CN106243678A - The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified - Google Patents

The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified Download PDF

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CN106243678A
CN106243678A CN201610612828.1A CN201610612828A CN106243678A CN 106243678 A CN106243678 A CN 106243678A CN 201610612828 A CN201610612828 A CN 201610612828A CN 106243678 A CN106243678 A CN 106243678A
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graphene
polyurethane
ultrasonic
nano
tio
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黎淑娟
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Foshan Gaoming Technology Co Ltd
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Foshan Gaoming Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses the aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified, it is made up of the raw material of following weight portion meter: polyurethane 90 ~ 100 parts, inorganic filler 5 ~ 10 parts, Graphene/TiO2Cleaning material 0.5 ~ 1 part, multi-walled carbon nano-tubes/nano-ZnO removes aldehyde material 1 ~ 5 part, graphene quantum dot and porous graphene, light stabilizer 0.1 ~ 1 part, coupling agent 5 ~ 10 parts, levelling agent 0.1 ~ 2 part, dispersed lubricant 1 ~ 6 part and 0.1 ~ 1 part of antioxidant；Wherein, Graphene/TiO2The weight part ratio that cleaning material removes aldehyde material with multi-walled carbon nano-tubes/nano-ZnO is 1:(3 ~ 5), it is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polyurethane, and it is 0.5 ~ 2% that described porous graphene accounts for the percentage by weight of polyurethane.The described Thermoplastic polyurethane composite material prepared has good pliability and excellent mechanical property, also has excellent automatically cleaning antifouling property and except aldehyde effect, has widened the range of application that 3D prints further.

Description

The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified
Technical field
The present invention relates to field of compound material, the aldehyde removing type 3D printing polyurethane of a kind of Graphene modification is combined Material.
Background technology
3D printing technique is also known as a kind of emerging technology of increasing material manufacturing technology, actually rapid shaping field, and it is one Kind based on mathematical model file, use powdery metal or plastics etc. can jointing material, come by the way of successively printing The technology of constructed object.Ultimate principle is layered manufacturing, successively increases material and generates the technology of 3D solid.At present, 3D beats Print technology is applied primarily to product prototype, Making mold and the field such as artistic creation, jewelry-making, substitutes these tradition and depends on The retrofit technique relied.It addition, 3D printing technique is gradually applied to the necks such as medical science, biological engineering, building, clothing, aviation Territory, has opened up wide space for innovation.But, the product that 3D printing technique prints is storing, and transports and used Cheng Zhong, due to humidity in surrounding and air, the impact of deleterious particle and gas etc., easily grows carefully at its surface Bacterium, enrichment polluter etc., health can be adversely affected.At present, the most popular 3D printed product and former The antibacterial antifouling self-cleaning function of material is not highly desirable, need to improve.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides the modified aldehyde removing type 3D of a kind of Graphene and print use Compound polyurethane material, it also has good pliability and excellent mechanical property, has widened the application that 3D prints further Scope.
