CN1624033A - Method of preparing modified imvite for polymer/inorganic nano composite material - Google Patents
Method of preparing modified imvite for polymer/inorganic nano composite material Download PDFInfo
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- CN1624033A CN1624033A CN 200410051956 CN200410051956A CN1624033A CN 1624033 A CN1624033 A CN 1624033A CN 200410051956 CN200410051956 CN 200410051956 CN 200410051956 A CN200410051956 A CN 200410051956A CN 1624033 A CN1624033 A CN 1624033A
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Abstract
A process for preparing the modified montmorillonite used to prepare composite polymer/montmorillonite nano-material with excellent properties features the direct reaction between powdered montmorillonite and organic modifier. Its advantages are no need of water and solvent, and no environmental pollution.
Description
Technical field
The present invention relates to polymer/inorganic thing field of nanocomposite materials, specifically be meant the preparation method of a kind of polymer/inorganic thing nano composite material with modified montmorillonoid.
Background technology
Nano composite material (Nanocomposites) be meant the disperse phase yardstick at least on the one dimension direction less than the matrix material of 100nm.Because the small size and the bigger serface of nanophase, make the rapid increase that reduces of surface atom number, surface tension and surface energy with particle diameter, thereby have significant small-size effect, quantum size effect, surface effects and macro quanta tunnel effect etc., give the characteristic and the rule of the many novelties of material, for wide prospect has been showed in the research and the application of nano composite material.
The nano composite material that polymkeric substance and inorganics are formed is to study the most active nano composite material in recent years.The compound use of polymkeric substance and inorganics has had the history of decades, and inorganic minerals such as clay, lime carbonate, mica are used widely as the weighting agent of polymkeric substance.The development of nano combined notion and technology has given this class composite organic-inorganic material new vitality, not only make the remarkable over-all properties of improving this type of material become possibility, even can make matrix material many beyond thought new physical and chemical performances occur, thereby shown vast potential for future development in the novel material Application Areas.
Polymer/inorganic thing nano composite material has multiple preparation method, intercalation compounding wherein or claim to embed composite algorithm and at home and abroad study at most, tool use value and development prospect.This method is to utilize some inorganic materials (if you would take off soil, kaolin, modified graphite etc.) to have the characteristics of nano-lamellar structure, its interlayer surface is being carried out on the organically-modified basis, with between the monomer interposed layer, and carry out home position polymerization reaction, or macromole is under solution, melt, the emulsion state directly between interposed layer, and finally obtaining complete isolating leafing nano composite material of nanometer lamella (Exifoliated nanocomposites) or interlamellar spacing is the intercalated nano-composite (Intercalated nanocomposites) of nano-scale.
Polynite is a kind of natural stratiform silicate inorganic material with nano-lamellar structure because it has particular structure, the source easily, price is low, thus the preparation of polymer/inorganic thing nano composite material with use in especially be subject to people's attention.Polymkeric substance and polynite make characteristics such as material has light specific gravity, good heat resistance, barrier height, ageing resistance is good, flame retardant resistance is good nanoscale compound.
Polynite main component be montmorillonite.Montmorillonite belongs to 2: 1 type layered silicates, and promptly each unit cell is made of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connects the about 1nm of entire structure sheet bed thickness, each about 100nm of length and width between the two by shared Sauerstoffatom.Since alumina octahedral top aluminium atom by the low price atom (as Mg
2+, Fe
2+, Na
+Deng) replace, layer internal surface has negative charge, and superfluous negative charge is by being free on the Mg of interlayer
2+, Fe
2+, Na
+Deng cation balance.Because the wetting ability on polynite surface, be unfavorable for that it disperses and is aggregated the wetting and intercalation of thing in polymkeric substance.For overcoming this shortcoming, must carry out modification in advance and make the polynite interlayer surface be hydrophobicity.Carrying out effectively organically-modified to polynite is the key that successfully prepares nano composite polymer-montmorillonoid material.
