CN108164980A - Carbon nano-tube modification TPU materials for 3D printing and preparation method thereof - Google Patents

Carbon nano-tube modification TPU materials for 3D printing and preparation method thereof Download PDF

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Publication number
CN108164980A
CN108164980A CN201711460942.8A CN201711460942A CN108164980A CN 108164980 A CN108164980 A CN 108164980A CN 201711460942 A CN201711460942 A CN 201711460942A CN 108164980 A CN108164980 A CN 108164980A
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carbon nano
tube
printing
carbon nanotube
carbon
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代金辉
李龙飞
罗杰
张宁
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Shandong Inov Polyurethane Co Ltd
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Shandong Inov Polyurethane Co Ltd
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Priority to CN201711460942.8A priority Critical patent/CN108164980A/en
Publication of CN108164980A publication Critical patent/CN108164980A/en
Priority to PCT/CN2018/114370 priority patent/WO2019128484A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Abstract

The invention belongs to synthesis of polymer material fields, and in particular to a kind of for carbon nano-tube modification TPU materials of 3D printing and preparation method thereof.Including following raw material：Thermoplastic polyurethane elastomer, modified carbon nano-tube, hydrolysis agent, ultra-violet absorber, plasticizer and antioxidant；Carbon nanotube is carried out surface oxidation treatment by the present invention, introduces carbonyl, hydroxy functional group, through silanization treatment after, introduces active site, finally to carbon nano tube surface grafting and modifying, is introduced amido functional group, is obtained modified carbon nano-tube.The present invention has both TPU and the excellent properties of carbon nanotube, carbon nanotube is after modified, the compatibility that can be obviously improved between carbon nanotube and basis material, it can be homogeneously dispersed in TPU basis materials, modified TPU materials have excellent wear-resisting property, antistatic property, thermal stability can be used as a kind of 3D printing material.

Description

Carbon nano-tube modification TPU materials for 3D printing and preparation method thereof
Technical field
The invention belongs to synthesis of polymer material fields, and in particular to a kind of carbon nano-tube modification TPU for 3D printing Material and preparation method thereof.
Background technology
Thermoplastic polyurethane elastomer (Thermoplastic polyurethane, TPU) material is excellent comprehensive by its Performance is closed to be widely used in each field.However there is also some shortcomings for performance of TPU materials itself, limiting it should With, relative to other engineering plastics, TPU materials are there is the shortcomings that wear-resisting property is insufficient, antistatic property is insufficient at present, because This TPU material is difficult individually as structural material.The carbon nanomaterial nano-filled object very high as potential value, can be very big Improve the intensity, wearability, antistatic property of various types of materials.Therefore carbon nanotube becomes polymer composites and preferably enhances Body, but since carbon nanotube is easily gathered into bundles or wound, surface is with respect to 'inertia', in common organic solvent or polymerization Dispersion degree in object material is low, this greatlys restrict its extensive use.At present, the critical issue of carbon nano tube-doped TPU is How carbon nanotube compatibility and dispersion problem in basis material is realized, so as to give full play to the superiority of carbon nanotube Can, the comprehensive performance of enhancing TPU materials.
In recent years, 3D printing technique high speed development at home, the most important part of 3D printing is exactly 3D printing consumptive material Selection.For TPU as a kind of novel organic polymer synthetic material, properties are excellent, and the material of this excellent properties is promoted And be fully applicable to 3D printing technique, maximum bottleneck be how the excellent 3D printing material of processability.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of carbon nano-tube modification TPU for 3D printing Material, has excellent wear-resisting property, antistatic property, and thermal stability can be used as a kind of 3D printing material；The present invention also carries For preparation method.
Carbon nano-tube modification TPU materials of the present invention for 3D printing, including following raw material：Thermoplastic polyurethane Elastomer, modified carbon nano-tube, hydrolysis agent, ultra-violet absorber, plasticizer and antioxidant；Carbon is is received by modified carbon nano-tube Mitron carries out oxidation processes, silanization treatment and amination and handles to obtain.
