CN106046756A - Graphene modified and enhanced polyurethane composite material for 3D printing - Google Patents

Graphene modified and enhanced polyurethane composite material for 3D printing Download PDF

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CN106046756A
CN106046756A CN201610612858.2A CN201610612858A CN106046756A CN 106046756 A CN106046756 A CN 106046756A CN 201610612858 A CN201610612858 A CN 201610612858A CN 106046756 A CN106046756 A CN 106046756A
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polyurethane
graphene
parts
ultrasonic
ultrasonic agitation
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黎淑娟
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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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
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    • 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
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    • 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
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    • 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
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Abstract

The invention discloses a graphene modified and enhanced polyurethane composite material for 3D printing. The graphene modified and enhanced polyurethane composite material is prepared from the following raw materials in parts by weight: 90 to 100 parts of polyurethane, 5 to 10 parts of composite packing, 1 to 5 parts of a functional material, graphene quantum dots and porous graphene, 0.1 to 1 part of a light stabilizer, 5 to 10 parts of a coupling agent, 0.1 to 2 parts of a leveling agent, 1 to 6 parts of a dispersion lubricating agent and 0.1 to 1 part of an antioxidant, wherein the functional material comprises a nano silver/TiO2 antibacterial material and a multi-wall carbon nano tube/nano ZnO formaldehyde removal material; the graphene quantum dots account for 0.5 to 1 percent of the weight of polyurethane, and the porous graphene accounts for 0.5 to 2 percent of the weight of polyurethane. According to the graphene modified and enhanced polyurethane composite material for 3D printing, by the use of the adsorption and slow release functions of kieselguhr and a capsule slow release technology, the antibacterial and formaldehyde removal materials are stored in kieselguhr and then slowly released, to enhance the antibacterial and formaldehyde removal effects of a product to the maximum extent; furthermore, the prepared thermoplastic polyurethane composite material is further high in toughness and excellent in mechanical property, so that the application range of 3D printing is further expanded.

Description

A kind of Graphene modification strengthens 3D printing compound polyurethane material
Technical field
The present invention relates to field of compound material, particularly a kind of Graphene modification strengthens 3D printing polyurethane composite 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 a kind of Graphene modification enhancing 3D printing and use poly-ammonia Ester composite, it also has good pliability and excellent mechanical property, has widened the application model that 3D prints further Enclose.
The technical problem to be solved is achieved by the following technical programs:
A kind of Graphene modification strengthens 3D printing compound polyurethane material, and it is made up of the raw material of following weight portion meter: poly-ammonia Ester 90 ~ 100 parts, compounded mix 5 ~ 10 parts, functional 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, described function material Material includes nanometer silver/TiO2Anti-biotic material and multi-walled carbon nano-tubes/nano-ZnO are except aldehyde material；Described compounded mix is by weight 3:2 is by Graphene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix；Described graphene quantum dot accounts for polyurethane Percentage by weight 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 this compound polyurethane material, 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/SiO2Compounded mix 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；By graphene/carbon acid calcium compounded mix Ultrasonic agitation (300 ~ 500KW ultrasonic vibration and the stirring of 1000 ~ 1400r/min centrifugal speed) is scattered in pure water, obtains second point Dissipate liquid, standby；Under heating-up temperature (50 ~ 60 DEG C), the pretreatment polyurethane of 3/5ths is dissolved in organic solvent, obtains Polyurethane solutions, one dividing into three obtains first part, second part, the 3rd