CN100564497C - The preparation method of the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite - Google Patents
The preparation method of the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite Download PDFInfo
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- CN100564497C CN100564497C CNB2007100512921A CN200710051292A CN100564497C CN 100564497 C CN100564497 C CN 100564497C CN B2007100512921 A CNB2007100512921 A CN B2007100512921A CN 200710051292 A CN200710051292 A CN 200710051292A CN 100564497 C CN100564497 C CN 100564497C
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Abstract
The invention discloses a kind of preparation method of electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite.The shell material of this mixture is the anion polyurethane that a class side chain has acidic-group, and the nuclear material is a silicon-dioxide; The electrorheological fluid of this mixture is to be disperse phase with the silicon dioxide-aqueous polyurethane nano composite, with the dimethyl silicone oil is dispersion liquid, and making the anion polyurethane that has an acidic-group with tetraethoxy and side chain by following method is raw material, make tetraethoxy in the polyurethane nano micro-capsule, realize hydrolysis on the throne, polymerization, and through alkali neutralization, steam solvent, and make the silicon dioxide-aqueous polyurethane nano composite dispersion liquid; Then through freezing, dry, make powder after grinding, making itself and dimethyl silicone oil again is (30～40) with mass ratio: 70 mix and get final product.Technology of the present invention is simple, and prepared electrorheological fluid ER properties is remarkable, and leakage current density is very little, is more satisfactory er material.
Description
Technical field
The present invention relates to a class inorganic/organic composite material is used to prepare the technical field of electrorheological fluid, particularly relates to a kind of preparation method of electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite.
Background technology
Electrorheological fluid is a kind of faster intelligent material of development in recent years, and it under electric field action quick, reversible, controlled response can take place.The theoretical basis of electrorheological fluid technology is electric rheological effect.Electric rheological effect is meant certain special liquid, under electric field action or control, characterizes the viscosity of liquid-flow attribute, under certain shearing rate, the phenomenon of considerable change can take place, and this variation is a reversible, electrodeless and can control continuously.This variation can make flowable liquid retrogradation, hardening even stop to flow, reach and solidify, and make the liquid of this moment have solid-state attribute, promptly keep shape or have tangible anti-shearing yielding stress occurring, the Young's modulus of perhaps representing solid features has obvious variation, and when electric field disappeared, current liquid was thinning immediately, recovered original liquid state.At present, what prepare the electrorheological fluid disperse phase mainly is inorganic materials, and organic materials is used to prepare the kind more single (mainly being polyaniline compound) of electrorheological fluid.
The key of electrorheological fluid technology of preparing is the preparation dispersion particle.Take all factors into consideration the various factors that influences electric rheological effect, spherical is the optimum shape of current liquid dispersed phase particles.In order to prepare stable electrorheological fluid, the particle diameter of dispersed phase particles can not be excessive can not be too little, too macroparticle precipitates in dispersion liquid easily, particle diameter is too little, and pedesis takes place easily, influences electric rheological effect.The micron order discrete particles has good electric rheological effect.The method of existing preparation SiO 2-polymer nano composite material is to utilize tetraethoxy as the silicon dioxide granule source, makes its hydrolysis in polyurethane shell, aggregates into silicon-dioxide.The silica sphere of Sheng Chenging contains a large amount of hydroxyls like this, can form hydrogen bond with the urethane of shell, makes this nucleocapsid structure stable, and has avoided the silicon-dioxide aggregation phenomenon.At present, the macromolecular material kind that is used for preparing electro-rheologic fluid material mainly is the matrix material of polyaniline and polyaniline and other inorganics seldom.Contain a large amount of hydroxyls, ester group, amino groups in the polyurethane material structure, these groups have good polarizability, can infer that polyurethane material has good ER properties.But, be unfavorable for synthetic urethane is made powder because urethane has good visco-elasticity.Therefore, the ER properties key that investigate urethane is exactly the powder for preparing urethane.