Wherein：The preparation method of modified carbon nano-tube is as follows：
(1) oxidation processes carbon nanotube
By carbon nanotube ultrasonic disperse, heating sequentially adds the concentrated sulfuric acid and concentrated nitric acid, carries out oxidation reaction, and reaction is completed Afterwards, it is post-treated to obtain the carbon nanotube of oxidation processes；
(2) silanization treatment oxide/carbon nanometer tube
By the carbon nanotube of oxidation processes, methacryloxypropyl trimethoxy silane, absolute ethyl alcohol and deionization Water mixing ultrasonic disperse；It reheats and carries out Silanization reaction, whole logical N in reaction process2, after the completion of reaction, post-treated To silane carbon nano tube；
(3) the amination processing of silane carbon nano tube
Nitrogen is passed through into reaction bulb, by silane carbon nano tube, N, N- methylene-bisacrylamides, deionized water and mistake Potassium sulfate solution is sequentially added in reaction bulb, formation mixed liquor, re-ultrasonic dispersion, and then heating stirring carries out polymerisation, It is post-treated to obtain modified carbon nano-tube after the completion of reaction.
The preparation method of carbon nanotube has arc discharge method, chemical vapour deposition technique (hydrocarbon gas pyrolysismethod), consolidates at present Phase pyrolysismethod, gas combustion method and polymerisation synthetic method etc..The carbon nanotube of the present invention before modified is chemical vapor deposition Prepared by method, first ultrasound is removed and reduces multiwall nanotube and agglomeration when modified.
The rate of charge of carbon nanotube, the concentrated sulfuric acid and concentrated nitric acid is 5 in step (1)：95-105：45-55, carbon nanotube is with g Meter, the concentrated sulfuric acid and concentrated nitric acid are in terms of mL；The temperature of oxidation reaction is 48-52 DEG C in step (1), and the reaction time is 95-105 points Clock.
The carbon nanotube of oxidation processes in step (2), methacryloxypropyl trimethoxy silane, absolute ethyl alcohol and The rate of charge of deionized water is 3：0.4-0.5：42-48：14-16, the carbon nanotube of oxidation processes is in terms of g, methacryloxypropyl Base propyl trimethoxy silicane, absolute ethyl alcohol and deionized water are in terms of mL；The temperature of Silanization reaction is 60-65 in step (2) DEG C, the reaction time is 115-125 minutes.
Silane carbon nano tube, N,N methylene bis acrylamide, deionized water and persulfate aqueous solution in step (3) Rate of charge be 2：0.07-0.08：24-26：1-1.1, a concentration of 1-1.1mmol/L of persulfate aqueous solution, silanization carbon Nanotube, N, N- methylene-bisacrylamides are in terms of g, and deionized water and persulfate aqueous solution are in terms of mL；It polymerize in step (3) Reaction temperature is 65-70 DEG C, and the reaction time is 300-360 minutes.
It is post-processed in step (1), (2) and (3) and is：Product by absolute ethyl alcohol is washed, is filtered, vacuum drying.
Preferably, the carbon nano-tube modification TPU materials of the present invention for 3D printing, including following parts by weight Raw material：
Thermoplastic polyurethane elastomer includes one kind in polyether polyurethane elastomer or polyester polyurethane elastomer Or two kinds, shore hardness is 55A~75D, and particle size is 3~5mm.
Hydrolysis agent is technical grade single second carbide imine or technical grade polycarbodiimide；
Ultra-violet absorber is one or more of benzophenone class, benzotriazole or hindered amines；
Plasticizer is one kind in aliphatic dibasic acid ester, Phthalates, benzene polyacid esters or benzoates It is or several；
Antioxidant is Hinered phenols antioxidant, phosphite ester kind antioxidant or one kind or several in monothioester kind antioxidant Kind；
Organic solvent is any one in DMF (n,N dimethylformamide) or DMA (N, N dimethyl acetamide).
The preparation method of carbon nano-tube modification TPU materials of the present invention for 3D printing, it is characterised in that：Including Following steps：
(1) thermoplastic polyurethane elastomer, modified carbon nano-tube are sequentially added in organic solvent, ultrasonic disperse is into mixing Liquid, is thermally formed pasty mixture, pelletizing after vacuum drying, and product is modified primary master batch for TPU；
(2) TPU modifications primary master batch, hydrolysis agent, antioxidant, ultra-violet absorber, plasticizer is weighed to be placed at a high speed It is sufficiently mixed in kneading machine, adds double screw extruder and carry out extruding pelletization；Product is obtained after vacuum drying.