part of polyurethane solutions, standby；Under temperature constant state (50 ~ 60 DEG C), Limit high-speed stirred (1000 ~ 1400r/min) limit ultrasonic (power 300 ~ 500KW) first part of polyurethane solutions, dropping the first dispersion Liquid, ultrasonic agitation 30 ~ 60min；Continue second part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping second point Dissipate liquid, ultrasonic agitation 30 ~ 60min；Continue the 3rd part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping graphite Alkene quantum dot solution, ultrasonic agitation 30 ~ 60min, obtain polyurethane mixed liquor；Polyurethane mixed liquor is passed through spray dryer Stocking in groove, polyurethane mixed liquor is ejected in spray dryer by the speed with 200～300ml/min, is dried to 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 120～ 160℃；
(3) prepare the 2nd PU master batch: by functional material ultrasonic agitation (300 ~ 500KW ultrasonic vibration and 1000 ~ 1400r/min from Heart speed stirs) it is scattered in pure water, obtain functional material dispersion liquid, standby；By porous graphene ultrasonic agitation (300 ~ 500KW Ultrasonic vibration and the stirring of 1000 ~ 1400r/min centrifugal speed) it is scattered in pure water, obtain porous graphene dispersing solution, standby；? Under heating-up temperature (50 ~ 60 DEG C), the pretreatment polyurethane of 1/5th is dissolved in organic solvent, obtains polyurethane solutions, Be divided into two to obtain the 4th part, the 5th part of polyurethane solutions；Under temperature constant state (50 ~ 60 DEG C), limit high-speed stirred (1000 ~ 1400r/ Min) limit ultrasonic (power 300 ~ 500KW) the 4th part of polyurethane solutions, drips functional material dispersion liquid, and ultrasonic agitation 30 ~ 60min；Continue the 5th part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping porous graphene dispersion liquid, ultrasonic Stirring 30 ~ 60min, obtains polyurethane mixed liquor；What polyurethane mixed liquor was passed through spray dryer stocks in groove, with 200 ~ Polyurethane mixed liquor is ejected in spray dryer by the speed of 300ml/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, 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 the present invention, described functional material preparation method is as follows: by nanometer silver/TiO in vacuum mixing machine2Antibacterial material Material and multi-walled carbon nano-tubes/nano-ZnO remove in the diatom Rhizoma Panacis Japonici soil that aldehyde material joins 40 parts by weight 3:5, at vacuum bar Part, 120r/min speed under stir 30 minutes, allow each component adsorb in kieselguhr；20 parts are added in the kieselguhr obtained Polyacrylate dispersion, vacuum mixing machine stirs 20 minutes under the speed of 300r/min, makes polyacrylate dispersion by silicon Diatomaceous earth cladding is got up, and is formed with kieselguhr as core, and polyacrylate is the capsule of shell, makes a diameter of 1mm's in pellet processing machine Granule, then by prepared granule natural drying 12 hours.
There is advantages that
The present invention utilizes diatomaceous absorption and slow-release function, capsule slow release method, by antibacterial and except aldehyde material is stored in diatom In soil and discharge slowly, farthest increase the antibacterial of product and except aldehyde effect；And the described thermoplasticity prepared Compound polyurethane material also has good pliability and excellent mechanical property, has widened the application model that 3D prints further Enclose.
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) quantum dot calcium carbonate, its preparation method refers to a kind of microemulsion disclosed in Chinese patent CN103570051B System prepares the method for nano calcium carbonate quantum dot, the most first prepares the nano-calcium carbonate microemulsion of 1 ~ 3nm, more rotated Evaporate and be dried and prepare quantum dot calcium carbonate powder.
(3) Graphene/SiO2Compounded mix preparation method is as follows: by Graphene ultrasonic agitation (700KW ultrasonic vibration and 1300r/min centrifugal speed stirs) it is scattered in ethanol；Add a certain proportion of (1:4) water and ammonia afterwards, after stirring The mass ratio adding tetraethyl orthosilicate and Graphene is 1.6:1, and regulation pH value is 9, and reaction temperature is 25 DEG C, and reaction 4.2 is little Time, it is centrifuged and cleans 3 times with acetone and deionized water, deionized water successively obtaining precipitation；This is deposited in 90oDo under C Dry 2h, to obtain being coated with SiO2Graphene compounded mix.