Polynite is easily carried out ion exchange reaction generation organic modified silicate with alkyl quaternary ammonium salts, pyridine derivatives or other organic cation.Organic modified silicate is lipophilicity, and the interlamellar spacing increase, can carry out effective intercalation with monomer or polymkeric substance, is dispersed in the polymeric matrix with nanoscale, thereby forms nano composite material.
Quaternary ammonium salt modified polynite process commonly used is at present carried out in aqeous suspension or organic solvent usually, technology is comparatively complicated, need by disperseing series of processes such as slurrying, ion exchange reaction, ageing, filtration, washing, drying, grinding, screening, starting material and energy consumption are big, cause that the organic modification montmonrillonite cost increases sharply, cause environmental pollution simultaneously, thereby influence applying of intercalation nano compounding technology.
Summary of the invention
The objective of the invention is earlier numerous and diverse organic modification to be carried out in polynite at existing polymer/montmorillnoite nano intercalation compounding technology needs, to make water or organic solvent in the preparation process, the cost height, shortcoming such as be unfavorable for promoting the use of, a kind of simple and feasible polymer/inorganic thing nano composite material preparation method of modified montmorillonoid is provided, with polynite with a kind of organic modifiers or mix organic modifiers and under the pressed powder state, directly carry out reaction modifying, the modified montmorillonoid that obtains can be directly used in nano composite polymer-montmorillonoid material, realize the effective intercalation of polymer macromolecule between cheating engaging layer, obtain the nano composite material of excellent property.That this method has is simple and easy to do, production cost is low, need not make water or advantages such as solvent, non-environmental-pollution, has favorable industrial application prospect.
Polymer/inorganic thing nano composite material of the present invention comprises the steps: with the preparation method of modified montmorillonoid
(1) with the organic modifiers of the Powdered polynite of 100 weight parts and 1～50 weight part in room temperature～150 ℃ mixing and stirring;
(2) solid phase stirring reaction 10～100min ℃ carries out in mixture heating up to 50～150 that (1) is obtained;
(3) product that (2) are obtained is cooled to normal temperature and promptly obtains polymer/inorganic thing nano composite material modified montmorillonoid;
Preferred version of the present invention:
(1) with the organic modifiers of the Powdered polynite of 100 weight parts and 10～30 weight parts 50～120 ℃ of mixing and stirring;
(2) solid phase stirring reaction 30～80min ℃ carries out in mixture heating up to 80～120 that (1) is obtained;
(3) product that (2) are obtained is cooled to normal temperature and promptly obtains polymer/inorganic thing nano composite material modified montmorillonoid.
Described polynite comprises wherein one or more mixtures of the calcium base of all size or sodium-based montmorillonite;
Organic modifiers comprises one or more mixtures in various organic amines or the organic quaternary ammonium salt.Organic quaternary ammonium salt such as palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride or octadecyl trimethylammonium bromide, dimethylaminoethyl acrylate methyl ammonia ethyl ester trimethyl ammonium chloride, to (vinyl benzene) trimethyl ammonium chloride, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, (to the Ethenylbenzene methyl) 12 (or 16) alkyl-dimethyl ammonium chloride etc.;
Organic amine such as aniline, amino dodecane, stearylamine, hexanolactam, 6-aminocaprolc acid etc., silane coupling agent such as γ-(2,3 glycidoxies) oxypropyl trimethyl silane, the ethylene methacrylic base silane, N, N '-two (2-methyl-2-nitro propyl group)-1, the 6-diamino hexane, bis(3-triethoxy silylpropyl)tetrasulfide, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane, methacryloxypropyl trimethoxy silane, quadrol Union carbide A-162 etc., titante coupling agent such as isopropoxy three Unimac 5680 titaniums, isopropoxy three (dioctylphosphoric acid ester) titanium, isopropoxy three (dioctyl pyrophosphate) titanium, two (dioctylphosphoric acid ester) ethylene titanate, two (dioctyl pyrophosphate) hydroxyethanoic acid titanium etc.