The technical problem to be solved is achieved by the following technical programs:
The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified, it is made up of the raw material of following weight portion meter: Polyurethane 90 ~ 100 parts, inorganic filler 5 ~ 10 parts, Graphene/TiO2Cleaning material 0.5 ~ 1 part, multi-walled carbon nano-tubes/nano-ZnO Except aldehyde material 1 ~ 5 part, graphene quantum dot and porous graphene, light stabilizer 0.1 ~ 1 part, coupling agent 5 ~ 10 parts, levelling agent 0.1 ~ 2 parts, dispersed lubricant 1 ~ 6 part and 0.1 ~ 1 part of antioxidant；Wherein, Graphene/TiO2Cleaning material and multi-walled carbon nano-tubes/receive Rice ZnO is 1:(3 ~ 5 except the weight part ratio of aldehyde material)；Described graphene quantum dot account for the percentage by weight of polyurethane be 0.5 ~ 1%, it is 0.5 ~ 2% that described porous graphene accounts for the percentage by weight of polyurethane；
The preparation method of the compound polyurethane material that described 3D prints, comprises the following steps:
(1) pretreatment urethane raw: urethane raw is ground into 300 mesh powder, is scattered in pure water, ultrasonic (power 200 ~ 300W) after 1 hour, ultrasonic limit, limit microwave exposure (2500 ~ 3000MHz, temperature controls at 80 ~ 90 DEG C) 1 hour；Stop ultrasonic And microwave exposure, washing, discharging, it is dried, obtains pretreatment polyurethane；
(2) a PU master batch is prepared: by Graphene/TiO2Cleaning material ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~ 1400r/min centrifugal speed stirs) it is scattered in pure water, obtain the first dispersion liquid, standby；Multi-walled carbon nano-tubes/nano-ZnO is removed Aldehyde material ultrasonic agitation (300 ~ 500KW ultrasonic vibration and the stirring of 1000 ~ 1400r/min centrifugal speed) is scattered in pure water, Second dispersion liquid, standby；Under heating-up temperature (50 ~ 60 DEG C), the pretreatment polyurethane of 3/5ths is dissolved in organic solvent In, obtaining polyurethane solutions, one dividing into three obtains first part, second part, the 3rd part of polyurethane solutions, standby；Temperature constant state (50 ~ 60 DEG C) under, limit high-speed stirred (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW) first part of polyurethane solutions, dropping First dispersion liquid, ultrasonic agitation 30 ~ 60min；Continue second part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue to drip Add the second dispersion liquid, ultrasonic agitation 30 ~ 60min；Continue the 3rd part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue Dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain polyurethane mixed liquor；Polyurethane mixed liquor is passed through spraying Exsiccator stock in groove, polyurethane mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, be dried Obtain a PU master batch；The nozzle diameter of described spray dryer is 0.5～0.7mm, and dry air flow rates is 30～35m3/ h, temperature Spend 120～160 DEG C；
(3) the 2nd PU master batch is prepared: by porous graphene ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~ 1400r/min Centrifugal speed stirs) it is scattered in pure water, obtain porous graphene dispersing solution, standby；Under heating-up temperature (50 ~ 60 DEG C), by five The pretreatment polyurethane of/mono-is dissolved in organic solvent, obtains polyurethane solutions；Under temperature constant state (50 ~ 60 DEG C), Bian Gao Speed stirring (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW) polyurethane solutions, drips porous graphene dispersion liquid, super Sound stirring 30 ~ 60min, obtains Graphene polyurethane mixed liquor；Graphene polyurethane mixed liquor is passed through the storage of spray dryer In standby groove, with the speed of 200 ~ 300ml/min, Graphene polyurethane mixed liquor is ejected in spray dryer, be dried second PU master batch；
(4) pretreatment polyurethane will be remained, a PU master batch, the 2nd PU master batch, light stabilizer, coupling agent, levelling agent, dispersion profit Joining after lubrication prescription and antioxidant melting mixing in mechanical lapping pulverizer, obtaining mean diameter after pulverizing is the poly-of 30 ~ 40 μm Urethane composite powder, is placed at 95 DEG C and is dried 2h；Dried powder is added double screw extruder, then cools down molding Obtain shape wire, rolling, obtain the Thermoplastic polyurethane composite material of 3D printer.
In invention, described Graphene/TiO2Cleaning material and multi-walled carbon nano-tubes/nano-ZnO are except the weight of aldehyde material Part ratio is 1:4.
In invention, described Graphene/TiO2Cleaning material preparation method is as follows: by Graphene ultrasonic agitation, 700KW surpasses Acoustic vibration and the stirring of 1300r/min centrifugal speed, be scattered in ethanol, obtain graphene dispersing solution；By TiO2Powder adds In 100ml ethanol, after disperseing 100min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir, prepare TiO2Dispersion Liquid；Lower in graphene dispersing solution, it is slowly added dropwise TiO 100kW is ultrasonic2Dispersion liquid, ultrasonic 60min, then sucking filtration, drying, system Obtain Graphene/TiO2Cleaning material, wherein, described Graphene and TiO2Mass ratio be 1:3.