(4) preparation method of graphene/carbon acid calcium compounded mix is as follows: 1 part of Graphene is added 100ml deionized water In, prepare graphene dispersing solution after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir；By 73 Part quantum dot calcium carbonate adds in 500ml deionized water, divides under 1300kW ultrasonic vibration and 1500r/min centrifugal speed stir Calcium carbonate dispersion liquid is prepared after dissipating 300min；Lower in graphene dispersing solution, it is slowly added dropwise calcium carbonate dispersion liquid 100kW is ultrasonic, Ultrasonic 60min, then sucking filtration, drying, prepare graphene/carbon acid calcium compounded mix.
(5) described nanometer silver/TiO2Anti-biotic material preparation method is as follows: to the 0.01mol L of 200ml-1HNO3Solution Middle interpolation 0.79g AgNO respectively3, 5g TiO2Nanotube, 0.5g dispersant sodium cetanesulfonate, after ultrasonic disperse 60min, Magnetic agitation 24h in camera bellows again.After having stirred, by 0.3mol L-1NaOH solution be added dropwise to this suspension, adjust Save its pH to 12.Filtering, gained powder sample, with after distilled water cyclic washing 3 times, is dispersed in 500ml distilled water, Add 1.0ml hole remover propylene glycol, be placed under ultra-violet lamp (125W, λ max=365nm), irradiate 6 hours. Gained sample filtering separates, and with distilled water wash 4 times.Sample after washing is put in drying baker, is dried 10 at 80 DEG C little Time, grind, obtain nanometer silver/TiO2Anti-biotic material.
(6) 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.
(7) described functional material preparation method is as follows: by nanometer silver/TiO in vacuum mixing machine2Anti-biotic material and Duo Bi Carbon nanotube/nano ZnO removes in the diatom Rhizoma Panacis Japonici soil that aldehyde material joins 40 parts by weight 3:5, at vacuum condition, 120r/ Stir 30 minutes under the speed of min, allow each component adsorb in kieselguhr；The polypropylene of 20 parts is added in the kieselguhr obtained Acid esters emulsion, vacuum mixing machine stirs 20 minutes under the speed of 300r/min, makes polyacrylate dispersion be coated with by kieselguhr Getting up, formed with kieselguhr as core, polyacrylate is the capsule of shell, makes the granule of a diameter of 1mm in pellet processing machine, then By prepared granule natural drying 12 hours.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
A kind of Graphene modification strengthens 3D printing compound polyurethane material, and it is made up of the raw material of following weight portion meter: poly-ammonia Ester 100 parts, compounded mix 8 parts, functional material 2 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersion lubrication Agent 3 parts and 0.5 part of antioxidant.Described compounded mix 3:2 by weight is by Graphene/SiO2Compounded mix and graphene/carbon acid Calcium compounded mix forms.
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/SiO2Compounded mix ultrasonic agitation (500KW ultrasonic vibration and 1200r/min Centrifugal speed stirs) it is scattered in pure water, obtain the first dispersion liquid, standby；By graphene/carbon acid calcium compounded mix ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；In heating temperature Under degree (60 DEG C), 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 (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 second part to gather Urethane solution, ultrasonic agitation 30min；Continue dropping the second dispersion liquid, ultrasonic agitation 30min；Continue the 3rd part of polyurethane of dropping Solution, ultrasonic agitation 30min, obtain polyurethane mixed liquor；What polyurethane mixed liquor was passed through spray dryer stocks in groove, with Polyurethane mixed liquor is ejected in spray dryer by the speed of 300ml/min, is dried to obtain a PU master batch；Described spray drying The nozzle diameter of device is 0.6mm, and dry air flow rates 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 functional material ultrasonic agitation Mix) it is scattered in pure water, obtain functional material dispersion liquid, standby；Under heating-up temperature (60 DEG C), the pretreatment by 1/5th gathers Urethane 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 functional material dispersion liquid, ultrasonic agitation 60min, obtains polyurethane mixed liquor； What polyurethane mixed liquor was passed through spray dryer stocks in groove, is ejected into by polyurethane mixed liquor with the speed of 300ml/min In spray dryer, it is dried to obtain the 2nd PU master batch；The nozzle diameter of described spray dryer is 0.6mm, and dry air flow rates exists 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.
