CN106751741A - A kind of preparation method of polyurethane nano composite material - Google Patents

A kind of preparation method of polyurethane nano composite material Download PDF

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CN106751741A
CN106751741A CN201611125878.3A CN201611125878A CN106751741A CN 106751741 A CN106751741 A CN 106751741A CN 201611125878 A CN201611125878 A CN 201611125878A CN 106751741 A CN106751741 A CN 106751741A
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polyurethane
tpue
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cnt
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CN106751741B (en
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周钰明
丁彬彬
任慧
何曼
张卫
张一卫
黄镜怡
王泳娟
申华
黄裕中
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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Abstract

The preparation method of a kind of polyurethane nano composite material that the present invention is provided is：Modified carbon nano-tube composite nano materials are added in TPUE (TPU) by solution molten blending method, the mechanical property and heat resistance of TPUE are improve, and then prepares the nano combined flexible pipe of high performance polyurethane.By in acidifying carbon nano tube surface growth in situ nano silicon (SiO2) and nano titanium oxide (TiO2) nucleocapsid integument, hud typed carbon nano tube composite nano material is formed, make CNT (CNTs), SiO2And TiO2Three can realize dispersed and compound, effectively it is combined by the coupling modifier and TPU of silane coupler, improve the mechanical property and heat resistance of TPUE well, improve inorganic material dispersiveness in the composite, and then the nano combined flexible pipe of high performance polyurethane is prepared, polyurethane nano composite material has expanded the application field of TPUE.

Description

A kind of preparation method of polyurethane nano composite material
Technical field
The present invention relates to a kind of preparation method of polyurethane nano composite material, it is mainly used in improving thermoplastic polyurethane Mechanical property and thermal stability heat resistance, and then prepare the nano combined flexible pipe of high performance polyurethane.
Background technology
Thermoplastic polyurethane (TPU) is that a class is added with unique energy obtained in polyisocyanates and polyol reaction Hot plasticization, the high polymer being soluble in certain solvent.TPU has high rigidity, high resiliency, good oil resistivity and excellent Different cryogenic property, is widely used, and can be used as various tracheaes, hydraulic oil pipe, chemical drugs QC, it is also possible to make plant equipment and instrument Specific function flexible pipe in the products such as table, because its long service life, use cost are low, social benefit is higher than rubber, will be turned into The upgraded product of rubber hose.But there are some obvious shortcomings, greatly limit its range of application.Intensity is not Height, heat resistance is poor, easily softens decompose at high temperature, its mechanical performance is drastically declined, generally, in temperature more than 80 DEG C when be unable to long-term use, and Short-range Temperature is no more than 120 DEG C.Effectively changed in itself by thermoplastic polyurethane material Property treatment can fundamentally make up deficiency in performance, will so as to meet high performance polyurethane composite soft tube field practical application Ask.
CNT (CNTs) has high intensity, toughness and elastic modelling quantity, mainly point multi-walled carbon nano-tubes or single wall CNT.SWCN is made up of individual layer cylindrical type graphite linings, and diameter distribution is small, defect is few, with higher Homogeneity；Multi-walled carbon nano-tubes has sandwich construction, layer by layer between readily become Trapping Centers and capture various defects, because And the defect of duck eye is generally discontented with the tube wall of multi-walled pipes.Using CNTs as composite material reinforcement body, can show good light Degree, elasticity, anti-fatigue performance etc., this is conducive to the development of composite.Additionally, CNT have excellent mechanical property, Electric property, heat endurance and non-linear optical property, are to prepare the preferable filler of functional composite material at present.Silica (SiO2) and titanium dioxide (TiO2) there is the premium properties such as good chemical stability, heat endurance, nontoxic, and preparation method It is simple ripe and cheap and easy to get, it is widely used in modified polyurethane elastomer.Nano silicon size is small, specific surface area big, energy High temperature resistant, silica can improve mechanical strength, elongation percentage, anti-wear performance and the ageing-resistant performance of thermoplastic polyurethane. Titanium dioxide is not only obviously improved the mechanical property of polyurethane, and the heat resistance to elastomer also improves, and, add Elastomer after titanium dioxide also has rotproofness and antibiotic property.