In invention, described multi-walled carbon nano-tubes/nano-ZnO is as follows except aldehyde material preparation method: by multi-walled carbon nano-tubes Add in 100ml deionized water, prepare after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir Carbon nano tube dispersion liquid；Nanometer ZnO powder is added in 100ml ethanol, in the centrifugal speed of 1300kW ultrasonic vibration and 1500r/min Nano-ZnO dispersion solution is prepared after the lower dispersion 100min of degree stirring；Ultrasonic lower toward addition nanometer in carbon nano tube dispersion liquid at 300kW ZnO dispersion liquid, ultrasonic 90min, then sucking filtration, drying, prepare multi-walled carbon nano-tubes/nano-ZnO and remove aldehyde material, wherein, described Multi-walled carbon nano-tubes is 1:4 with the mass ratio of nano-ZnO.
There is advantages that
The described Thermoplastic polyurethane composite material prepared has good pliability and excellent mechanical property, also has excellence Automatically cleaning antifouling property and except aldehyde effect, has widened the range of application that 3D prints further；By nano-ZnO and nano-TiO2Powder Formation composite on multi-walled carbon nano-tubes and Graphene is adsorbed at end respectively, and obtains scientific matching by test of many times, While realizing the mechanical property that preferably 3D prints goods, improve further the self-cleaning surface of 3D printed product and antibacterial press down Bacterium function and except aldehyde ability.
Detailed description of the invention
In the present invention,
(1) Graphene is prepared by following methods: taking a certain amount of acid flat band ink, 1000 DEG C process 2 hours, then 8% in atmosphere H2Nitrogen and hydrogen mixture in 1100 DEG C of in-situ reducing process 1.0 hours, add macrogol ester and the mass ratio of mass ratio 3% Tetracarboxylic dianhydride's dinaphthyl of 5.0%, is made into, with water, the slurry that concentration is 82.0%, first enters under the ultrasonic assistant that power is 700W Row 4000 turns/min ball milling 10 hours, then adjust and to 300W ultrasound wave, carry out 2000 turns/min ball milling 5 hours, through height after ball milling Speed 10000 turns/min of centrifuge separates, lyophilization, it is thus achieved that Graphene solid.
(2) described Graphene/TiO2Cleaning material preparation method is as follows: by Graphene ultrasonic agitation, 700KW ultrasonic vibration Stir with 1300r/min centrifugal speed, be scattered in ethanol, obtain graphene dispersing solution；By TiO2Powder adds 100ml ethanol In, prepare TiO after disperseing 100min under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir2Dispersion liquid；? 100kW is ultrasonic lower is slowly added dropwise TiO in graphene dispersing solution2Dispersion liquid, ultrasonic 60min, then sucking filtration, drying, prepare stone Ink alkene/TiO2Cleaning material, wherein, described Graphene and TiO2Mass ratio be 1:3.Described TiO2Powder is preferably average particle The titanium dioxide granule of footpath about 15nm.
(3) described multi-walled carbon nano-tubes/nano-ZnO except aldehyde material preparation method as follows: by multi-walled carbon nano-tubes add In 100ml deionized water, prepare carbon after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir and receive Mitron dispersion liquid；Nanometer ZnO powder is added in 100ml ethanol, stir at 1300kW ultrasonic vibration and 1500r/min centrifugal speed Nano-ZnO dispersion solution is prepared after mixing lower dispersion 100min；Ultrasonic lower toward addition nano-ZnO in carbon nano tube dispersion liquid at 300kW Dispersion liquid, ultrasonic 90min, then sucking filtration, drying, prepare multi-walled carbon nano-tubes/nano-ZnO except aldehyde material, wherein, described many walls CNT is 1:4 with the mass ratio of nano-ZnO.The preferred mean diameter of described nano-ZnO is the ZnO nano powder of 20nm, excellent Elect bar-shaped or flower-shaped ZnO nano powder as.