The granular size of pelletizing is 6mm*3mm*6mm after step (1) vacuum drying.
Carbon nanotube is carried out surface oxidation treatment by the present invention, introduces carbonyl, hydroxy functional group, after through silanization at Reason introduces active site, finally to carbon nano tube surface grafting and modifying, introduces amido functional group, obtains modified carbon nano-tube.
It dries and is granulated after being then sufficiently mixed TPU materials and modified carbon nano-tube by solution blended process, obtain TPU and change Property primary master batch；After TPU is modified the uniform mixing of primary master batch, plasticizer, antioxidant, hydrolysis agent again, finally by double spiral shells Bar extruder extruding pelletization.
Compared with prior art, the present invention has the following advantages：
(1) carbon nano-tube modification TPU prepared by the present invention is the excellent mechanical property for utilizing carbon nanotube, electric conductivity And thermodynamic stability, in preparation process, carbon nano-tube material is ground, after ultrasonic stripping, substantially with few layer or individual layer Based on carbon nanotube, targetedly surface is carried out to carbon nanotube and is modified, can be obviously improved carbon nanotube and basis material it Between compatibility, can be homogeneously dispersed in TPU basis materials.
(2) the present invention also provides preparation methods, compare melt-blending process, and solution blended process can significantly improve carbon nanometer Dispersibility of the pipe in basis material, while the auxiliary agents such as antioxidant, hydrolysis agent, plasticizer are introduced, modified TPU materials tool There are excellent wear-resisting property, antistatic property, thermal stability can be used as a kind of 3D printing material.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of carbon nano-tube modification TPU materials for 3D printing are prepared from the following raw materials in parts by weight：
Specific preparation process is as follows：
It weighs dry TPU particles (thermoplastic polyurethane elastomer) 100g, modified carbon nano-tube 1g and sequentially adds 50mL bis- Methylformamide is placed in ultrasonic wave separating apparatus and is disperseed, is dissolved into mixed liquor.Mixed solution is then placed in evaporating dish In, under the conditions of 50 DEG C, heating time 40min eventually forms pasty mixture, pelletizing after vacuum drying, granular size 6mm* 3mm*6mm, product are modified primary master batch for TPU.It weighs TPU and is modified primary master batch 100g, carbodiimides 0.1g, antioxidant 0.1g, ultra-violet absorber 0.1g, plasticizer 0.5g, which is placed in high speed mixing smelting machine, to be sufficiently mixed, and above-mentioned pre-composition is added in double spiral shells Bar extruder carries out extruding pelletization.Product is placed in vacuum drying chamber and is dried, dried product exhibited is to be beaten available for 3D The carbon nano-tube modification TPU materials of print.
The preparation method of modified carbon nano-tube is as follows：
1st, oxidation processes carbon nanotube
5g carbon nanotubes is taken to add in three-necked flask, is placed on ultrasonic wave separating apparatus and carries out ultrasonic disperse 30min.By three mouthfuls Flask is placed on electric heating magnetic stirring apparatus, sequentially adds the 100mL concentrated sulfuric acids, 50mL concentrated nitric acids, oxidation reaction is carried out at 50 DEG C, Stop heating after reacting 100min, reaction solution is cooled to 25 DEG C.Resultant product is washed by absolute ethyl alcohol, filtered, vacuum drying, Dried oxide/carbon nanometer tube has abundant carbonyl, carboxyl, hydroxy functional group；
2nd, silanization treatment oxide/carbon nanometer tube
By oxidation processes carbon nanotube 3g, methacryloxypropyl trimethoxy silane (KH-570) 0.5mL, anhydrous Ethyl alcohol 45mL, deionized water 15mL are added in three-necked flask；Three-necked flask is placed on ultrasonic wave separating apparatus and carries out ultrasonic disperse 30min；After dispersion, three-necked flask is placed on electric heating blender, Silanization reaction 120min is carried out at 65 DEG C of heating temperature, Whole process starts to input N2, reaction product is silane carbon nano tube C-C9H17O5Si.Suction filtration then is washed with absolute ethyl alcohol, is retained Filter cake, vacuum drying, dried product exhibited are silane carbon nano tube.