At present, the applied research of aqueous polyurethane is mainly concentrated in tackiness agent and the coating, as for the performance of the electrorheological fluid of aqueous polyurethane how, the also rarely seen report of the preparation method of its electrorheological fluid.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite is provided, and this method technology is simple, the advantages of nontoxic raw materials that is adopted, and prepared electrorheological fluid performance is good.
The technical scheme that the present invention solves its technical problem employing is: described silicon dioxide-aqueous polyurethane nano composite, its shell material are the anion polyurethane that a class side chain has acidic-group, and the nuclear material is a silicon-dioxide; Its electrorheological fluid is to be disperse phase with the silicon dioxide-aqueous polyurethane nano composite, is dispersion liquid with the dimethyl silicone oil, and is made by following steps:
(1) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid: the anion polyurethane that has acidic-group with tetraethoxy and side chain is a raw material, and press the feed ratio (35～55) of tetraethoxy and urethane: 100, in the polyurethane nano micro-capsule, realize hydrolysis on the throne, polymerization making tetraethoxy under 60 ℃, and through alkali neutralization, steam solvent, and make silicon dioxide-poly-ammonia ester water nano mixture dispersion liquid with a nucleoid shell structure.Described silicon dioxide-poly-ammonia ester water nano mixture forms the aqueous dispersions of stable particle diameter at 80～120nm in alkaline medium.
(2) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite: earlier above-mentioned silicon dioxide-aqueous polyurethane nano composite dispersion liquid is made powder after freezing, dry and grinding, be (30～40) with dimethyl silicone oil with mass ratio with this powder again: 70 mix, and by ultra-sonic dispersion it are mixed to get final product.
The anion polyurethane that above-mentioned side chain has acidic-group is the anionic polyurethane performed polymer, its preparation method is: with polyester polyol, 4, after 4 '-diphenylmethanediisocyanate or hexamethylene diisocyanate mix, add solvent ethyl acetate, heat with oil bath again, be warming up to 65～80 ℃, isothermal reaction 1.8～2 hours; In the time of 75 ℃, add the chainextender dimethylol propionic acid, reacted 0.8～1 hour; When being cooled to 45～50 ℃, add the Virahol end-blocking, keep reaction to get final product half an hour.
The invention has the advantages that: have hydrophilic acidic-group and hydrophobic polyethers or polyester segment on the anion polyurethane molecular chain that is adopted, it is the comparatively ideal protein model compound of a class, because their the intermolecular interaction that hydrogen bond, ionic linkage are arranged, produce extremely strong hydrophilic-hydrophobic interaction, the main power that can reflect the polymer self-assembly also is the ideal model of a family macromolecule self-assembly ultimative function material.And the straight chain polyester polyol that selection has good hardness is avoided the mutual winding of molecular chain, helps mixture and disperses in the aqueous solution.The adding of silicon-dioxide not only can increase the hardness of mixture, and can increase the mixture dielectric coefficient, thereby improves the polarizability of mixture, makes mixture have more obvious electric rheological effect.The prepared dispersion particle size of the present invention is little, and organic solvent content is few.The sample that contains a large amount of organic solvents is to carry out cryodesiccatedly, and the hud typed silicon dioxide-poly-ammonia ester water nano mixture of our institute's synthetic is an aqueous product, contains trace or does not have organic solvent, and guaranteeing does not have any damage to machine.
In a word, preparation technology of the present invention is simple, and prepared electrorheological fluid ER properties is remarkable, and leakage current density is very little, and solids are stable in dispersion liquid, be difficult for sedimentation takes place, and be a kind of more satisfactory er material.
Description of drawings
Fig. 1 is the relation curve of the ER liquid shear-stress-shearing rate of different dioxide-containing silicas.
Fig. 2 is the relation curves of different dioxide-containing silicas to the influence of leakage current.
