CN1156538C - Exfoliated silicone rubber/clay nanocomposite material and preparation method thereof - Google Patents
Exfoliated silicone rubber/clay nanocomposite material and preparation method thereof Download PDFInfo
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- CN1156538C CN1156538C CNB011082879A CN01108287A CN1156538C CN 1156538 C CN1156538 C CN 1156538C CN B011082879 A CNB011082879 A CN B011082879A CN 01108287 A CN01108287 A CN 01108287A CN 1156538 C CN1156538 C CN 1156538C
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Abstract
本发明提供了一种新型的剥离型硅橡胶/粘土纳米复合材料及其制备方法。其方法是利用经过有机硅表面活性剂改性的层状硅酸盐和硅橡胶生胶反应，在反应过程中硅橡胶分子链插层进入改性的层状硅酸盐的片层之间，由于插层驱动力为化学作用，所以层状硅酸盐很容易剥离成纳米量级的微粒均匀分散在硅橡胶基体中，最后得到的层状硅酸盐/硅橡胶的界面为化学键合且纳米复合材料的机械性能大幅度提高。The invention provides a novel stripping silicone rubber/clay nanocomposite material and a preparation method thereof. The method is to use the layered silicate modified by organosilicon surfactant to react with silicone rubber raw rubber. During the reaction, the molecular chain of silicone rubber is intercalated into the sheets of the modified layered silicate. Since the intercalation driving force is chemical, the layered silicate is easily exfoliated into nanometer-sized particles and uniformly dispersed in the silicone rubber matrix, and the interface of the finally obtained layered silicate/silicone rubber is chemically bonded and nanometer-sized. The mechanical properties of composite materials are greatly improved.
Description
The invention provides a kind of peel-off silastic/clay nanometer composite material and preparation method thereof, specially refer to the organic silicon surfactant of a class response type and with the organic silicon surfactant modified sheet silicate and be filled in the silicon rubber and the exfoliated nano-composite that forms.
In general, and polymer/laminated silicate (Polymer Layered Silicate, PLS) nano composite material can be divided into three types: 1. macroscopical matrix material; In this case, layered silicate generally keeps original state of aggregation, and polymkeric substance does not have intercalation in silicate layer, and promptly inorganics and polymkeric substance just mechanically mix.At this moment, layered silicate plays conventional fillers.2. intercal type hybrid material; Be that polymkeric substance is inserted in the silicate layer, but silicate still keeps original crystalline structure, the content of silicate content in the intercal type hybrid material is than higher, and general silicate content must be increased to higher degree, and mechanical property just can have more significantly raising.3. exfoliated nano-composite.Silicate layer (1nm is thick) is dispersed in the successive polymeric matrix.Compare with intercal type hybrid material mesosilicic acid salts contg, the content of modified Portland generally is very low in exfoliated nano-composite, but mechanical property can increase substantially, under the situation of same amount, the mechanical property of exfoliated nano-composite is much higher than the intercal type hybrid material, and the character of exfoliated nano-composite depends on the character of original polymer consumingly.
The cationite that Chinese patent CN1163288A selects for use is a hexadecyl trimethyl ammonium bromide, the polynite of resultant modification/silicon rubber system is the intercal type hybrid material, the intercalation motivating force of this method is a physical action, disperse phase is the body of combining closely of multilayer clay crystal layer, phase farmland size is bigger, its polynite/silicon rubber interface belongs to physical action, thereby influenced the mechanical property of matrix material, and this system must be added 10～20% modified Portland, silicon rubber just can have use value, and has increased the cost of matrix material so greatly.If make it produce the chemical graft motivating force by molecular designing, thereby form exfoliated nano-composite, then this technology will have more wide application prospect.