The present invention adds properties-correcting agent or mixed modifier in polynite, carry out the modification of polynite under the solid phase condition, has saved the present general organically-modified numerous and diverse step of polynite, the convenient use when saving cost.Physics and the chemical action of properties-correcting agent during on the one hand by solid state reaction enters between cheating engaging layer and with polynite and combines, on the other hand in the preparation of follow-up polymer-montmorillonoid matrix material and the course of processing by physics and/or chemical action and polymer molecule chain combination, thereby make the polymer macromolecule chain embed the modified montmorillonoid interlayer, enlarge the cheating engaging layer spacing even produce peeling off of lamella, realize the nano combined of polymkeric substance and polynite, thereby the performance of nano composite polymer-montmorillonoid material is significantly improved.
For example, the tensile strength of the general cross-linked rubber of natural rubber and 5 parts of unmodified polynites, tensile yield, tear strength are respectively 16.6Mpa, 620% and 20.8kN/m, and tensile strength, tensile yield, the tear strength of 5 parts of polynites being carried out the nano combined cross-linked rubber that makes with natural rubber after the solid phase method modification are respectively 24.4Mpa, 546% and 36.8kN/m, reach the reinforcement level of 30 parts of high abrasion furnace black(HAF) (N330).These results show that the solid phase method modified montmorillonoid is used for the preparation of polymer nanocomposites, have obtained good effect.
The modified montmorillonoid of the present invention's preparation can be applicable to various macromolecular materials and matrix materials thereof such as plastics, rubber, fiber, tackiness agent, coating, has broad application prospects.
The present invention compared with prior art has following advantage and beneficial effect:
1. the organically-modified method of solid phase method polynite among the present invention, technical simple and easy to do, save the organically-modified numerous and diverse step of existing water method polynite, had advantages such as technology is simple, production cost is low, solvent-free recovery problem, non-environmental-pollution, had favorable industrial application prospect.
2, the modified montmorillonoid with the inventive method preparation can be used for preparing various high performance polymer/Nano composite material of montmorillonite.
Embodiment
Embodiment 1
(1) gets under the 100 gram polynite room temperatures, add palmityl trimethyl ammonium chloride 1 gram, stir;
(2) with said mixture at 150 ℃ of stirring reaction 10min;
(3) above-mentioned reaction product cool to room temperature is promptly obtained modified montmorillonoid of the present invention;
Get natural rubber 100 grams, add various Synergist S-421 95s and above-mentioned modified montmorillonoid by rubber compounding commonly used, carry out mixing and sulfuration, the gained cured properties sees Table 1.By table 1 as seen, the performance of natural rubber/Nano composite material of montmorillonite modified obviously is better than the matrix material of natural rubber and unmodified polynite, add 1-10 part modified montmorillonoid and can show significant reinforcing effect, and ageing-resistant performance improves.
The physical and mechanical properties of table 1 natural rubber/Nano composite material of montmorillonite modified
| Natural rubber | Natural rubber/polynite (10phr) | Natural rubber/modified montmorillonoid | |||
| The polynite consumption | |||||
| ????1 | ????10 | ????20 | |||
| 100% stress at definite elongation/Mpa | ????0.81 | ??0.75 | ????0.83 | ????1.21 | ????1.16 |
| 300% stress at definite elongation/Mpa | ????1.83 | ??1.84 | ????2.71 | ????4.23 | ????4.20 |
| 500% stress at definite elongation/Mpa | ????5.61 | ??5.35 | ????5.49 | ????11.83 | ????10.56 |
| Tensile strength/Mpa | ????20.53 | ??14.74 | ????19.64 | ????27.17 | ????25.68 |
| Tensile yield/% | ????765 | ??700 | ????715 | ????713 | ????705 |
| Tear strength/KN/m | ????20.6 | ??21.12 | ????22.77 | ????40.30 | ????30.56 |
| Setafter break/% | ????18 | ??17 | ????23 | ????25 | ????26 |
| Hardness (Shao Shi A)/degree | ????42 | ??43 | ????45 | ????49 | ????51 |
| Aged properties rate of descent/% (in the air 100 ℃ * 48h) | ????46.2 | ??38.2 | ????29.3 | ????26.8 | ????33.6 |
Annotate: (1) rubber unvulcanizate prescription: NR100, stearic acid 2, zinc oxide 4, accelerant CZ 1.0, altax 0.5, antioxidant 4010NA 1.0, sulphur 1.5.143 ℃ * T90 of cure conditions.