The method of polyurethane nano composite material is prepared at present mainly using physical blending method, and its is simple to operate, two kinds Material volume fraction is easily controllable, but interface interaction is weaker between CNT and polyurethane matrix, CNT addition mistake It is easy to reunite when many, so as to influence its dispersing uniformity in the composite, influences the performance of composite.Chinese patent 20111043537.X has invented a kind of preparation method of CNT/thermoplastic polyurethane photoresponse intelligent drives material, prepares Material have good mechanical performance, shape recovery ratio high, and Young's modulus is also improved；Chinese patent 201510094594.1 disclose a kind of modified nano-titanium dioxide compound polyurethane material and its preparation technology, in polyurethane Adding modifying titanium dioxide, the composite of preparation has the features such as photolytic activity is higher, antibiotic property is strong.
In recent years, the study on the modification to polyurethane is more and more, but multiple material is combined with each other, and then goes to be modified again Polyurethane is seldom seen, therefore the various common modified polyurethanes of inorganic material of exploration seem highly important important.In addition, Nano material γ-glycidyl ether oxygen propyl trimethoxy silicane to preparing is coupling agent modified, makes the nano material of preparation Chemical bond is formed between polyurethane, is not simple physical blending, composite property improved and is played an important roll.This hair Bright elder generation is hydrolyzed by tetraethyl orthosilicate, butyl titanate in acidifying carbon nano tube surface, the growth in situ two on acidifying CNT The composite Nano layer of silica and titanium dioxide, obtains carbon nano tube composite nano material (CNTs@SiO2-TiO2), then use again γ-glycidyl ether oxygen propyl trimethoxy silicane coupling agent carbon nano tube composite nano material is carried out coupling modifier be obtained change Property carbon nano tube composite nano material (modified CNTs@SiO2-TiO2), finally by the coupling modifier CNT composite Nano material Material solution process is evenly spread in TPUE, compound to prepare with preferable heat resistance and mechanical property Polyurethane nano composite material, and then prepare the nano combined flexible pipe of high performance polyurethane.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of preparation method of polyurethane nano composite material, the method week Phase is short, energy consumption is low, machine-shaping is convenient, easily controllable, and mechanical property and the heat resistance of the composite of preparation have larger Improve.
Technical scheme：A kind of preparation method of polyurethane nano composite material of the invention is：
A. at room temperature, it is that 65wt.%~68wt.% nitric acid adds reactor bottom by mass fraction, is received with carbon by nitric acid The mass ratio of mitron (CNTs) is 5:1~20:1, CNT is put into core acidifier, and the core acidifier is hanging It is placed in reactor, reactor is then warming up to 160 DEG C~200 DEG C 4~7h of closed acidifying, after being cooled to room temperature, will reacts Nitric acid discharge in kettle, is neutral, 60 DEG C~80 DEG C 12~24h of vacuum drying with distillation water washing CNT to filtrate, is obtained Acidifying CNT；
