirring;
(c) dropwise after, rising temperature of reaction to 60～80 ℃, initiation reaction makes it to begin polymerization;
(d) continuous elevated temperature makes its polymerization, when solution becomes coffee-like thick liquid, stops to heat up and stirring; To in the product of (d) step is poured 1000～5000 parts precipitation agent into, obtain white depositions at last, after filtration, washing, drying, obtain the white powder product.
The present invention obtains polystyrene-maleic anhydride/kaolin nano composite material by the kaolin after the organic intercalation modification and maleic anhydride and cinnamic monomer are carried out in-situ suspension polymerization.Kaolin is exfoliated by superpolymer in this matrix material, and is dispersed in nano-scale in the matrix of phenylethylene/maleic anhydride copolymer.This kind matrix material has outstanding high temperature resistance, and the second-order transition temperature ratio does not have the compound superpolymer can improve about 20 ℃.According to the kaolin content, matrix material is compared with blank sample, and heat decomposition temperature improves 80～125 ℃, and the carbon deposition rate in the time of 550 ℃ (char residue) improves 3～20%, has improved Properties of Polymer greatly, has a good application prospect.
Embodiment
Embodiment 1
0.25g DMSO intercalation modifying kaolin and 14g maleic anhydride are dissolved in the solvent of 15ml, and high-speed stirring 1 hour obtains homodisperse liquid A, A slowly is added dropwise in the 10g vinylbenzene that contains the 0.1g benzoyl peroxide, and stirs, be warming up to 70 ℃ then, stirred 1 hour, and be warming up to 95 ℃ again and make its polymerization 1 hour, obtain coffee-like thick liquid, stirring at normal temperature 1 hour is poured in the methyl alcohol of 150ml then, and the limit bevelling stirs, obtain white precipitate, filter, washing obtains white powder B.B placed under 60 ℃ of the vacuum drying ovens slough unreacted vinylbenzene and residual solvent, obtain product.Product is dissolved in the solvent, the system film, oven dry obtains transparent coffee-like film.
Embodiment 2
1.2g DMSO intercalation modifying kaolin and 10g maleic anhydride are dissolved in the solvent of 17ml, and high-speed stirring 1 hour obtains homodisperse liquid A, A slowly is added dropwise in the 12g vinylbenzene that contains the 0.2g benzoyl peroxide, and stirs, be warming up to 75 ℃ then, stirred 1.5 hours, and be warming up to 98 ℃ again and make its polymerization 1 hour, obtain coffee-like thick liquid, stirring at normal temperature 1 hour is poured in the methyl alcohol of 200ml then, and the limit bevelling stirs, obtain white precipitate, filter, washing obtains white powder B.B placed under 60 ℃ of the vacuum drying ovens slough unreacted vinylbenzene and residual solvent, obtain product.Product is dissolved in the solvent, the system film, oven dry obtains transparent light coffee color film.
Embodiment 3
2.4g DMSO intercalation modifying kaolin and 10g maleic anhydride are dissolved in the solvent of 20ml, and high-speed stirring 1 hour obtains homodisperse liquid A, A slowly is added dropwise in the 10g vinylbenzene that contains the 0.05g ammonium persulphate, and stirs, be warming up to 65 ℃ then, stirred 1 hour, and be warming up to 100 ℃ again and make its polymerization, obtain coffee-like thick liquid, stirring at normal temperature 1 hour is poured in the methyl alcohol of 130ml then, and the limit bevelling stirs, obtain white precipitate, filter, washing obtains white powder B.B placed under 60 ℃ of the vacuum drying ovens slough unreacted vinylbenzene and residual solvent, obtain product.Product is dissolved in the solvent, the system film, oven dry obtains transparent coffee-like film.
Embodiment 4
3.6g DMSO intercalation modifying kaolin and 10g maleic anhydride are dissolved in the solvent of 25ml, and high-speed stirring 1 hour obtains homodisperse liquid A, A slowly is added dropwise in the 14g vinylbenzene that contains the 0.2g ammonium persulphate, and stirs, be warming up to 65 ℃ then, stirred 1.5 hours, and be warming up to 100 ℃ again and make its polymerization 1 hour, obtain coffee-like thick liquid, stirring at normal temperature 0.5 hour is poured in the methyl alcohol of 170ml then, and the limit bevelling stirs, obtain white precipitate, filter, washing obtains white powder B.B placed under 60 ℃ of the vacuum drying ovens slough unreacted vinylbenzene and residual solvent, obtain product.Product is dissolved in the solvent, the system film, oven dry obtains transparent coffee-like film.