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic fills out Expect 8 parts, Graphene/TiO2Cleaning material 0.5 part, multi-walled carbon nano-tubes/nano-ZnO remove aldehyde material 2 parts, light stabilizer 0.2 part, Coupling agent 5 parts, levelling agent 0.1 part, dispersed lubricant 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps:
(1) pretreatment urethane raw: urethane raw is ground into 300 mesh powder, is scattered in pure water, ultrasonic (power 300W) after 1 hour, ultrasonic limit, limit microwave exposure (2500MHz, temperature controls at 85 DEG C) 1 hour；Stop ultrasonic and microwave spoke According to, washing, discharging, it is dried, obtains pretreatment polyurethane；
(2) a PU master batch is prepared: by Graphene/TiO2Cleaning material ultrasonic agitation (500KW ultrasonic vibration and 1200r/min Centrifugal speed stirs) it is scattered in pure water, obtain the first dispersion liquid, standby；Multi-walled carbon nano-tubes/nano-ZnO is surpassed except aldehyde material Sound stirring (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；? Under heating-up temperature (60 DEG C), the pretreatment polyurethane of 3/5ths is dissolved in organic solvent, obtains polyurethane solutions, one point Be three first part, second part, the 3rd part of polyurethane solutions, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/ Min) limit ultrasonic (power 500KW) first part of polyurethane solutions, drips the first dispersion liquid, ultrasonic agitation 30min；Continue dropping the Two parts of polyurethane solutions, ultrasonic agitation 30min；Continue dropping the second dispersion liquid, ultrasonic agitation 30min；Continue dropping the 3rd part Polyurethane solutions, ultrasonic agitation 30min, obtain polyurethane mixed liquor；Polyurethane mixed liquor is passed through stocking of spray dryer In groove, with the speed of 300ml/min, polyurethane mixed liquor is ejected in spray dryer, is dried to obtain a PU master batch；Described The nozzle diameter of spray dryer is 0.6mm, and dry air flow rates is at 35m3/ h, temperature 150 DEG C；
(3) pretreatment polyurethane, a PU master batch, light stabilizer, coupling agent, levelling agent, dispersed lubricant and antioxygen will be remained Join in mechanical lapping pulverizer after agent melting mixing, after pulverizing, obtain the polyurethane composite that mean diameter is 30 ~ 40 μm Material powder, is placed at 95 DEG C and is dried 2h；Dried powder adds double screw extruder, and then cooling molding obtains form wire Material, rolling, obtain the Thermoplastic polyurethane composite material of 3D printer.
The hot strength of prepared compound polyurethane material is 23.25MPa, and Young's modulus is 0.05GPa.
Embodiment 2
Based on embodiment 1, difference is: Graphene/TiO2Cleaning material 1 part, multi-walled carbon nano-tubes/nano-ZnO removes aldehyde Material 3 parts.The hot strength of prepared compound polyurethane material is 24.05MPa, and Young's modulus is 0.05GPa.
Embodiment 3
Based on embodiment 1, difference is: Graphene/TiO2Cleaning material 0.8 part, multi-walled carbon nano-tubes/nano-ZnO removes Aldehyde material 4 parts.The hot strength of prepared compound polyurethane material is 22.95MPa, and Young's modulus is 0.05GPa.
Embodiment 4
Based on embodiment 1, difference is: increase Graphene 3 parts.The hot strength of prepared compound polyurethane material is 43.57MPa, Young's modulus is 0.06GPa.