B. at room temperature, it is 1 by ethanol and water volume ratio:1~1:2 prepare ethanol water mixed solution, mix molten by ethanol water Liquid is 100 with the mass ratio of acidifying CNT:1~200:1, respectively by obtained acidifying CNT, ethanol water in step a Mixed solution is added in reactor, and pH to 9.0~10.0, ultrasound are adjusted with the ammoniacal liquor that mass fraction is 25wt.%~28wt.% 1~2h of dispersion, is 1 by tetraethyl orthosilicate and butyl titanate mass ratio:1~2:1 is mixed to prepare silicon titanium mixture, by ethanol with The mass ratio of silicon titanium mixture is 20:1~60:1 again mixture be made silicon titanium alcohol mixed solution, by the silicon titanium ethanol in 1~2h Mixed solution is added drop-wise in reactor, continues to react 8~12h, filtering, first with more than 100 times of acidifying CNT after dripping off The ethanol of quality is washed three times, then washs three times, 60 DEG C~80 with the deionized water of more than 100 times of acidifying carbon nanotube mass DEG C vacuum drying 12~24h, acidifying carbon nano tube surface growth in situ nano silicon and nano titanium oxide nucleocapsid bag Covering layer, forms hud typed carbon nano tube composite nano material；
C. at room temperature, it is 20 by ethanol and γ-glycidyl ether oxygen propyl trimethoxy silicane mass ratio:1~40:1, will γ-glycidyl ether oxygen propyl trimethoxy silicane is compounded into silane ethanol solution with ethanol, by silane ethanol solution and nucleocapsid Type carbon nano tube composite nano material mass ratio is 200:1~400:1, hud typed CNT obtained in step b is combined and is received Rice material is added in silane ethanol solution, and 4~6h is heated to reflux after 1~2h of ultrasonic disperse, is cooled to room temperature, is filtered, with 100 The deionized water of the hud typed carbon nano tube composite nano material quality more than times is washed three times, in 60 DEG C~80 DEG C vacuum drying 12~24h, obtains coupling modifier carbon nano tube composite nano material；
D. at room temperature, it is 10 by DMF and TPUE mass ratio:1~30:1, will DMF is added in reactor with TPUE, by TPUE and coupling Modified carbon nano-tube composite nano materials mass ratio is 20:1~1000:1, coupling modifier CNT obtained in step c is answered Close nano material be added in above-mentioned TPUE solution, 1~2h of ultrasonic disperse, at 70~90 DEG C stir 4~ After 7h, the removed under reduced pressure solvent at 80 DEG C~100 DEG C obtains polyurethane nano composite material；
CNT described in the preparation method step a of above-mentioned material is multi-walled carbon nano-tubes or SWCN In one or two kinds of combination；TPUE described in preparation method step d is polyether thermoplastic The combination of the one or two kinds of of polyurethane elastomer or polyester-type TPUE.
Beneficial effect：Modified carbon nano-tube composite nano materials are added to thermoplastic poly by the present invention by molten blending method In urethane elastomer (TPU), the mechanical property and heat resistance of TPUE are improve, be conducive to preparing high-performance Polyurethane nano composite soft tube.In the present invention, nano silicon is grown by acidifying CNT (CNTs) surface in situ (SiO2) and nano titanium oxide (TiO2) nucleocapsid integument, hud typed carbon nano tube composite nano material is formed, and use silane idol Connection agent is modified treatment and coupling modifier carbon nano tube composite nano material is obtained, and is then added to thermoplastic polyurethane bullet In gonosome, make modified thermoplastic polyurethane nano composite material that there is CNTs, SiO2And TiO2Three kinds of nano materials are compound Special performance, can well improve the mechanical property and heat resistance of TPUE, while the carbon after coupling modifier Nanotube composite nano materials surface epoxide group is had an effect with the urethano in polyurethane, promote it is organic with it is inorganic between Crosslinking, improve inorganic material dispersiveness in the composite, and then prepare the nano combined flexible pipe of high performance polyurethane.Poly- ammonia Ester nano composite material can expand the application field of TPUE.