(2) the aged properties rate of descent is the rate of descent of tensile strength and tensile yield product.
When Fig. 1 is 10 parts for the modified montmorillonoid consumption, the TEM photo of natural gum/Nano composite material of montmorillonite modified, as we can see from the figure, modified montmorillonoid disperses to reach nanometer level in material, and the size of most polynite disperse phase is in 10nm.From the XRD figure of Fig. 2 can see find polynite this material interlamellar spacing from original 1.6nm expanded support to 4.3nm, illustrate that the modified montmorillonoid that uses present method to prepare has successfully made rubber/Nano composite material of montmorillonite.
Embodiment 2
(1) gets 100 gram polynites and be heated to 50 ℃, add γ-(2,3 glycidoxy) oxypropyl trimethyl silane 50 grams, stir;
(2) with said mixture at 50 ℃ of stirring reaction 30min;
(3) above-mentioned reaction product cool to room temperature is promptly obtained modified montmorillonoid of the present invention;
Get cis-1,4-polybutadiene rubber 100 grams, add modified montmorillonoid 5 grams, and add various Synergist S-421 95s by rubber compounding commonly used, carry out mixing and sulfuration, the gained cured properties sees Table 2.By table 2 as seen, the performance of cis-1,4-polybutadiene rubber/Nano composite material of montmorillonite modified obviously is better than the cis-1,4-polybutadiene rubber/montmorillonite matrix material, and 5 parts of modified montmorillonoids can show and 20 parts of significant reinforcing effects that carbon black is close.
The physical and mechanical properties of the in-situ inserted method cis-1,4-polybutadiene rubber/montmorillonite composite nano-materials of table 2 mechanical blending
| Cis-1,4-polybutadiene rubber | Cis-1,4-polybutadiene rubber/montmorillonite (5 parts) | Cis-1,4-polybutadiene rubber/modified montmorillonoid (5 parts) | Cis-1,4-polybutadiene rubber/carbon black (N330,20 parts) | |
| 300% stress at definite elongation (Mpa) breaking strength/Mpa elongation at break/% setafter break/% tearing strength/KN/m hardness (Shao Shi A)/degree | 1.38 1.53 320 6 11.56 39 | 1.18 1.49 305 6 12.81 41 | 4.56 5.68 501 6 26.19 46 | 3.13 6.46 383 6 28.78 49 |
Annotate: the rubber unvulcanizate prescription is as follows: cis-1,4-polybutadiene rubber 100, stearic acid 2, zinc oxide 4, accelerant CZ 1.0, altax 0.5, antioxidant 4010NA 1.0, sulphur 1.5.151 ℃ * T90 of cure conditions.
When Fig. 3 is 5 parts for the modified montmorillonoid consumption, the TEM photo of cis-1,4-polybutadiene rubber/Nano composite material of montmorillonite modified, as we can see from the figure, modified montmorillonoid disperses to reach nanometer level in material, and the size of most polynite disperse phase is in 20nm.From the XRD figure of Fig. 4 can see find polynite this material interlamellar spacing from original 1.3nm expanded support to 4.2nm, illustrate that the modified montmorillonoid that uses present method to prepare has successfully made rubber/Nano composite material of montmorillonite.
Embodiment 3
(1) gets 100 gram polynites and be heated to 80 ℃, add hexanolactam, each 15 gram of isopropoxy three Unimac 5680 titaniums, stir;
(2) with said mixture at 100 ℃ of abundant stirring reaction 100min;
(3) above-mentioned reaction product cool to room temperature is promptly obtained organic modification montmonrillonite.