The purpose of this invention is to provide a kind of peel-off silastic/clay nanometer composite material and preparation method thereof.The intercalation motivating force of present method is a chemical action, and disperse phase is peeled off and is nano level individual layer clay layer, and phase farmland size is little, and its silastic/clay interface belongs to chemical action, thereby the mechanical property of matrix material significantly improves.The present invention need only add 1% modified Portland just can surpass the mechanical property that above-mentioned interpolation 20% just can reach, thereby the cost of nano composite material is reduced.
Purpose of the present invention can reach by following measure:
Peel-off silastic/clay nanometer composite material of the present invention is characterized in that the feed composition of described matrix material and content are as follows: (weight part)
Raw-silastic continuously 100
Clay 1～20
Organic silicon surfactant 0.5～10
Dispersion medium 40～1000
Linking agent 1～10
Promotor 0.1～1
The raw-silastic continuously that the present invention was suitable for is room temperature silicon rubber, high temperature silicon rubber, addition-type silicon rubber of different molecular weight etc.
The clay that the present invention was suitable for is the inorganics that a class has laminate structure, belong to the 2:1 type, each unit cell is by carrying the layer of aluminum oxygen octahedra in the middle of two silicon-oxy tetrahedrons secretly, connect by public Sauerstoffatom between the two, this tetrahedron and octahedral close-packed structure make its crystal arrangement with high-sequential, and the about 1nm of every layer thickness, length * wide is 100 * 100nm
2Lamella, interfloor distance is approximately about 1nm, the alumina octahedral top trivalent aluminium of layered silicate is made a layer internal surface have negative charge by divalence magnesium isomorphous substitution, superfluous negative charge compensates by the positively charged ion of interlayer absorption, as Na
+, K
+, Ca
2+, Mg
2+Deng, after the organic silicon surfactant effect of response type, can make polysiloxane macromonomer be inserted into interlayer at an easy rate, and then form exfoliated nano-composite.In the matrix material, smectite content in the clay＞90%, particle diameter are 30～40 μ m, and its cationic exchange total volume is preferably 70～120meq/100g.
Organic silicon surfactant of the present invention is the organic silicon surfactant of a class response type, and its structural formula skeleton symbol is (RO)
3SiR
1N
+R
2R
3R
4X
-, R is CH
3Or C
2H
5, R
1For-CH
2-or-C
3H
6-, R
2Be CH
3-or C
2H
5-, R
3Be CH
3-or C
2H
5-, R
4Be chain alkyl or aliphatics vinylformic acid and ester derivative thereof, X is Cl.
Chain alkyl of the present invention is dodecyl, hexadecyl, octadecyl; Aliphatics vinylformic acid and ester derivative thereof are CH
2=CHCOO C
2H
4-or CH
2=C (CH
3) COO C
2H
4-.
The used dispersion medium of the present invention is water, alcohols, dimethyl formamide etc., and this class dispersion medium can make clay particles disperse and cation exchange reaction carry out.
The used linking agent of the present invention can be the alkyl silane of multiple functional radical, the organoalkoxysilane of multiple functional radical etc., as tetraethoxy, silane coupling agent etc.
The used promotor of the present invention can be dibutyl tin laurate.
A kind of preparation method of peel-off silastic/clay nanometer composite material is characterized in that following these steps to carrying out:
With cation exchange capacity is 1～20 part of the clay of 50～120meq/100g, and high-speed stirring in the presence of 40～1000 parts dispersion medium forms steady suspension.0.5～10 part of organic silicon surfactant is added in the dispersion medium, and 20～40 ℃ were reacted 24～96 hours.The floss of gained after filtration, washing, dry, be organoclay composites after pulverizing.
Above-mentioned organoclay composites through the organic silicon surfactant reaction is scattered in 100 parts of raw-silastic continuouslies for 1～20 part, stir after 5～10 hours and to add 1～10 part of linking agent, 0.1～1 part of promotor is poured in the mould, at least placed 0.2～24 hour, and promptly got product for 20～135 ℃.