The hot strength of prepared compound polyurethane material is 25.35MPa, and Young's modulus is 0.05GPa.
Embodiment 2
Based on embodiment 1, difference is: functional material 1 part.The hot strength of prepared compound polyurethane material is 24.05MPa, Young's modulus is 0.05GPa.
Embodiment 3
Based on embodiment 1, difference is: functional material 5 parts.The hot strength of prepared compound polyurethane material is 23.95MPa, 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 40.35MPa, Young's modulus is 0.06GPa.
Embodiment 5
A kind of Graphene modification strengthens 3D printing compound polyurethane material, and it is made up of the raw material of following weight portion meter: poly-ammonia Ester 100 parts, compounded mix 8 parts, functional material 2 parts, graphene quantum dot 0.5 part, porous graphene 1 part, light stabilizer 0.2 Part, coupling agent 5 parts, levelling agent 0.1 part, dispersed lubricant 3 parts and 0.5 part of antioxidant.Described compounded mix by weight 3:2 by Graphene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix；
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/SiO2Compounded mix ultrasonic agitation (500KW ultrasonic vibration and 1200r/min Centrifugal speed stirs) it is scattered in pure water, obtain the first dispersion liquid, standby；By graphene/carbon acid calcium compounded mix ultrasonic agitation (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；In heating temperature Under degree (60 DEG C), 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 (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 second part to gather Urethane solution, ultrasonic agitation 30min；Continue dropping the second dispersion liquid, ultrasonic agitation 30min；Continue the 3rd part of polyurethane of dropping Solution, ultrasonic agitation 30min；Continue dropping graphene quantum dot solution, ultrasonic agitation 30min, obtain polyurethane mixed liquor；Will What polyurethane mixed liquor was passed through spray dryer stocks in groove, with the speed of 300ml/min, polyurethane mixed liquor is ejected into spray In mist exsiccator, it is dried to obtain a PU master batch；The nozzle diameter of described spray dryer is 0.6mm, and dry air flow rates exists 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 functional material ultrasonic agitation Mix) it is scattered in pure water, obtain functional material dispersion liquid, standby；By porous graphene ultrasonic agitation (500KW ultrasonic vibration and 1200r/min centrifugal speed stirs) it is scattered in pure water, obtain porous graphene dispersing solution, standby；At heating-up temperature (60 DEG C) Under, the pretreatment polyurethane of 1/5th is dissolved in organic solvent, obtains polyurethane solutions, be divided into two the 4th part, 5th part of polyurethane solutions；Under temperature constant state (60 DEG C), ultrasonic (the power 500KW) the 4th in limit high-speed stirred (1200r/min) limit Part polyurethane solutions, drips functional material dispersion liquid, ultrasonic agitation 60min；Continue the 5th part of polyurethane solutions of dropping, ultrasonic stir Mix 30 ~ 60min；Continue dropping porous graphene dispersion liquid, ultrasonic agitation 60min, obtain polyurethane mixed liquor；Polyurethane is mixed That closes that liquid is passed through spray dryer stocks in groove, with the speed of 300ml/min, polyurethane mixed liquor is ejected into spray dryer In, it is dried to obtain the 2nd PU master batch；The nozzle diameter of described spray dryer is 0.6mm, and dry air flow rates is at 35m3/ h, temperature 150℃；
(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 78.56MPa, 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 87.48MPa, 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 82.55MPa, poplar Family name's modulus is 0.08GPa.
