CN106009618A - Modification-reinforced antimicrobial polyurethane composite material - Google Patents
Modification-reinforced antimicrobial polyurethane composite material Download PDFInfo
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- CN106009618A CN106009618A CN201610612842.1A CN201610612842A CN106009618A CN 106009618 A CN106009618 A CN 106009618A CN 201610612842 A CN201610612842 A CN 201610612842A CN 106009618 A CN106009618 A CN 106009618A
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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
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- 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
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- 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
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- 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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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
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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
- 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
Abstract
The invention discloses a modification-reinforced antimicrobial polyurethane composite material which is composed of the following raw materials in parts by weight: 90-100 parts of polyurethane, 5-10 parts of inorganic filler, 0.5-1 part of graphene/TiO2 clean material, 0.5-1 part of multi-wall carbon nanotube/nano silver antimicrobial material, graphene quantum dots and porous graphene, 0.1-1 part of light stabilizer, 5-10 parts of coupling agent, 0.1-2 parts of leveling agent, 1-6 parts of dispersing and lubricating agent and 0.1-1 part of antioxidant. The weight ratio of the graphene/TiO2 clean material to the multi-wall carbon nanotube/nano silver antimicrobial material is (2-3):(1-3); the graphene quantum dots account for 0.5-1 wt% of the polyurethane; and the porous graphene accounts for 0.5-2 wt% of the polyurethane. The prepared thermoplastic polyurethane composite material has the advantages of favorable flexibility, excellent mechanical properties, excellent self-cleaning property and excellent antifouling property, and further widens the application range of 3D printing.
Description
Technical field
The present invention relates to field of compound material, a kind of modified antimicrobial form compound polyurethane material strengthened.
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., in the easy breed bacteria in its surface, richness
Collection polluters etc., can adversely affect health.At present, the most popular 3D printed product and raw-material
Antibacterial antifouling self-cleaning function 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 modified antimicrobial form polyurethane strengthened and be combined
Material, it also has good pliability and excellent mechanical property, has widened the range of application that 3D prints further.
The technical problem to be solved is achieved by the following technical programs:
A kind of modified antimicrobial form compound polyurethane material strengthened, 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 silver antibacterial material
0.5 ~ 1 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-walled carbon nano-tubes/nanometer silver
The weight part ratio of anti-biotic material is (2 ~ 3): (1 ~ 3)；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polyurethane,
It is 0.5 ~ 2% that described porous graphene accounts for the percentage by weight of polyurethane；
The preparation method of the Thermoplastic polyurethane composite 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/nanometer silver is resisted
Bacterium 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 the present invention, described Graphene/TiO2Cleaning material and the weight of multi-walled carbon nano-tubes/nano silver antibacterial material
Part ratio is 2:3.
In the present invention, described Graphene/TiO2Cleaning material preparation method is as follows: by Graphene ultrasonic agitation, 700KW
Ultrasonic 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 the present invention, described multi-walled carbon nano-tubes/nano silver antibacterial material preparation method is as follows: 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；Ultrasonic lower toward addition nano-Ag particles, ultrasonic 90min in carbon nano tube dispersion liquid at 500kW, then take out
Filter, drying, prepare multi-walled carbon nano-tubes/nano silver antibacterial material, wherein, described multi-walled carbon nano-tubes and the mass ratio of nanometer silver
For 2:5.
There is advantages that
The described Thermoplastic polyurethane composite material prepared has good pliability and excellent mechanical property, also has excellence
Automatically cleaning and antifouling property, widened the range of application that 3D prints further；By nano-Ag particles and nano-TiO2Powder is respectively
Absorption forms composite on multi-walled carbon nano-tubes and Graphene, and obtains scientific matching by test of many times, is realizing relatively
While good 3D prints the mechanical property of goods, improve self-cleaning surface and the antibacterial bacteriostatic merit of 3D printed product further
Energy.
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 silver antibacterial material preparation method is as follows: added by multi-walled carbon nano-tubes
In 100ml deionized water, prepare carbon after disperseing 200min under 800kW ultrasonic vibration and 1300r/min centrifugal speed stir and receive
Mitron dispersion liquid；Ultrasonic lower toward carbon nano tube dispersion liquid adds nano-Ag particles at 500kW, ultrasonic 90min, then sucking filtration,
Drying, prepare multi-walled carbon nano-tubes/nano silver antibacterial material, wherein, described multi-walled carbon nano-tubes with the mass ratio of nanometer silver is
2:5.Described nano-Ag particles is preferably the nano-Ag particles of mean diameter about 10nm.
Below in conjunction with embodiment, the present invention will be described in detail.
Embodiment 1
A kind of compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic filler 8 parts, stone
Ink alkene/TiO2Cleaning material 0.6 part, multi-walled carbon nano-tubes/nano silver antibacterial material 0.9 part, light stabilizer 0.2 part, coupling agent 5
Part, 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；By ultrasonic for multi-walled carbon nano-tubes/nano silver antibacterial material
Stirring (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；Adding
At hot temperature (60 DEG C), being dissolved in organic solvent by the pretreatment polyurethane of 3/5ths, obtain polyurethane solutions, one is divided into
Three obtain 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
For 23.41MPa, Young's modulus is 0.05GPa.