Embodiment 5
The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified, it is made up of the raw material of following weight portion meter: Polyurethane 100 parts, inorganic filler 8 parts, graphene quantum dot 0.5 part, porous graphene 1 part, Graphene/TiO2Cleaning material 0.5 part, multi-walled carbon nano-tubes/nano-ZnO removes aldehyde material 2 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, divides Dissipate lubricant 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps:
(1) pretreatment urethane raw: urethane raw is ground into 300 mesh powder, is scattered in pure water, ultrasonic (power 300W) after 1 hour, ultrasonic limit, limit microwave exposure (2500MHz, temperature controls at 85 DEG C) 1 hour；Stop ultrasonic and microwave spoke According to, washing, discharging, it is dried, obtains pretreatment polyurethane；
(2) a PU master batch is prepared: by Graphene/TiO2Cleaning material ultrasonic agitation (500KW ultrasonic vibration and 1200r/min Centrifugal speed stirs) it is scattered in pure water, obtain the first dispersion liquid, standby；Multi-walled carbon nano-tubes/nano-ZnO is surpassed except aldehyde material Sound stirring (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；? Under heating-up temperature (60 DEG C), the pretreatment polyurethane of 3/5ths is dissolved in organic solvent, obtains polyurethane solutions, one point Be three first part, second part, the 3rd part of polyurethane solutions, standby；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/ Min) limit ultrasonic (power 500KW) first part of polyurethane solutions, drips the first dispersion liquid, ultrasonic agitation 30min；Continue dropping the Two parts of polyurethane solutions, ultrasonic agitation 30min；Continue dropping the second dispersion liquid, ultrasonic agitation 30min；Continue dropping the 3rd part Polyurethane solutions, ultrasonic agitation 30min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30min, obtain polyurethane and mix Close liquid；What polyurethane mixed liquor was passed through spray dryer stocks in groove, is sprayed by polyurethane mixed liquor with the speed of 300ml/min It is mapped in spray dryer, is dried to obtain a PU master batch；The nozzle diameter of described spray dryer is 0.6mm, dry air stream Speed is at 35m3/ h, temperature 150 DEG C；
(3) the 2nd PU master batch is prepared: (500KW ultrasonic vibration and 1200r/min centrifugal speed are stirred by porous graphene ultrasonic agitation Mix) it is scattered in pure water, obtain porous graphene dispersing solution, standby；Under heating-up temperature (60 DEG C), by the pretreatment of 1/5th Polyurethane is dissolved in organic solvent, obtains polyurethane solutions；Under temperature constant state (60 DEG C), limit high-speed stirred (1200r/min) Limit ultrasonic (power 500KW) polyurethane solutions, drips porous graphene dispersion liquid, ultrasonic agitation 60min, obtains the poly-ammonia of Graphene Ester mixed liquor；What Graphene polyurethane mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min by graphite Alkene polyurethane mixed liquor is ejected in spray dryer, is dried to obtain the 2nd PU master batch；The nozzle diameter of described spray dryer is 0.6mm, dry air flow rates is at 35m3/ h, temperature 150 DEG C；
(4) pretreatment polyurethane will be remained, a PU master batch, the 2nd PU master batch, light stabilizer, coupling agent, levelling agent, dispersion profit Joining after lubrication prescription and antioxidant melting mixing in mechanical lapping pulverizer, obtaining mean diameter after pulverizing is the poly-of 30 ~ 40 μm Urethane composite powder, is placed at 95 DEG C and is dried 2h；Dried powder is added double screw extruder, then cools down molding Obtain shape wire, rolling, obtain the Thermoplastic polyurethane composite material of 3D printer.Prepared compound polyurethane material Hot strength be 75.48MPa, Young's modulus is 0.07GPa.
The preparation method of described porous graphene is with reference to the embodiment 1 of Chinese patent application CN104555999A；Described stone The preparation method of ink alkene quantum dot is with reference to the embodiment 5 of Chinese patent CN102190296B.It should be noted that prepare graphite Alkene quantum dot, is scattered in second further according to actual amount ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) In alcohol, this is only a kind of embodiment, it is also possible to obtain by other means.
Embodiment 6
Based on embodiment 5, difference is: it is 0.8% that described graphene quantum dot accounts for the mass percent of polyurethane；Porous It is 2% that Graphene accounts for the mass percent of polyurethane.The hot strength of prepared compound polyurethane material is 83.61MPa, poplar Family name's modulus is 0.09GPa.
Embodiment 7
Based on embodiment 5, difference is: it is 1% that described graphene quantum dot accounts for the mass percent of polyurethane；Porous stone It is 0.5% that ink alkene accounts for the mass percent of polyurethane.The hot strength of prepared compound polyurethane material is 81.35MPa, poplar Family name's modulus is 0.08GPa.
Comparative example 1
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic fills out Expect 8 parts, TiO20.8 part, nano-ZnO 4 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersed lubricant 3 parts With 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps: weigh various raw material in proportion；Each raw materials melt is mixed After join in mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing End, is placed at 95 DEG C and is dried 2h；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, Rolling, obtains the Thermoplastic polyurethane composite material of 3D printer.The hot strength of prepared compound polyurethane material is 16.55MPa, Young's modulus is 0.03GPa.