The present invention has following advantage compared to existing technology:
The present invention has well solved the nanoparticle scattering problem, and the clay of modification is easy to be dispersed in the raw-silastic continuously, because the particle of modified clay is bigger and consumption seldom (1～4%), so there is not the problem of reuniting.Usually used fumed silica particle diameter is very little, and (5～20nm), very easily reunion is difficult for being dispersed in the rubber, is difficult to obtain the even blend of nanoscale, so influenced the raising of mechanical property.And with the system of hexadecyl trimethyl ammonium bromide as intercalator, be intercal type hybrid material rather than exfoliated nano-composite owing to what form, so also influenced the raising of mechanical property.
The present invention has adopted the organic silicon surfactant of a class response type to come modified clay, because the intercalation motivating force of present method is a chemical action, thereby after making silicon rubber molecular chain intercalation enter the lamella of silicate, the particulate that layered silicate is easy to peel off into nanometer scale is dispersed in the silicon rubber matrix, thereby the mechanical property of matrix material significantly improves.If layered silicate/silicon rubber system is the intercal type hybrid material, because this layered silicate/silicon rubber interface belongs to physical action, disperse phase is the body of combining closely of multilayer clay crystal layer, and phase farmland size is big, improves so the mechanical property of matrix material is difficult to obtain ideal.
Silastic/clay matrix material of the present invention is a kind of exfoliated nano composite material, the reinforcement silicon rubber performance that obtains at last increases substantially, thermotolerance also is improved simultaneously, adds 1～4% modified layered silicate and can make the tensile strength of silicon rubber improve 200～300%; Elongation improves about 100%.
Embodiment 1
With cation exchange capacity is clay 1 gram of 100meq/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 0.8 gram is added in the suspension, 35 ℃ of reactions 72 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.Its performance sees Table 1.
Embodiment 2
With cation exchange capacity is clay 2 grams of 100meq/100g, adds water 80ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 1.6 grams are added in the suspension, 25 ℃ of reactions 80 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 14 hours, and promptly got the compound material of silastic/clay nanometer.Its performance sees Table 1.
Embodiment 3
With cation exchange capacity is clay 3 grams of 120meq/100g, adds water 120ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(trimethoxy is silica-based) propyl group] octadecyl methyl ethyl ammonium chloride 2.4 grams are added in the suspension, 20 ℃ of reactions 96 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 10 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20 ℃ 24 hours, and promptly got silastic/clay nanometer composite material.
Embodiment 4
With cation exchange capacity is clay 4 grams of 100meq/100g, adds water 160ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 3.2 grams are added in the suspension, 35 ℃ of reactions 70 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.Its performance sees Table 1.
Embodiment 5
With cation exchange capacity is clay 6 grams of 50meq/100g, adds water 240ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(trimethoxy is silica-based) propyl group] dimethyl cetyl chloride ammonium 4.8 grams are added in the suspension, 40 ℃ of reactions 24 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 3 hours, add 8 gram tetraethoxys and 0.1 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.
Embodiment 6
With cation exchange capacity is clay 10 grams of 100meq/100g, adds water 400ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(triethoxy is silica-based) propyl group] octadecyl alkyl dimethyl ammonium chloride 1.5 grams are added in the suspension, 30 ℃ of reactions 78 hours.The floss of gained after filtration.Washing with water to filtrate does not have chlorion (silver nitrate solution with 0.2% detects), and the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 35 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.Its performance sees Table 1.
Embodiment 7 (Comparative Examples 1)
Add 6 gram tetraethoxys and 0.5 gram dibutyl tin laurate in the 100 gram polydimethylsiloxanes, stir, pour in the polytetrafluoroethyldisk disk, placed at least 20 hours under 36 ℃, promptly get Comparative Examples 1.Its performance sees Table 1.
Embodiment 8 (Comparative Examples 2)
With cation exchange capacity is clay 2 grams of 100meq/100g, adds water 80ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Tensio-active agent hexadecyl trimethyl ammonium bromide 1.2 grams are dissolved in the hot water of 24ml, are added drop-wise to then in the above-mentioned suspension, 70～75 ℃ of reactions 2 hours.The floss of gained after filtration, washing with water to filtrate does not have bromide anion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 8 gram tetraethoxys and 0.5 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.Its performance sees Table 1.