Embodiment
The invention will be further described below in conjunction with embodiment, but do not limit the present invention.
[embodiment 1] tetraethoxy content is 35% (calculation formula is: tetraethoxy percentage composition=tetraethoxy quality/PU quality * 100%, as follows)
(1) preparation anionic polyurethane performed polymer:
Being equipped with in the there-necked flask of condensing works, electric mixer one, is n by the mole proportioning
NCO/ n
OHAdd polyester polyol, 4,4 '-diphenylmethanediisocyanate (MDI) or hexamethylene diisocyanate (HDI), and the solvent ethyl acetate of 5～10ml at=1.5: 1; With the oil bath heating, be warming up to 70～80 ℃, isothermal reaction 1.8～2 hours; In the time of 75 ℃, be n by the mole proportioning
COOH/ n
OHAdd chainextender dimethylol propionic acid (DMPA) at=3: 1, reacted 0.8～1 hour; Be cooled to 45～50 ℃, add about 2.4 gram Virahol end-blockings, keep reaction to get final product half an hour.
(2) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
Get 41.42 gram performed polymers and be warming up to 60 ℃, added for 14.50 gram tetraethoxys reaction half an hour, be cooled to 40 ℃ and added a certain amount of neutralizing agent triethylamine and carboxyl salt-forming reaction 15 minutes.Add 138.17ml water, steaming desolventizes.Can reach solid content and be silicon-dioxide-anionic polyurethane aqueous dispersions of 30%.
(3) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Get the silicon-dioxide-anionic polyurethane aqueous dispersions for preparing and be placed on and be frozen into the ice shape in the refrigerator, be placed on the freeze drier dry 24 hours then.The good mixture of drying ground obtain silicon-dioxide-anionic polyurethane composite powder.Prepared powder is made the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite in dimethyl silicone oil after evenly according to 30: 70 mixed, and the electricity consumption rheometer is studied its ER properties (seeing Fig. 1, Fig. 2).
[embodiment 2] tetraethoxy content is 45%
(1) preparation anionic polyurethane performed polymer: with embodiment 1.
(2) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
Get 41.42 gram performed polymers and be warming up to 60 ℃, added for 18.64 gram tetraethoxys reaction half an hour, be cooled to 40 ℃ and added a certain amount of neutralizing agent triethylamine and carboxyl salt-forming reaction 15 minutes.Add 147.21ml water, steaming desolventizes.Can reach solid content and be silicon-dioxide-anionic polyurethane aqueous dispersions of 30%.
(3) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Get the silicon-dioxide-anionic polyurethane aqueous dispersions for preparing and be placed on and be frozen into the ice shape in the refrigerator, be placed on the freeze drier dry 24 hours then.The good mixture of drying ground obtain silicon-dioxide-anionic polyurethane composite powder.Prepared powder is made the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite in dimethyl silicone oil after evenly according to 30: 70 mixed, and the electricity consumption rheometer is studied its ER properties (seeing Fig. 1, Fig. 2).
[embodiment 3] tetraethoxy content is 55%
(1) preparation anionic polyurethane performed polymer: with embodiment 1.
(2) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
Get 41.42 gram performed polymers and be warming up to 60 ℃, added for 22.78 gram tetraethoxys reaction half an hour, be cooled to 40 ℃ and added a certain amount of neutralizing agent triethylamine and carboxyl salt-forming reaction 15 minutes.Add 156.87ml water, steaming desolventizes.Can reach solid content and be silicon-dioxide-anionic polyurethane aqueous dispersions of 30%.
(3) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Get the silicon-dioxide-anionic polyurethane aqueous dispersions for preparing and be placed on and be frozen into the ice shape in the refrigerator, be placed on the freeze drier dry 24 hours then.The good mixture of drying ground obtain silicon-dioxide-anionic polyurethane composite powder.Prepared powder is made the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite in dimethyl silicone oil after evenly according to 30: 70 mixed, and the electricity consumption rheometer is studied its ER properties (seeing Fig. 1, Fig. 2).