The features of the present invention：
(1) acidification is carried out to CNT first, carboxyl is connected in carbon nano tube surface, and carboxyl is titanium dioxide Silicon, the in-situ preparation of titanium dioxide provide active sites.CNT is positioned in acidifier and is separated with salpeter solution, adopted CNT is acidified with nitric acid vapor, and traditional acidization tool is that CNT is immersed in nitric acid-sulfuric acid mixed solution. CNT is acidified using nitric acid vapor method, it is possible to reduce loss of the CNT in acidization, and this mode has Beneficial to the washing drying of carbon pipe, the acidizing effect of nitric acid vapor method is better than general nitration mixture acidization；
(2) in the basic conditions, tetraethyl orthosilicate and butyl titanate are hydrolyzed in CNT carboxyl surface in situ and grown Silica, two kinds of inorganic nano materials of titanium dioxide, silica and oxygen are coated using in-situ hydrolysis method in carbon nano tube surface Change titanium and form multilayer core shell nanocomposite, silica is formed covalently with titanium dioxide with the carboxyl of carbon nano tube surface Key, improves silica and disperses with the uniform high-efficiency of titanium dioxide.In situ synthesis can be by silica, titanium dioxide and carbon Nanotube table is closely coupled, and in situ synthesis reduce silica and hydrolyzed in the solution with titanium dioxide.The inorganic of preparation receives Rice material is a compound system, is not single mixing, can comprehensively utilize CNT and be received with silica, titanium dioxide The performance of rice material, enables the polyurethane composite nano materials of preparation while having CNT, silica, titanium dioxide The performance of three's synergistic combination modified polyurethane, the preferable method of property CNT.Core-shell type nano silica and titanium oxide Formation will not only reduce effect of the CNT in reinforcement polyurethane elastomer aspect of performance, on the contrary can be by its organic-inorganic Interface interaction plays excellent dispersion nanotube effect；
(3) it is inorganic material-modified to what is prepared with γ-glycidyl ether oxygen propyl trimethoxy silicane, make the inorganic of preparation Material surface has epoxide group, and epoxide group can react with the carbamate in polyurethane, can strengthen nothing Interaction between machine material and polyurethane, inorganic nano is carried out on the basis of not destroying carbon nanometer tube structure to its surface Particle is coated and organic coupling agent modified synergic can be substantially improved its compatibility in polyurethane system, can effectively overcome nanometer Pipe is easily reunited, easy entanglement the shortcomings of, while the wearability of nano composite material, tensile strength and thermally-stabilised can also further be strengthened Property.
(4) present invention is prepared for polyurethane nano composite material by the molten blending method of one kind, by thermoplastic polyurethane bullet Gonosome is well mixed in the solution with the inorganic nano material for preparing, and then deviates from solvent and prepares composite nano materials, is processed into Type is convenient；
(5) polyurethane nano composite material for preparing has more preferable heat resistance and mechanical property, enables polyurethane It is applied under higher temperature environment, and good mechanical property can be kept, can be applied to prepare high performance polyurethane nano combined Flexible pipe.
Specific embodiment
A kind of polyurethane nano composite material of the invention is by TPUE and coupling modifier carbon nanometer Pipe composite nano materials are prepared from using solution process is compound, and coupling modifier carbon nano tube composite nano material is with γ-shrink Glycerine ether oxygen propyl trimethoxy silicane is obtained to carbon nano tube composite nano material coupling modifier, and hud typed CNT is combined Nano material is obtained in acidifying carbon nano tube surface hydrolysis growth in situ by tetraethyl orthosilicate, butyl titanate.What is prepared is poly- In urethane nano composite material, the weight/mass percentage composition 95wt.%~99.9wt.% of polyurethane, the quality percentage of CNT Content 0.03wt.%~4wt.%, the weight/mass percentage composition 0.01wt.%~1wt.% of silica, the quality of titanium dioxide Percentage composition 0.01wt.%~1wt.%.The polyurethane nano composite material is cut into the 5A type dumbbell battens of 75mm × 4mm, The tensile property of sample is tested with electronic universal tester by GB/T1040.2-2006, rate of extension is 50mm/min, Thermogravimetric analysis is carried out under nitrogen atmosphere.