3rd, the amination modification of silane carbon nano tube
Nitrogen, silane carbon nano tube 2g, N, N- methylene bisacrylamide acyls are passed through into preprepared three-necked flask Amine 0.075g, deionized water 25mL, 2mmol/L persulfate aqueous solution 1mL are sequentially added in three-necked flask, form mixed liquor, The three-necked flask for filling mixed liquor is placed on ultrasonic wave separating apparatus and is disperseed, then puts the three-necked flask for filling mixed liquor In on electrical heating blender, under the conditions of 70 DEG C, 360min is stirred, carries out polymerisation, end product C-C22H38N4O8Si：Ammonia The carbon nanotube of base.It finally washs, filter, vacuum drying, being the modified carbon nano-tube of aminated modification after dry.
Embodiment 2
A kind of carbon nano-tube modification TPU materials for 3D printing are prepared from the following raw materials in parts by weight：
Preparation process is as follows：
Dry TPU particles 100g is weighed, modified carbon nano-tube 2g sequentially adds 50mL dimethylformamides, is placed in ultrasound Disperseed in wave separating apparatus, be dissolved into mixed liquor.Then mixed solution is placed in evaporating dish, under the conditions of 50 DEG C, during heating Between 40min, eventually form pasty mixture, pelletizing after vacuum drying, granular size 6mm*3mm*6mm, product is that TPU is modified Primary master batch.Weigh TPU be modified primary master batch 100g, carbodiimides 0.1g, antioxidant 0.1g, ultra-violet absorber 0.1g, Plasticizer 0.5g, which is sequentially placed into high speed mixing smelting machine, to be sufficiently mixed, and above-mentioned pre-composition addition double screw extruder squeeze out and is made Grain.Product is placed in vacuum drying chamber and is dried, dried product exhibited is the carbon nano-tube modification TPU available for 3D printing Material.
Modified carbon nano-tube used is same as Example 1.
Embodiment 3
A kind of carbon nano-tube modification TPU materials for 3D printing are prepared from the following raw materials in parts by weight：
Preparation process is as follows：
Dry TPU particles 100g is weighed, modified carbon nano-tube 3g sequentially adds 50mL dimethylformamides, is placed in ultrasound Disperseed in wave separating apparatus, be dissolved into mixed liquor.Then mixed solution is placed in evaporating dish, under the conditions of 50 DEG C, during heating Between 40min, eventually form pasty mixture, pelletizing after vacuum drying, granular size 6mm*3mm*6mm, product is that TPU is modified Primary master batch.It weighs TPU and is modified primary master batch 100g, carbodiimides 0.1g, antioxidant 0.1g, ultra-violet absorber 0.1g, Plasticizer 0.5g, which is placed in high speed mixing smelting machine, to be sufficiently mixed, and above-mentioned pre-composition is added in double screw extruder carries out extruding pelletization. Product is placed in vacuum drying chamber and is dried, dried product exhibited is the carbon nano-tube modification TPU materials available for 3D printing Material.
Modified carbon nano-tube used is same as Example 1.
Comparative example 1
A kind of carbon nano-tube modification TPU materials for 3D printing are prepared from the following raw materials in parts by weight：
Specific preparation process is as follows：
Dry TPU particles 100g is weighed, original non-modified carbon nanotube 1g sequentially adds 50mL dimethyl formyls Amine is placed in ultrasonic wave separating apparatus and is disperseed, is dissolved into mixed liquor.Then mixed solution is placed in evaporating dish, 50 DEG C of items Under part, heating time 40min eventually forms pasty mixture, pelletizing after vacuum drying, granular size 6mm*3mm*6mm, production Object is modified primary master batch for TPU.It weighs TPU and is modified primary master batch 100g, carbodiimides 0.1g, antioxidant 0.1g, ultraviolet light Absorbent 0.1g, plasticizer 0.5g are placed in high speed mixing smelting machine and are sufficiently mixed, by above-mentioned pre-composition add in double screw extruder into Row extruding pelletization.Product is placed in vacuum drying chamber and is dried, dried product exhibited is the carbon nanometer available for 3D printing Pipe modified TPU material.