Comparative example 1
A kind of 3D printings compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, is combined and fills out Expect 8 parts, TiO21 part, nanometer silver 2 parts, nano-ZnO 5 parts, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersion profit Lubrication prescription 3 parts and 0.5 part of antioxidant.
The preparation method of this composite comprises the following steps: weigh various raw material in proportion；The various raw materials that will weigh It is placed in 95 DEG C of dry 3h in vacuum drying oven so that each feed moisture content is down to 0.27%；Join after each raw materials melt is mixed In mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing, be placed in 95 2h it is dried at DEG C；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 19.55MPa, Young's modulus is 0.04GPa.
Comparative example 2
A kind of 3D printings compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, is combined and fills out Expect 8 parts, nanometer silver/TiO2Anti-biotic material 3 parts, nano-ZnO 5 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；The various raw materials that will weigh It is placed in 95 DEG C of dry 3h in vacuum drying oven so that each feed moisture content is down to 0.27%；Join after each raw materials melt is mixed In mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing, be placed in 2h it is dried at 95 DEG C；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, rolling, obtains Thermoplastic polyurethane composite material to 3D printer.The hot strength of prepared compound polyurethane material is 19.49MPa, Young's modulus is 0.04GPa.
Comparative example 3
Based on embodiment 1, difference is: nanometer silver/TiO in described functional material2Anti-biotic material and multi-walled carbon nano-tubes/ Nano-ZnO is 1:1 except the weight ratio of aldehyde material.The hot strength of prepared compound polyurethane material is 19.35MPa, Young Modulus is 0.04GPa.
Comparative example 4
Based on embodiment 1, difference is: nanometer silver/TiO in described functional material2Anti-biotic material and multi-walled carbon nano-tubes/ Nano-ZnO is 5:3 except the weight ratio of aldehyde material.The hot strength of prepared compound polyurethane material is 19.55MPa, Young Modulus is 0.04GPa.
Comparative example 5
A kind of 3D printing compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, calcium carbonate 4 Part, SiO24 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；The various raw materials that will weigh It is placed in 95 DEG C of dry 3h in vacuum drying oven so that each feed moisture content is down to 0.27%；Join after each raw materials melt is mixed In mechanical lapping pulverizer, obtain the Thermoplastic polyurethane composite material powder that mean diameter is 30 ~ 40 μm after pulverizing, be placed in 2h it is dried at 95 DEG C；Dried powder adds double screw extruder, and then cooling molding obtains shape wire, rolling, obtains Thermoplastic polyurethane composite material to 3D printer.The hot strength of prepared compound polyurethane material is 9.2MPa, Young's modulus is 0.02GPa.
Measure of merit
The finished product obtaining embodiment 1 ~ 7 and comparative example 1 ~ 5 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 (2)

1. Graphene modification strengthens a 3D printing compound polyurethane material, and it is made up of the raw material of following weight portion meter: poly- Urethane 90 ~ 100 parts, compounded mix 5 ~ 10 parts, functional 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, described merit Nanometer silver/TiO can be included by material2Anti-biotic material and multi-walled carbon nano-tubes/nano-ZnO are except aldehyde material；Described compounded mix is by weight Measure than 3:2 by Graphene/SiO2Compounded mix forms with graphene/carbon acid calcium compounded mix；Described graphene quantum dot accounts for poly- The percentage by weight of urethane is 0.5 ~ 1%, and it is 0.5 ~ 2% that described porous graphene accounts for the percentage by weight of polyurethane；
The preparation method of described 3D printing 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/SiO2Compounded mix ultrasonic agitation is scattered in pure water, obtains the first dispersion liquid, Standby；Graphene/carbon acid calcium compounded mix ultrasonic agitation is scattered in pure water, obtains the second dispersion liquid, standby；In heating-up temperature Under, the pretreatment polyurethane of 3/5ths is dissolved in organic solvent, obtains polyurethane solutions, one dividing into three obtain first part, Second part, the 3rd part of polyurethane solutions, standby；Under temperature constant state, the ultrasonic first part of polyurethane solutions in high-speed stirred limit, limit, 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；
(3) prepare the 2nd PU master batch: functional material ultrasonic agitation be scattered in pure water, obtain functional material dispersion liquid, standby；Will Porous graphene ultrasonic agitation is scattered in pure water, obtains porous graphene dispersing solution, standby；At the heating temperature, by five/ The pretreatment polyurethane of one is dissolved in organic solvent, obtains polyurethane solutions, and be divided into two to obtain the 4th part, the 5th part of polyurethane Solution；Under temperature constant state, the ultrasonic 4th part of polyurethane solutions in high-speed stirred limit, limit, drip functional material dispersion liquid, ultrasonic agitation 30~60min；Continue the 5th part of polyurethane solutions of dropping, ultrasonic agitation 30 ~ 60min；Continue dropping porous graphene dispersion liquid, Ultrasonic agitation 30 ~ 60min, obtains polyurethane mixed liquor；What polyurethane mixed liquor was passed through spray dryer stocks in groove, with Polyurethane mixed liquor is ejected in spray dryer by the speed of 200 ~ 300ml/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.