Embodiment 1：
At 25 DEG C, 0.5g multi-walled carbon nano-tubes (MWCNTs) is added in core acidifier, core acidifier is hanging It is placed in the 100mL closed reactors containing 2.5mL (mass fraction 65wt.%) nitric acid, then heats to 160 DEG C, is acidified 4h. Reaction end is cooled to room temperature, removes salpeter solution, is washed with deionized to neutrality, and 60 DEG C of vacuum drying ovens obtain acid after drying Carbon nano tube.Then 0.1g acidifying CNTs are taken to be added in reactor, and adds 5mL ethanol and 5mL water, ultrasonic disperse 1h.PH to 9.0~10.0 is adjusted with the ammoniacal liquor that mass fraction is 25wt.%~28wt.%, with constant pressure funnel to reactant The 60mL alcohol mixed solutions containing 1mL tetraethyl orthosilicates and 1mL tetrabutyl titanates are added dropwise in system in 1h, 8h is reacted.Cross Filter, is washed three times with 50mL ethanol, is then washed three times with 50mL deionized waters, and 24h is dried in 60 DEG C of vacuum drying ovens, obtains core Shell mould carbon nano tube composite nano material (MWCNTs@SiO2-TiO2)；
At 25 DEG C, 0.1g MWCNTs@SiO are taken2-TiO2Composite nano materials add 20mL ethanol solutions, then add 1mL γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560), 4h is heated to reflux after ultrasonic disperse 1h, is cooled to room temperature, Filtering, is washed three times with 50mL deionized waters, and 24h is dried in 60 DEG C of vacuum drying ovens, obtains coupling modifier MWCNTs@SiO2-TiO2 Composite nano materials；
At 25 DEG C, the coupling modifier MWCNTs@SiO of the above-mentioned preparations of 0.0025g are taken2-TiO2Composite nano materials, are added to In reactor, 25mL DMFs (DMF) solution, 2.5g Polyether-type thermoplastic polyurethane elastomers are subsequently adding (TPU), ultrasonic disperse 1h.70 DEG C are warming up to, 4h is stirred, the compound polyurethane material that will finally prepare removed under reduced pressure at 80 DEG C DMF, obtains polyurethane nano composite material (TPU/MWCNTs@SiO2-TiO2)；
The polyurethane nano composite material fracture strength has reached 36MPa, than pure Polyether-type thermoplastic polyurethane elastomer 3% is improve, elongation at break has reached 700%, 25% is improve than pure Polyether-type thermoplastic polyurethane elastomer.In nitrogen Corresponding temperature has reached 317 DEG C than pure polyether thermoplastic elastic polyurethane when thermogravimetric analysis, mass loss 10% under atmosphere Body improves 1.6%.
Embodiment 2：
At 25 DEG C, 0.5g multi-walled carbon nano-tubes (MWCNTs) is added in core acidifier, core acidifier is hanging It is placed in the 100mL closed reactors containing 5mL (mass fraction 65wt.%) nitric acid, then heats to 170 DEG C, is acidified 5h.Instead Should terminate to be cooled to room temperature, remove salpeter solution, be washed with deionized to neutrality, 65 DEG C of vacuum drying ovens are acidified after drying CNT.Then take 0.1g acidifyings MWCNTs to be added in reactor, and add 6mL ethanol and 6mL water, ultrasonic disperse 1h. PH to 9.0~10.0 is adjusted with the ammoniacal liquor that mass fraction is 25wt.%~28wt.%, with constant pressure funnel to reaction system In be added dropwise the 90mL alcohol mixed solutions containing 1.5mL tetraethyl orthosilicates and 1.5mL tetrabutyl titanates in 1h, react 9h. Filtering, is washed three times with 50mL ethanol, is then washed three times with 50mL deionized waters, and 24h is dried in 60 DEG C of vacuum drying ovens, is obtained Hud typed carbon nano tube composite nano material (MWCNTs@SiO2-TiO2)；
At 25 DEG C, 0.1g MWCNTs@SiO are taken2-TiO2Composite nano materials add 25mL ethanol solutions, then add 1mL γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560), 4.5h is heated to reflux after ultrasonic disperse 1h, is cooled to room Temperature, filtering, is washed three times with 50mL deionized waters, and 24h is dried in 65 DEG C of vacuum drying ovens, obtains coupling modifier MWCNTs@SiO2- TiO2Composite nano materials；
At 25 DEG C, the MWCNTs@SiO after the above-mentioned coupling modifiers of 0.0125g are taken2-TiO2Composite nano materials, are added to anti- Answer in device, be subsequently adding 50mL DMFs (DMF) solution, 2.5g polyester-type TPUEs (TPU), ultrasonic disperse 1h.75 DEG C are warming up to, 5h is stirred, the compound polyurethane material that will finally prepare removed under reduced pressure at 85 DEG C DMF, obtains TPU/MWCNTs@SiO2-TiO2Nano composite material；
The polyurethane nano composite material fracture strength has reached 37MPa, than pure polyester-type TPUE 5.7% is improved, elongation at break has reached 869%, 40% is improved than pure polyester-type TPUE.In blanket of nitrogen Lower thermogravimetric analysis is enclosed, corresponding temperature is 320 DEG C than the raising of pure polyester-type TPUE during mass loss 10% 2.5%.