Comparative example 2
Preparation process is as follows：
TPU material 100g are weighed, are dissolved in 50mL DMF, after drying, are granulated again, it is then that TPU particles, carbonization two is sub- Amine 0.1g, antioxidant 0.1g, ultra-violet absorber 0.1g, plasticizer 0.5g, which is placed in high speed mixing smelting machine, to be sufficiently mixed, will be above-mentioned Pre-composition adds in double screw extruder and carries out extruding pelletization.Product is placed in vacuum drying chamber and is dried, dried product exhibited It as can be used for the carbon nano-tube modification TPU materials of 3D printing.
The modified TPU material that embodiment 1-3 and comparative example 1-2 is obtained, with tensilon, thermal-analysis instrumentation (TGA), DIN abrasion machines, four probe resistance rate testers carry out the TPU materials of carbon nano-tube modification phenetic analysis, test knot Fruit is shown in Table 1.
1 modified TPU material property of table
TPU raw material are compared it can be seen from 1 data of table, carbon nano-tube modification TPU materials prepared by the present invention can be shown It writes and improves its tensile strength, thermal stability, wear-resisting property reduces its surface resistivity.The production prepared using modified carbon nano-tube Product ratio is promoted significantly using unmodified properties of product, and modified carbon nano tube-doped TPU materials are compared comparative example 2 and more had Be obviously improved, this also demonstrate the present invention carbon nano tube-doped modification can be promoted its dispersibility in TPU materials and Compatibility, so as to promote the mechanical strength of TPU materials, thermal stability, wear-resisting property and antistatic property.

Claims (10)

1. a kind of carbon nano-tube modification TPU materials for 3D printing, it is characterised in that：Including following raw material：Thermoplastic poly ammonia Ester elastomer, modified carbon nano-tube, hydrolysis agent, ultra-violet absorber, plasticizer and antioxidant；Modified carbon nano-tube is by carbon Nanotube carries out oxidation processes, silanization treatment and amination and handles to obtain.
2. the carbon nano-tube modification TPU materials according to claim 1 for 3D printing, it is characterised in that：Carbon modified is received The preparation method of mitron is as follows：
(1) oxidation processes carbon nanotube
By carbon nanotube ultrasonic disperse, heating sequentially adds the concentrated sulfuric acid and concentrated nitric acid, carries out oxidation reaction, after the completion of reaction, warp Post processing obtains the carbon nanotube of oxidation processes；
(2) silanization treatment oxide/carbon nanometer tube
The carbon nanotube of oxidation processes, methacryloxypropyl trimethoxy silane, absolute ethyl alcohol and deionized water are mixed Close ultrasonic disperse；It reheats and carries out Silanization reaction, whole logical N in reaction process2, it is post-treated to obtain silicon after the completion of reaction Alkanisation carbon nanotube；
(3) the amination processing of silane carbon nano tube
Nitrogen is passed through into reaction bulb, by silane carbon nano tube, N, N- methylene-bisacrylamides, deionized water and persulfuric acid Aqueous solutions of potassium is sequentially added in reaction bulb, forms mixed liquor, re-ultrasonic dispersion, then heating stirring progress polymerisation, reacts After the completion, it is post-treated to obtain modified carbon nano-tube.
3. the carbon nano-tube modification TPU materials according to claim 2 for 3D printing, it is characterised in that：In step (1) The rate of charge of carbon nanotube, the concentrated sulfuric acid and concentrated nitric acid is 5：95-105：45-55, carbon nanotube is in terms of g, the concentrated sulfuric acid and concentrated nitric acid In terms of mL；The temperature of oxidation reaction is 48-52 DEG C in step (1), and the reaction time is 95-105 minutes.
4. the carbon nano-tube modification TPU materials according to claim 2 for 3D printing, it is characterised in that：In step (2) The carbon nanotubes of oxidation processes, methacryloxypropyl trimethoxy silane, absolute ethyl alcohol and deionized water rate of charge It is 3：0.4-0.5：42-48：14-16, the carbon nanotube of oxidation processes is in terms of g, methacryloxypropyl trimethoxy silicon Alkane, absolute ethyl alcohol and deionized water are in terms of mL；The temperature of Silanization reaction is 60-65 DEG C in step (2), reaction time 115- 125 minutes.