Comparative example 2
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic fills out Expect 8 parts, Graphene/TiO2Cleaning material 0.8 part, nano-ZnO 4 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 Part, dispersed lubricant 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps: weigh various raw material in proportion；Each raw materials melt is mixed After join in mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing End, is placed at 95 DEG C and is dried 2h；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, Rolling, obtains the Thermoplastic polyurethane composite material of 3D printer.The hot strength of prepared compound polyurethane material is 18.49MPa, Young's modulus is 0.04GPa.
Comparative example 3
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic fills out Expect 8 parts, TiO20.8 part, multi-walled carbon nano-tubes/nano-ZnO 4 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, Dispersed lubricant 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps: weigh various raw material in proportion；Each raw materials melt is mixed After join in mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing End, is placed at 95 DEG C and is dried 2h；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, Rolling, obtains the Thermoplastic polyurethane composite material of 3D printer.The hot strength of prepared compound polyurethane material is 18.35MPa, Young's modulus is 0.04GPa.
Comparative example 4
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, light is stable Agent 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersed lubricant 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps: weigh various raw material in proportion；Each raw materials melt is mixed After join in mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing End, is placed at 95 DEG C and is dried 2h；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, Rolling, obtains the Thermoplastic polyurethane composite material of 3D printer.The hot strength of prepared compound polyurethane material is 8.2MPa, Young's modulus is 0.02GPa.
Measure of merit
The finished product obtaining embodiment 1 ~ 6 and comparative example 1 ~ 4 is tested:
(1) anti-microbial property test: detect according to GB/T23763-2009 national standard, select escherichia coli ATCC8739 and Staphylococcus aureus ATCC6538P is strain.
(2) test of soil resistance: detect according to GB/T3810.14-2006 national standard, selects chrome green for polluting Agent.
(3) except the test of aldehyde rate: use JC/T 1074-2008 standard to measure.
Testing result: as shown in the table:
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained Case, all should fall within the scope and spirit of the invention.

Claims (4)

1. the aldehyde removing type 3D printing compound polyurethane material that Graphene is modified, it is by the raw material group of following weight portion meter Become: polyurethane 90 ~ 100 parts, inorganic filler 5 ~ 10 parts, Graphene/TiO2Cleaning material 0.5 ~ 1 part, multi-walled carbon nano-tubes/nanometer ZnO removes aldehyde material 1 ~ 5 part, graphene quantum dot and porous graphene, light stabilizer 0.1 ~ 1 part, coupling agent 5 ~ 10 parts, levelling agent 0.1 ~ 2 part, dispersed lubricant 1 ~ 6 part and 0.1 ~ 1 part of antioxidant；Wherein, Graphene/TiO2Cleaning material and multi-wall carbon nano-tube Pipe/nano-ZnO is 1:(3 ~ 5 except the weight part ratio of aldehyde material)；Described graphene quantum dot accounts for the percentage by weight of polyurethane 0.5 ~ 1%, it is 0.5 ~ 2% that described porous graphene accounts for the percentage by weight of polyurethane；
The preparation method of described compound polyurethane material, comprises the following steps:
(1) pretreatment urethane raw: urethane raw is ground into 300 mesh powder, is scattered in pure water, after ultrasonic 1 hour, Ultrasonic limit, limit microwave exposure 1 hour；Stop ultrasonic and microwave exposure, washing, discharging, it is dried, obtains pretreatment polyurethane；