Embodiment 5
6.0g DMSO intercalation modifying kaolin and 10g maleic anhydride are dissolved in the solvent of 25ml, and high-speed stirring 1 hour obtains homodisperse liquid A, A slowly is added dropwise in the 14g vinylbenzene that contains the 0.2g ammonium persulphate, and stirs, be warming up to 70 ℃ then, stirred 1.5 hours, and be warming up to 110 ℃ again and made its polymerase 10 .5 hour, obtain coffee-like thick liquid, stirring at normal temperature 1 hour is poured in the methyl alcohol of 200ml then, and the limit bevelling stirs, obtain white precipitate, filter, washing obtains white powder B.B placed under 60 ℃ of the vacuum drying ovens slough unreacted vinylbenzene and residual solvent, obtain product.Product is dissolved in the solvent, the system film, oven dry obtains translucent coffee-like film.
Claims (10)
1, a kind of polystyrene-maleic anhydride/kaolin nano composite material, the inorganic phase of nano kaoline that in polystyrene-maleic anhydride superpolymer external phase, is scattered here and there, wherein the weight content of inorganic phase is the 1-30% of superpolymer weight.
2, the matrix material of claim 1, wherein the polystyrene-maleic anhydride superpolymer is a random copolymers, molecular weight is 1～30,000.
3, claim 1 or 2 matrix material, wherein the size of inorganic phase is between 10～200nm, and weight is the 1-15% of superpolymer weight.
4, the preparation method of the arbitrary matrix material of claim 1～3, be in layered silicate, to carry out reaction in and dispersion by polymer monomer, compound with the assembling, synthesize and have molecular level compound polymer/inorganic nano composite material, its step comprises: the kaolin through the organic intercalation modification of 100 parts maleic anhydrides and 1.0～30 parts is scattered in 100～500 parts the solvent, high-speed stirring, form stabilized uniform suspension system, join in 100～140 parts of styrene monomers that contain 0.01～4 part of radical initiator thereafter, high-speed stirring, and elevated temperature to 60～80 ℃ quick initiation reaction, between 60～110 ℃, stirring reaction 2～4 hours is poured polymers soln in 1000～5000 parts the precipitation agent then, makes its precipitation, and filtration washing, drying obtains the white powder product; Above umber all by weight.
5, the method for claim 4, wherein kaolinic organic intercalation properties-correcting agent is selected from dimethyl sulfoxide (DMSO), methane amide, dimethyl formamide.
6, claim 4 or 5 method, wherein modified kaolin is crushed to 1～30 μ m, and the consumption umber is 1～15.
7, claim 4 or 5 method, wherein radical initiator is peroxide type initiator or oxidation-reduction type initiator.
8, the method for claim 7, wherein radical initiator is selected from Potassium Persulphate, ammonium persulphate and benzoyl peroxide.
9, claim 4 or 5 method, wherein solvent is selected from benzene, toluene, acetone.
10, claim 4 or 5 method, wherein precipitation agent is selected from pure type organic.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410026502 CN1268682C (en) | 2004-03-17 | 2004-03-17 | Nano composite material of polystyrene-maleic anhydride/kaoline |
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| CN 200410026502 CN1268682C (en) | 2004-03-17 | 2004-03-17 | Nano composite material of polystyrene-maleic anhydride/kaoline |
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| CN1563177A CN1563177A (en) | 2005-01-12 |
| CN1268682C true CN1268682C (en) | 2006-08-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696014B (en) * | 2009-11-12 | 2011-11-09 | 福州大学 | High-performance kaolin and in-situ polymerization preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1838764A4 (en) * | 2005-01-14 | 2009-11-04 | Agency Science Tech & Res | Thermoplastic polymer based nanocomposites |
| CN106832568B (en) * | 2016-12-21 | 2019-02-12 | 湖南登科材料科技有限公司 | A kind of enhancement filling plastic lubrication masterbatch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101696014B (en) * | 2009-11-12 | 2011-11-09 | 福州大学 | High-performance kaolin and in-situ polymerization preparation method thereof |
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