[embodiment 4] tetraethoxy content is 40%
(1) preparation anionic polyurethane performed polymer: with embodiment 1.
(2) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
Get 41.42 gram performed polymers and be warming up to 60 ℃, added for 16.57 gram tetraethoxys reaction half an hour, be cooled to 40 ℃ and added a certain amount of neutralizing agent triethylamine and carboxyl salt-forming reaction 15 minutes.Add 156.87ml water, steaming desolventizes.Can reach solid content and be silicon-dioxide-anionic polyurethane aqueous dispersions of 30%.
(3) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Get the silicon-dioxide-anionic polyurethane aqueous dispersions for preparing and be placed on and be frozen into the ice shape in the refrigerator, be placed on the freeze drier dry 24 hours then.The good mixture of drying ground obtain silicon-dioxide-anionic polyurethane composite powder.Prepared powder is made the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite in dimethyl silicone oil after evenly according to 35: 70 mixed, and the electricity consumption rheometer is studied its ER properties (seeing Fig. 1, Fig. 2).
[embodiment 5] tetraethoxy content is 50%
(1) preparation anionic polyurethane performed polymer: with embodiment 1.
(2) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
Get 41.42 gram performed polymers and be warming up to 60 ℃, added for 20.71 gram tetraethoxys reaction half an hour, be cooled to 40 ℃ and added a certain amount of neutralizing agent triethylamine and carboxyl salt-forming reaction 15 minutes.Add 156.87ml water, steaming desolventizes.Can reach solid content and be silicon-dioxide-anionic polyurethane aqueous dispersions of 30%.
(3) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Get the silicon-dioxide-anionic polyurethane aqueous dispersions for preparing and be placed on and be frozen into the ice shape in the refrigerator, be placed on the freeze drier dry 24 hours then.The good mixture of drying ground obtain silicon-dioxide-anionic polyurethane composite powder.Prepared powder is made the electrorheological fluid of silicon dioxide-aqueous polyurethane nano composite in dimethyl silicone oil after evenly according to 40: 70 mixed, and the electricity consumption rheometer is studied its ER properties (seeing Fig. 1, Fig. 2).
Below in conjunction with accompanying drawing the prepared electrorheological fluid of the foregoing description is described by the result after the electrorheological instrument test.
Fig. 1 is under electric field E=1kv/mm, the shearing rate of the electrorheological fluid of different dioxide-containing silicas-shear-stress relation curve.As seen from Figure 1, shear-stress increases along with the increase of shearing rate, but the shear-stress that dioxide-containing silica is high is more obvious with the trend that shearing rate increases, under identical shearing rate, dioxide-containing silica is high has a higher shear-stress, and this may be because along with the increase of dioxide-containing silica, particle density increases gradually, under identical shearing rate, the fiber chain-like structure that the particle that density is big forms has higher intensity, can bear bigger shear-stress.But the present invention is prepared that electrorheological fluid gets shear-stress and also has distance apart from desired electrical rheology liquid, therefore need to continue to seek new preparation condition and improve the specific inductivity of material, thereby prepare the electrorheological fluid of the electrorheological fluid of ideal silicon dioxide-aqueous polyurethane nano composite.
The leakage current numeric ratio of sample is less as seen from Figure 2, and changes little.This explanation, the fibrous strands number that our prepared ER liquid forms between two electrodes under electric field action is more even, and number is less.In the shear history, ER liquid is subjected to the effect of shearing force, the particle chain that forms is constantly cut off, is destroyed, while, chain break carried out repeatedly with reconstruction under therefore acting in electric field and shearing force field, under different shearing rates because intergranular polarized action power has again the trend of chaining again, the variation of leakage current is less, this explanation is under shear action, and current channel reaches balance in cutting off and rebuilding, and number is constant substantially.Therefore the dielectric loss of this electrorheological fluid is smaller.