(2) a PU master batch is prepared: by Graphene/TiO2Cleaning material ultrasonic agitation is scattered in pure water, obtains the first dispersion liquid, Standby；Multi-walled carbon nano-tubes/nano-ZnO is scattered in pure water except aldehyde material ultrasonic agitation, obtains the second dispersion liquid, standby；? Under heating-up temperature, being dissolved in organic solvent by the pretreatment polyurethane of 3/5ths, obtain polyurethane solutions, one dividing into three obtains First part, second part, the 3rd part of polyurethane solutions, standby；Under temperature constant state, the ultrasonic first part of polyurethane in high-speed stirred limit, limit is molten Liquid, drips the first dispersion liquid, ultrasonic agitation 30 ~ 60min；Continue second part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min； Continue dropping the second dispersion liquid, ultrasonic agitation 30 ~ 60min；Continue the 3rd part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain polyurethane mixed liquor；Polyurethane is mixed What liquid was passed through spray dryer stocks in groove, and polyurethane mixed liquor is ejected into spray drying by the speed with 200～300ml/min In device, it is dried to obtain a PU master batch；
(3) prepare the 2nd PU master batch: porous graphene ultrasonic agitation be scattered in pure water, obtain porous graphene dispersing solution, standby With；At the heating temperature, the pretreatment polyurethane of 1/5th is dissolved in organic solvent, obtains polyurethane solutions；Constant temperature Under state, the ultrasonic polyurethane solutions in high-speed stirred limit, limit, drip porous graphene dispersion liquid, ultrasonic agitation 30 ~ 60min, obtain Graphene polyurethane mixed liquor；What Graphene polyurethane mixed liquor was passed through spray dryer stocks in groove, with 200 ~ 300ml/ Graphene polyurethane mixed liquor is ejected in spray dryer by the speed of min, is dried to obtain the 2nd PU master batch；
(4) pretreatment polyurethane will be remained, a PU master batch, the 2nd PU master batch, light stabilizer, coupling agent, levelling agent, dispersion profit Joining after lubrication prescription and antioxidant melting mixing in mechanical lapping pulverizer, obtaining mean diameter after pulverizing is the poly-of 30 ~ 40 μm Urethane composite powder；It is placed at 95 DEG C and is dried 2h；Dried powder is added double screw extruder, then cools down molding Obtain shape wire, rolling, obtain the compound polyurethane material of 3D printer.
The aldehyde removing type 3D printing compound polyurethane material that Graphene the most according to claim 1 is modified, it is characterised in that Described Graphene/TiO2It is 1:4 that cleaning material and multi-walled carbon nano-tubes/nano-ZnO remove the weight part ratio of aldehyde material.
The aldehyde removing type 3D printing compound polyurethane material that Graphene the most according to claim 1 and 2 is modified, its feature exists In, described Graphene/TiO2Cleaning material preparation method is as follows: by Graphene ultrasonic agitation, 700KW ultrasonic vibration and 1300r/ Min centrifugal speed stirs, and is scattered in ethanol, obtains graphene dispersing solution；By TiO2Powder adds in 100ml ethanol, TiO is prepared after 1300kW ultrasonic vibration and the lower dispersion 100min of 1500r/min centrifugal speed stirring2Dispersion liquid；Ultrasonic at 100kW It is slowly added dropwise TiO down in graphene dispersing solution2Dispersion liquid, ultrasonic 60min, then sucking filtration, drying, prepare Graphene/TiO2Clearly Clean material, wherein, described Graphene and TiO2Mass ratio be 1:3.
The aldehyde removing type 3D printing compound polyurethane material that Graphene the most according to claim 1 and 2 is modified, its feature exists In, described multi-walled carbon nano-tubes/nano-ZnO is as follows except aldehyde material preparation method: multi-walled carbon nano-tubes adds 100ml deionization In water, after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir, prepare carbon nano tube dispersion liquid； Nanometer ZnO powder is added in 100ml ethanol, disperse under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir Nano-ZnO dispersion solution is prepared after 100min；Ultrasonic lower toward addition nano-ZnO dispersion solution in carbon nano tube dispersion liquid at 300kW, super Sound 90min, then sucking filtration, drying, prepare multi-walled carbon nano-tubes/nano-ZnO except aldehyde material, wherein, described multi-walled carbon nano-tubes It is 1:4 with the mass ratio of nano-ZnO.
CN201610612828.1A 2016-07-29 2016-07-29 The aldehyde removing type 3D printing compound polyurethane material that a kind of Graphene is modified Pending CN106243678A (en)

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