5. the carbon nano-tube modification TPU materials according to claim 2 for 3D printing, it is characterised in that：In step (3) Silane carbon nano tube, N,N methylene bis acrylamide, deionized water and persulfate aqueous solution rate of charge be 2：0.07- 0.08：24-26：1-1.1, a concentration of 1-1.1mmol/L of persulfate aqueous solution, silane carbon nano tube, N, N- methylene Bisacrylamide is in terms of g, and deionized water and persulfate aqueous solution are in terms of mL；Polymeric reaction temperature is 65-70 in step (3) DEG C, the reaction time is 300-360 minutes.
6. the carbon nano-tube modification TPU materials according to claim 2 for 3D printing, it is characterised in that：Step (1), (2) it and is post-processed in (3) and is：Product by absolute ethyl alcohol is washed, is filtered, vacuum drying.
7. the carbon nano-tube modification TPU materials according to claim 1 for 3D printing, it is characterised in that：Including following The raw material of parts by weight：
8. the carbon nano-tube modification TPU materials according to claim 1 for 3D printing, it is characterised in that：Thermoplastic poly Urethane elastomer includes one or both of polyether polyurethane elastomer or polyester polyurethane elastomer, and shore hardness is 55A~75D, particle size are 3~5mm.
9. the carbon nano-tube modification TPU materials according to claim 1 for 3D printing, it is characterised in that：
Hydrolysis agent is technical grade single second carbide imine or technical grade polycarbodiimide；
Ultra-violet absorber is one or more of benzophenone class, benzotriazole or hindered amines；
Plasticizer is aliphatic dibasic acid ester, Phthalates, benzene polyacid esters or one kind or several in benzoates Kind；
Antioxidant is one or more of Hinered phenols antioxidant, phosphite ester kind antioxidant or monothioester kind antioxidant；
Organic solvent is any one in DMF or DMA.
10. a kind of preparation method of any carbon nano-tube modification TPU materials for 3D printing of claim 1-9, It is characterized in that：Include the following steps：
(1) thermoplastic polyurethane elastomer, modified carbon nano-tube are sequentially added in organic solvent, ultrasonic disperse into mixed liquor, Pasty mixture, pelletizing after vacuum drying are thermally formed, product is modified primary master batch for TPU；
(2) TPU modifications primary master batch, hydrolysis agent, antioxidant, ultra-violet absorber, plasticizer is weighed to be placed in and be kneaded at a high speed It is sufficiently mixed in machine, adds double screw extruder and carry out extruding pelletization；Product is obtained after vacuum drying.
CN201711460942.8A 2017-12-28 2017-12-28 Carbon nano-tube modification TPU materials for 3D printing and preparation method thereof Pending CN108164980A (en)

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PCT/CN2018/114370 WO2019128484A1 (en) 2017-12-28 2018-11-07 Carbon nanotube modified tpu material for 3d printing and preparation method therefor

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CN109096740A (en) * 2018-07-20 2018-12-28 山东诺威聚氨酯股份有限公司 Antibacterial antistatic TPU film material and preparation method thereof
CN109456458A (en) * 2018-09-28 2019-03-12 山东诺威聚氨酯股份有限公司 Polyether ester type TPU and preparation method thereof for footwear material
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CN111040111A (en) * 2019-08-23 2020-04-21 苏州纤创智造新材料科技有限公司 Antistatic thermoplastic polyurethane and preparation method thereof
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CN115537065A (en) * 2022-11-04 2022-12-30 北京理工大学 Ink for 3D printing fire-resistant pressure sensor, preparation method and printing method
CN116178930A (en) * 2023-01-17 2023-05-30 昆明理工大学 Method for preparing carbon nanotube-based flexible temperature-sensitive material through 3D printing
CN116178930B (en) * 2023-01-17 2024-04-19 昆明理工大学 Method for preparing carbon nanotube-based flexible temperature-sensitive material through 3D printing

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