Graphene modification the most according to claim 1 strengthens 3D printing compound polyurethane material, it is characterised in that described Functional material preparation method is as follows: by nanometer silver/TiO in vacuum mixing machine2Anti-biotic material and multi-walled carbon nano-tubes/nanometer ZnO joins in the diatom Rhizoma Panacis Japonici soil of 40 parts except aldehyde material by weight 3:5, vacuum condition, 120r/min speed under stir Mix 30 minutes, allow each component adsorb in kieselguhr；The polyacrylate dispersion of 20 parts, vacuum is added in the kieselguhr obtained Mixer stirs 20 minutes under the speed of 300r/min, makes polyacrylate dispersion be coated with by kieselguhr, is formed with silicon Diatomaceous earth is core, and polyacrylate is the capsule of shell, makes the granule of a diameter of 1mm in pellet processing machine, then by prepared granule from So it is dried 12 hours.
CN201610612858.2A 2016-07-29 2016-07-29 Graphene modified and enhanced polyurethane composite material for 3D printing Pending CN106046756A (en)

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CN106907006A (en) * 2017-04-13 2017-06-30 蒋旭峰 Build contoured machine
CN106907006B (en) * 2017-04-13 2022-11-25 博湃建筑科技（上海）有限公司 Building outline forming machine
CN108262479A (en) * 2018-01-25 2018-07-10 宝鸡文理学院 A kind of preparation method of self-lubricating POROUS TITANIUM base graphene alloy material
CN108410157A (en) * 2018-03-06 2018-08-17 李宏伟 A kind of high tenacity TPU bases 3D printing material and its preparation method and application
CN111423715A (en) * 2020-04-21 2020-07-17 东莞市雄林新材料科技股份有限公司 Medical wrist strap material for carbon ribbon printing and preparation method thereof
CN112406095A (en) * 2020-11-05 2021-02-26 三阳纺织有限公司 Fabric with antibacterial function and rapid forming method thereof
CN112406095B (en) * 2020-11-05 2021-09-28 三阳纺织有限公司 Fabric with antibacterial function and rapid forming method thereof
CN112341799A (en) * 2020-12-03 2021-02-09 安徽嘉明新材料科技有限公司 Preparation method and application of modified antibacterial TPU
CN112979864A (en) * 2021-04-29 2021-06-18 青岛展辰新材料有限公司 Modified acrylate water-based wood paint emulsion and preparation method thereof
CN118006283A (en) * 2024-04-10 2024-05-10 衣联天下(辽宁)服装科技有限公司 Preparation method of polyurethane adhesive based on nano quantum dots
CN118006283B (en) * 2024-04-10 2024-06-11 衣联天下(辽宁)服装科技有限公司 Preparation method of polyurethane adhesive based on nano quantum dots

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