Embodiment 9 (Comparative Examples 3)
With cation exchange capacity is clay 10 grams of 100meq/100g, adds water 400ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Tensio-active agent hexadecyl trimethyl ammonium bromide 6 is restrained the hot water that is dissolved in 120ml, be added drop-wise to then in the above-mentioned suspension, 70～75 ℃ of reactions 2 hours.The floss of gained after filtration, washing with water to filtrate does not have bromide anion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, adding 8 gram tetraethoxys and 0.5 restrain hangs sour dibutyl tin February, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.Its performance sees Table 1.
Embodiment 10 (Comparative Examples 4)
(filler is gas phase SiO to commercially available room temperature vulcanized silicone rubber
2).Its performance sees Table 1.
Embodiment 11
With cation exchange capacity is clay 1 gram of 100meq/100g, adds water 40ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.Response type organic silicon surfactant [3-(trimethoxy is silica-based) propyl group] dodecyl dimethyl ammonium chloride 0.8 gram is added in the suspension, 40 ℃ of reactions 90 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram polydimethylsiloxanes with machine,massing, stirred 5 hours, add 1 gram tetraethoxy and 1 gram dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 24 hours, and promptly got silastic/clay nanometer composite material.
Embodiment 12
With cation exchange capacity is clay 1 gram of 120meq/100g, adds water 50ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.With response type organic silicon surfactant 2-[(methacryloxy) ethyl] dimethyl [3-(trimethoxy is silica-based) methyl] ammonium chloride 0.5 gram adds in the suspension, 20 ℃ of reactions 96 hours.The floss of gained after filtration, washing with water to filtrate does not have chlorion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram addition-type silicon rubbers (50 grams contain the siloxanes and the 50 gram containing hydrogen silicone oils of vinyl) with machine,massing, stirred 10 hours, add 10PPm gram Platinic chloride, after stirring, pour in the polytetrafluoroethyldisk disk, at least placed under 40 ℃ 14 hours, and promptly got silastic/clay nanometer composite material.
Embodiment 13
With cation exchange capacity is clay 20 grams of 100meq/100g, adds water 1000ml, and after waiting to be uniformly dispersed, high-speed stirring 30min forms steady suspension.With response type organic silicon surfactant 2-[(acryloxy) ethyl] dimethyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride 10 gram adds in the suspension, 40 ℃ of reactions 76 hours.The floss of gained after filtration, washing with water to filtrate does not have oxonium ion (detecting with 0.2% silver nitrate solution), the vacuum-drying constant weight is crushed to powder.This organoclay composites powder is scattered in the 100 gram high-temp glue (poly-ethylene methacrylic radical siloxane) with machine,massing, stirred 8 hours, add benzoyl peroxide 1 gram, stir, pour in the mould, under 5MPa pressure,, promptly get silastic/clay nanometer composite material in 125～135 ℃ of sulfurations 10～15 minutes.
Table 1
| Embodiment | Clay content (g) | Raw-silastic continuously content (g) | X ray d 001Interplanar distance (nm) | Tensile strength (MPa) | Elongation at break (%) | Thermal degradation temperature (℃) |
| ?1 | ?1 | ?100 | ?d 001The peak disappears | ?1.89 | ?388 | ?381.8 |
| ?2 | ?2 | ?100 | ?d 001The peak disappears | ?2.21 | ?316 | ?401.5 |
| ?4 | ?4 | ?100 | ?d 001The peak disappears | ?2.26 | ?302 | ?416.8 |
| ?6 | ?10 | ?100 | ?d 001The peak disappears | ?1.83 | ?299 | |
| ?7 | ?0 | ?100 | ?0.5 | ?135 | ?380.2 | |
| ?8 | ?2 | ?100 | ?4.1 | ?0.61 | ?226 | |
| ?9 | ?10 | ?100 | ?3.8 | ?1.46 | ?305 | |
| ?10 | ?100 | ?1.10 | ?150 |
Claims (5)
1, a kind of peel-off silastic/clay nanometer composite material is characterized in that the material component of described matrix material and content are as follows: (weight part)
Raw-silastic continuously 100
Clay 1-20
Organic silicon surfactant 0.5-10
Dispersion medium 40-1000
Linking agent 1-10
Promotor dibutyl tin laurate 0.1-1
Wherein said dispersion medium is selected from water, alcohols or dimethyl formamide; Described linking agent is selected from the alkyl silane of multiple functional radical or the organoalkoxysilane of multiple functional radical.