Embodiment 3：
At 25 DEG C, 0.5g SWCNs (SWCNTs) are added in core acidifier, core acidifier is hanging It is placed in the 100mL closed reactors containing 7.5mL (mass fraction 65wt.%~68wt.%) nitric acid, then heats to 180 DEG C, it is acidified 5.5h.Reaction end is cooled to room temperature, removes salpeter solution, is washed with deionized to neutrality, 70 DEG C of vacuum drying ovens Obtain being acidified CNT after drying.Then take 0.1g acidifyings SWCNTs to be added in reactor, and add 7mL ethanol and 7mL Water, ultrasonic disperse 1h.PH is adjusted to 9.0~10.0 with the ammoniacal liquor that mass fraction is 25wt.%~28wt.%, uses constant pressure addition Funnel is molten to the 120mL ethanol mixing being added dropwise in 1h in reaction system containing 2mL tetraethyl orthosilicates and 2mL tetrabutyl titanates Liquid, reacts 10h.Filtering, is washed three times with 50mL ethanol, is then washed three times with 50mL deionized waters, in 70 DEG C of vacuum drying ovens In dry 12h, obtain hud typed carbon nano tube composite nano material (SWCNTs@SiO2-TiO2)；
At 25 DEG C, 0.1g SWCNTs@SiO are taken2-TiO2Composite nano materials add 30mL ethanol solutions, then add 1mL γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560), 5h is heated to reflux after ultrasonic disperse 2h, is cooled to room temperature, Filtering, is washed three times with 50mL deionized waters, and 24h is dried in 60 DEG C of vacuum drying ovens, obtains coupling modifier SWCNTs@SiO2-TiO2 Composite nano materials；
At 25 DEG C, the SWCNTs@SiO after the above-mentioned coupling modifiers of 0.025g are taken2-TiO2Composite nano materials, are added to reaction In device, 60mL DMFs (DMF) solution, 2.5g Polyether-type thermoplastic polyurethane elastomers are subsequently adding (TPU), ultrasonic disperse 2h.80 DEG C are warming up to, 5.5h is stirred, the compound polyurethane material for preparing finally is depressurized de- at 90 DEG C Except DMF, TPU/SWCNTs@SiO are obtained2-TiO2Nano composite material；
The polyurethane nano composite material fracture strength has reached 40MPa, than pure Polyether-type thermoplastic polyurethane elastomer 14% is improved, elongation at break reaches 943%, 52% is improved than pure Polyether-type thermoplastic polyurethane elastomer.In nitrogen atmosphere Lower thermogravimetric analysis, corresponding temperature is 329 DEG C than the raising of pure Polyether-type thermoplastic polyurethane elastomer during mass loss 10% 5.7%.