Get styrene-butadiene rubber(SBR) 100 grams, add 30 gram modified montmorillonoids, and add various Synergist S-421 95s, carry out mixing and sulfuration by rubber compounding commonly used.Resulting cross-linked rubber is carried out X-ray diffraction analysis, and the interlamellar spacing of finding polynite in this material, illustrates and uses the modified montmorillonoid of present method preparation successfully to make rubber/Nano composite material of montmorillonite to 4.7nm from original 1.5nm expanded support.
Embodiment 4
(1) gets 100 gram polynites and be heated to 120 ℃, add vinyltriethoxysilane, each 5 gram of (to the Ethenylbenzene methyl) dodecyl dimethyl ammonium chloride
(2) with said mixture at 120 ℃ of abundant stirring reaction 80min;
(3) above-mentioned reaction product cool to room temperature is promptly obtained organic modification montmonrillonite.
Get paracril 100 grams, add 5 gram modified montmorillonoids, and add various Synergist S-421 95s, carry out mixing and sulfuration by rubber compounding commonly used.Resulting cross-linked rubber is carried out X-ray diffraction test, and the interlamellar spacing of finding polynite in this material to 4.2nm, illustrate that the modified montmorillonoid that uses present method to prepare has successfully made rubber/Nano composite material of montmorillonite from original 1.6nm expanded support.
Claims (5)
1, a kind of polymer/inorganic thing nano composite material is characterized in that comprising the steps: with the preparation method of modified montmorillonoid
(1) with the organic modifiers of the Powdered polynite of 100 weight parts and 1～50 weight part in room temperature～150 ℃ mixing and stirring;
(2) solid phase stirring reaction 10～100min ℃ carries out in mixture heating up to 50～150 that (1) is obtained:
(3) product that (2) are obtained is cooled to normal temperature and promptly obtains polymer/inorganic thing nano composite material modified montmorillonoid;
Described polynite comprises wherein one or more mixtures of the calcium base of all size or sodium-based montmorillonite; Organic modifiers comprises one or more mixtures in various organic amines or the organic quaternary ammonium salt.
2, the polymer/inorganic thing nano composite material according to claim 1 preparation method of modified montmorillonoid is characterized in that comprising the steps: preferred version of the present invention:
(1) with the organic modifiers of the Powdered polynite of 100 weight parts and 10～30 weight parts 50～120 ℃ of mixing and stirring;
(2) solid phase stirring reaction 30～80min ℃ carries out in mixture heating up to 80～120 that (1) is obtained;
(3) product that (2) are obtained is cooled to normal temperature and promptly obtains polymer/inorganic thing nano composite material modified montmorillonoid.
3, polymer/inorganic thing nano composite material according to claim 1 and 2 is with the preparation method of modified montmorillonoid, it is characterized in that organic quaternary ammonium salt comprise palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride or octadecyl trimethylammonium bromide, dimethylaminoethyl acrylate methyl ammonia ethyl ester trimethyl ammonium chloride, in (vinyl benzene) trimethyl ammonium chloride, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, (to the Ethenylbenzene methyl) 12 (or 16) the alkyl-dimethyl ammonium chloride one or more.
4, the polymer/inorganic thing nano composite material according to claim 1 and 2 preparation method of modified montmorillonoid, it is characterized in that organic amine comprises aniline, amino dodecane, stearylamine, hexanolactam, 6-aminocaprolc acid etc., silane coupling agent such as γ-(2,3 glycidoxies) oxypropyl trimethyl silane, the ethylene methacrylic base silane, N, N '-two (2-methyl-2-nitro propyl group)-1, the 6-diamino hexane, bis(3-triethoxy silylpropyl)tetrasulfide, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-oxyethyl group) silane, methacryloxypropyl trimethoxy silane, quadrol Union carbide A-162 etc., titante coupling agent such as isopropoxy three Unimac 5680 titaniums, isopropoxy three (dioctylphosphoric acid ester) titanium, isopropoxy three (dioctyl pyrophosphate) titanium, two (dioctylphosphoric acid ester) ethylene titanate, in two (dioctyl pyrophosphate) hydroxyethanoic acid titanium one or more.
5, the polymer/inorganic thing nano composite material modified montmorillonoid of the described method preparation of claim 1.
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