2, a kind of peel-off silastic/clay nanometer composite material according to claim 1 is characterized in that described raw-silastic continuously is room temperature silicon rubber or high temperature silicon rubber or addition-type silicon rubber.
3, a kind of peel-off silastic/clay nanometer composite material according to claim 1, the chemical structure skeleton symbol that it is characterized in that described organic silicon surfactant is (RO)
3SiR
1N
+R
2R
3R
4X
-, wherein R is CH
3-or C
2H
5-, R
1For-CH
2-or-C
3H
6-, R
2Be CH
3-or C
2H
5-, R
3Be CH
3-or C
2H
5-, R
4Be chain alkyl or aliphatics vinylformic acid and ester derivative thereof, X is Cl.
4, a kind of peel-off silastic/clay nanometer composite material according to claim 3 is characterized in that described chain alkyl is dodecyl, hexadecyl or octadecyl; Aliphatics vinylformic acid and ester derivative thereof are CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-.
5, a kind of preparation method who prepares the described peel-off silastic/clay nanometer composite material of claim 1, it is characterized in that following these steps to carry out: be the clay 1-20 weight part of 50-120meq/100g with cation exchange capacity, high-speed stirring in the presence of the dispersion medium of 40-1000 weight part, form steady suspension, organic silicon surfactant 0.5-10 weight part is added in the dispersion medium, 20-40 ℃ of reaction 24-96 hour, the floss of gained after filtration, washing, dry, be organoclay composites after pulverizing; Above-mentioned organoclay composites 1-20 weight part through the organic silicon surfactant reaction is scattered in the 100 weight part raw-silastic continuouslies, stir and add linking agent 1-10 weight part after 5-10 hour, dibutyl tin laurate promotor 0.1-1 weight part, pour in the mould, placed 14-24 hour, and promptly got product for 20-135 ℃; Wherein said dispersion medium is selected from water, alcohols or dimethyl formamide; Described linking agent is selected from the alkyl silane of multiple functional radical or the organoalkoxysilane of multiple functional radical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011082879A CN1156538C (en) | 2001-02-28 | 2001-02-28 | Exfoliated silicone rubber/clay nanocomposite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011082879A CN1156538C (en) | 2001-02-28 | 2001-02-28 | Exfoliated silicone rubber/clay nanocomposite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1308101A CN1308101A (en) | 2001-08-15 |
| CN1156538C true CN1156538C (en) | 2004-07-07 |
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ID=4657165
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|---|---|---|---|
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| CN1900180A (en) * | 2005-07-22 | 2007-01-24 | Sar控股国际有限公司 | Negative ion silica gel composition, its preparation method and its products |
| CN100402606C (en) * | 2006-03-30 | 2008-07-16 | 南京化工职业技术学院 | PET/clay nanocomposite material and preparation method thereof |
| WO2016206243A1 (en) * | 2015-06-24 | 2016-12-29 | 中国科学院过程工程研究所 | Arc-resistant silicon rubber composite material, preparation method, and uses thereof |
| CN108410173A (en) * | 2018-02-28 | 2018-08-17 | 天长市荣盛有机硅科技有限公司 | A kind of modified Portland silastic material and preparation method thereof |
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2001
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