Embodiment 4：
At 25 DEG C, 0.5g SWCNs (SWCNTs) are added in core acidifier, core acidifier is hanging It is placed in the 100mL closed reactors containing 8.5mL (mass fraction 65wt.%~68wt.%) nitric acid, then heats to 190 DEG C, it is acidified 6h.Reaction end is cooled to room temperature, removes salpeter solution, is washed with deionized to neutrality, and 75 DEG C of vacuum drying ovens are done Obtain being acidified CNT after dry.Then take 0.1g acidifyings SWCNTs to be added in reactor, and add 7mL ethanol and 9mL water, Ultrasonic disperse 1h.PH is adjusted to 9.0~10.0 with the ammoniacal liquor that mass fraction is 25wt.%~28wt.%, uses constant pressure funnel To the 90mL alcohol mixed solutions containing 2mL tetraethyl orthosilicates and 1mL tetrabutyl titanates are added dropwise in reaction system in 1h, instead Answer 11h.Filtering, is washed three times with 50mL ethanol, is then washed three times with 50mL deionized waters, is dried in 60 DEG C of vacuum drying ovens 24h, obtains hud typed carbon nano tube composite nano material (SWCNTs@SiO2-TiO2)；
At 25 DEG C, 0.1g SWCNTs@SiO are taken2-TiO2Nano material adds 35mL ethanol solutions, then plus 1mL γ-(2, The oxygen of 3- epoxies third) propyl trimethoxy silicane (KH-560), 5.5h is heated to reflux after ultrasonic disperse 2h, room temperature is cooled to, filter, Washed with 50mL deionized waters three times, 24h is dried in 70 DEG C of vacuum drying ovens, obtain coupling modifier SWCNTs@SiO2-TiO2It is compound Nano material；
At 25 DEG C, the SWCNTs@SiO after the above-mentioned coupling modifiers of 0.05g are taken2-TiO2Composite nano materials, are added to reaction In device, be subsequently adding 65mL DMFs (DMF) solution, 1.5g polyester-types TPUE and The mixing polyurethane elastomer (TPU) of 1.0g Polyether-type thermoplastic polyurethane elastomers, ultrasonic disperse 2h.85 DEG C are warming up to, are stirred 6h is mixed, the compound polyurethane material that will finally prepare removed under reduced pressure DMF at 95 DEG C obtains TPU/SWCNTs@SiO2-TiO2Nanometer Composite；
The fracture strength of the polyurethane nano composite material reaches 53MPa, and 51% is improved than mixing polyurethane elastomer, breaks Split elongation and reach 1194%, 93% is improved than mixing polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, mass loss Corresponding temperature is 348 DEG C than mixing polyurethane elastomer raising 11.5% when 10%.
Embodiment 5：
At 25 DEG C, 0.25g multi-walled carbon nano-tubes (MWCNTs) and 0.25g SWCNs (SWCNTs) are added to sand In core acidifier, core acidifier is vacantly placed in the 100mL containing 10mL (mass fraction 65wt.%~68wt.%) nitric acid In closed reactor, 200 DEG C are then heated to, be acidified 7h.Reaction end is cooled to room temperature, removes salpeter solution, uses deionization To neutrality, 80 DEG C of vacuum drying ovens obtain being acidified CNT water washing after drying.Then take 0.1g acidifyings CNTs and be added to reaction In device, and add 10mL ethanol and 10mL water, ultrasonic disperse 1h.Adjusted with the ammoniacal liquor that mass fraction is 25wt.%~28wt.% PH to 9.0~10.0, is added dropwise containing 3mL tetraethyl orthosilicates and 2mL titaniums in reaction system with constant pressure funnel in 1h The 160mL alcohol mixed solutions of sour N-butyl, react 12h.Filtering, is washed three times with 50mL ethanol, then uses 50mL deionizations Water washing three times, 24h is dried in 60 DEG C of vacuum drying ovens, obtains hud typed carbon nano tube composite nano material (MSWCNTs@SiO2- TiO2)；
At 25 DEG C, the above-mentioned MSWCNTs@SiO of 0.1g are taken2-TiO2Composite nano materials add 38mL ethanol solutions, Ran Houjia 1mL γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH-560), 6h is heated to reflux after ultrasonic disperse 2h, is cooled to room Temperature, filtering, is washed three times with 50mL deionized waters, and 24h is dried in 80 DEG C of vacuum drying ovens, obtains coupling modifier MSWCNTs@ SiO2-TiO2Composite nano materials；
At 25 DEG C, the MSWCNTs@SiO after the above-mentioned coupling modifiers of 0.125g are taken2-TiO2Composite nano materials, are added to anti- Answer in device, be subsequently adding 75mL DMFs (DMF) solution, 2.5g Polyether-type thermoplastic polyurethane elastomers (TPU), ultrasonic disperse 2h.90 DEG C are warming up to, 7h is stirred, the compound polyurethane material for preparing finally is depressurized de- at 100 DEG C Except DMF, TPU/MSWCNTs@SiO are obtained2-TiO2Nano composite material；
The polyurethane nano composite material fracture strength has reached 38MPa, than pure Polyether-type thermoplastic polyurethane elastomer 8.5% is improved, elongation at break reaches 1126MPa, 82% is improved than pure Polyether-type thermoplastic polyurethane elastomer.In blanket of nitrogen Lower thermogravimetric analysis is enclosed, corresponding temperature is 338 DEG C than the raising of pure Polyether-type thermoplastic polyurethane elastomer during mass loss 10% 8.3%.