The electrorheological fluid of the silicon dioxide-aqueous polyurethane nano composite that the present invention makes, its main technical details is (only for reference): be 0.3～0.4 at quality (disperse phase) mark, when field intensity is 3kV/mm, shear-stress is 4～5kPa, working temperature is-50 ℃-150 ℃, can not precipitate in addition, cause and be separated.
Claims (5)
1. the preparation method of the electrorheological fluid of a silicon dioxide-aqueous polyurethane nano composite is characterized in that described mixture, and its shell material is the anion polyurethane that a class side chain has acidic-group, and the nuclear material is a silicon-dioxide; Its electrorheological fluid is to be disperse phase with the silicon dioxide-aqueous polyurethane nano composite, is dispersion liquid with the dimethyl silicone oil, and this electrorheological fluid is made by following steps:
(1) preparation silicon dioxide-aqueous polyurethane nano composite dispersion liquid:
The anion polyurethane that has acidic-group with tetraethoxy and side chain is a raw material, and by the mass ratio that feeds intake (35～55) of tetraethoxy and urethane: 100, in the polyurethane nano micro-capsule, realize hydrolysis on the throne, polymerization making tetraethoxy under 60 ℃, and through alkali neutralization, steam solvent, and make silicon dioxide-poly-ammonia ester water nano mixture dispersion liquid with a nucleoid shell structure
The anion polyurethane that described side chain has acidic-group is the anionic polyurethane performed polymer, is made by following method:
With polyester polyol, 4, after 4 '-diphenylmethanediisocyanate or hexamethylene diisocyanate mix, add solvent ethyl acetate 5～10ml, with the oil bath heating, be warming up to 70～80 ℃, isothermal reaction 1.8～2 hours again; In the time of 75 ℃, add the chainextender dimethylol propionic acid, reacted 0.8～1 hour; When being cooled to 45～50 ℃, add the Virahol end-blocking, keep reacting half an hour;
(2) electrorheological fluid of preparation silicon dioxide-aqueous polyurethane nano composite:
Earlier with above-mentioned silicon dioxide-aqueous polyurethane nano composite dispersion liquid through freezing, dry and grind after make powder, be to mix at 30～40: 70 this powder and dimethyl silicone oil with mass ratio again, and it mixed by ultra-sonic dispersion.
2. the preparation method of electrorheological fluid according to claim 1 is characterized in that: described polyester polyol, 4, and 4 '--diphenylmethanediisocyanate or hexamethylene diisocyanate, its mole proportioning are n
NCO/ n
OH=1.5: 1.
3. the preparation method of electrorheological fluid according to claim 1 is characterized in that: described chainextender dimethylol propionic acid (DMPA), the mole proportioning of itself and polyester polyol is n
COOH/ n
OH=3: 1.
4. the preparation method of electrorheological fluid according to claim 1, it is characterized in that: the silicon dioxide-poly-ammonia ester water nano mixture with a nucleoid shell structure forms the aqueous dispersions of stable particle diameter at 80～120nm in alkaline medium.
5. the preparation method of electrorheological fluid according to claim 1 is characterized in that: with the prepared powder of silicon dioxide-aqueous polyurethane nano composite dispersion liquid, be to mix at 30: 70 with dimethyl silicone oil with mass ratio.
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| JP2021020970A (en) * | 2019-07-24 | 2021-02-18 | 日立オートモティブシステムズ株式会社 | Electroviscous fluid composition and cylinder device |
| JP2021191812A (en) * | 2020-06-05 | 2021-12-16 | 日立Astemo株式会社 | Electro-rheological fluid and cylinder device |
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| 一种新型材料－电流变液的研究现状及应用. 尹剑波.江苏化工，第28卷第7期. 2000 |
| 一种新型材料－电流变液的研究现状及应用. 尹剑波.江苏化工，第28卷第7期. 2000 * |
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