Claims (3)

1. a kind of preparation method of polyurethane nano composite material, it is characterised in that the preparation method is：
A. at room temperature, it is that 65wt.%~68wt.% nitric acid adds reactor bottom by mass fraction, by nitric acid and CNT Mass ratio be 5:1~20:1, CNT is put into core acidifier, and the core acidifier is vacantly placed in reactor In, reactor is then warming up to 160 DEG C~200 DEG C 4~7h of closed acidifying, after being cooled to room temperature, by the nitric acid in reactor Discharge, with distillation water washing CNT to filtrate to neutrality, 60 DEG C~80 DEG C 12~24h of vacuum drying must be acidified carbon nanometer Pipe；
B. at room temperature, it is 1 by ethanol and water volume ratio:1~1:2 prepare ethanol water mixed solutions, by ethanol water mixed solution with The mass ratio for being acidified CNT is 100:1~200:1, obtained acidifying CNT, ethanol water in step a are mixed respectively Solution is added in reactor, and pH to 9.0~10.0, ultrasonic disperse are adjusted with the ammoniacal liquor that mass fraction is 25wt.%~28wt.% 1~2h；It is 1 by tetraethyl orthosilicate and butyl titanate mass ratio:1~2:1, the two is mixed to prepare silicon titanium mixture, by second Alcohol is 20 with the mass ratio of silicon titanium mixture:1~60:1 again mixture be made silicon titanium alcohol mixed solution, by the silicon titanium in 1~2h Alcohol mixed solution is added drop-wise in reactor, continues to react 8~12h after dripping off, and filtering is first received with more than 100 times of acidifying carbon The ethanol of mitron quality is washed three times, then is washed three times, 60 DEG C with the deionized water of more than 100 times of acidifying carbon nanotube mass ~80 DEG C of 12~24h of vacuum drying, in acidifying carbon nano tube surface growth in situ nano silicon and nano titanium oxide core Shell integument, forms hud typed carbon nano tube composite nano material；
C. at room temperature, it is 20 by ethanol and γ-glycidyl ether oxygen propyl trimethoxy silicane mass ratio:1~40:1, by γ- Glycidyl ether oxygen propyl trimethoxy silicane is compounded into silane ethanol solution with ethanol, by silane ethanol solution and hud typed carbon Nanotube composite nano materials mass ratio is 200:1~400:1, by hud typed CNT composite Nano material obtained in step b Material be added in silane ethanol solution, be heated to reflux 4~6h after 1~2h of ultrasonic disperse, be cooled to room temperature, filter, with 100 times with On hud typed carbon nano tube composite nano material quality deionized water wash three times, 60 DEG C~80 DEG C be vacuum dried 12~ 24h, obtains coupling modifier carbon nano tube composite nano material；
D. at room temperature, it is 10 by DMF and TPUE mass ratio:1~30:1, by N, N- Dimethylformamide is added in reactor with TPUE, and TPUE solution is obtained, and is pressed TPUE is 20 with coupling modifier carbon nano tube composite nano material mass ratio:1~1000:1, by step c Obtained coupling modifier carbon nano tube composite nano material is added in above-mentioned TPUE solution, ultrasonic disperse 1~2h, after stirring 4~7h at 70~90 DEG C, the removed under reduced pressure DMF at 80 DEG C~100 DEG C obtains polyurethane Nano composite material.
2. the preparation method of polyurethane nano composite material according to claim 1, it is characterised in that the preparation method CNT described in step a is the combination of the one or two kinds of in multi-walled carbon nano-tubes or SWCN.
3. the preparation method of polyurethane nano composite material according to claim 1, it is characterised in that the preparation method TPUE described in step d is Polyether-type thermoplastic polyurethane elastomer or polyester-type thermoplastic poly ammonia The combination of the one or two kinds of in ester elastomer.
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