Embodiment 2
Based on embodiment 1, difference is: Graphene/TiO2Cleaning material 0.9 part, multi-walled carbon nano-tubes/nanometer silver antimicrobial
Material 0.6 part.The hot strength of prepared compound polyurethane material is 22.65MPa, 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/nanometer silver antimicrobial
Material 0.8 part.The hot strength of prepared compound polyurethane material is 23.15MPa, 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
42.46MPa, Young's modulus is 0.06GPa.
Embodiment 5
A kind of modified antimicrobial form compound polyurethane material strengthened, it is made up of the raw material of following weight portion meter: polyurethane 100
Part, inorganic filler 8 parts, Graphene/TiO2Cleaning material 0.6 part, multi-walled carbon nano-tubes/nano silver antibacterial material 0.9 part, graphite
Alkene 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
With 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；By ultrasonic for multi-walled carbon nano-tubes/nano silver antibacterial material
Stirring (500KW ultrasonic vibration and the stirring of 1200r/min centrifugal speed) is scattered in pure water, obtains the second dispersion liquid, standby；Adding
At hot temperature (60 DEG C), being dissolved in organic solvent by the pretreatment polyurethane of 3/5ths, obtain polyurethane solutions, one is divided into
Three obtain 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 78.98MPa, 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 85.65MPa, 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 80.28MPa, poplar
Family name's modulus is 0.08GPa.
Comparative example 1
A kind of modified antimicrobial form compound polyurethane material strengthened, it is made up of the raw material of following weight portion meter: polyurethane 100
Part, inorganic filler 8 parts, TiO20.8 part, nanometer silver 0.8 part, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersion
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
16.82MPa, Young's modulus is 0.03GPa.
Comparative example 2
A kind of compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic filler 8 parts, stone
Ink alkene/TiO2Cleaning material 0.8 part, nanometer silver 0.8 part, 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；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
18.62MPa, Young's modulus is 0.04GPa.
Comparative example 3
A kind of compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 parts, inorganic filler 8 parts,
TiO20.8 part, multi-walled carbon nano-tubes/nanometer silver 0.8 part, light stabilizer 0.2 part, coupling agent 5 parts, levelling agent 0.1 part, dispersion
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
17.95MPa, Young's modulus is 0.04GPa.
Comparative example 4
A kind of compound polyurethane material, it is made up of the raw material of following weight portion meter: polyurethane 100 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
8.5MPa, Young's modulus is 0.02GPa.
Measure of merit
The finished product obtaining embodiment 1 ~ 7 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.
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 modified antimicrobial form compound polyurethane material strengthened, 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 silver antibacterial material
0.5 ~ 1 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-walled carbon nano-tubes/nanometer silver
The weight part ratio of anti-biotic material is (2 ~ 3): (1 ~ 3)；It is 0.5 ~ 1% that described graphene quantum dot accounts for the percentage by weight of polyurethane,
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 silver antibacterial material ultrasonic agitation is scattered in pure water, obtains the second dispersion liquid, standby；Adding
At hot temperature, being dissolved in organic solvent by the pretreatment polyurethane of 3/5ths, obtain polyurethane solutions, one dividing into three obtains
A, 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 modified antimicrobial form compound polyurethane material strengthened the most according to claim 1, it is characterised in that described graphite
Alkene/TiO2The weight part ratio of cleaning material and multi-walled carbon nano-tubes/nano silver antibacterial material is 2:3.
The modified antimicrobial form compound polyurethane material strengthened the most according to claim 1 and 2, it is characterised in that described stone
Ink alkene/TiO2Cleaning material preparation method is as follows: by centrifugal to Graphene ultrasonic agitation, 700KW ultrasonic vibration and 1300r/min speed
Degree stirring, is scattered in ethanol, obtains graphene dispersing solution；By TiO2Powder adds in 100ml ethanol, in the ultrasonic shake of 1300kW
TiO is prepared after the lower dispersion 100min of dynamic and 1500r/min centrifugal speed stirring2Dispersion liquid；Divide at the ultrasonic lower past Graphene of 100kW
Dissipate in liquid and be slowly added dropwise TiO2Dispersion liquid, ultrasonic 60min, then sucking filtration, drying, prepare Graphene/TiO2Cleaning material, wherein,
Described Graphene and TiO2Mass ratio be 1:3.
The modified antimicrobial form compound polyurethane material strengthened the most according to claim 1 and 2, it is characterised in that described many
Wall carbon nano tube/nano silver antibacterial material preparation method is as follows: added by multi-walled carbon nano-tubes in 100ml deionized water,
Carbon nano tube dispersion liquid is prepared after 800kW ultrasonic vibration and the lower dispersion 200min of 1300r/min centrifugal speed stirring；At 500kW
Ultrasonic lower toward addition nano-Ag particles, ultrasonic 90min, then sucking filtration, drying in carbon nano tube dispersion liquid, prepare multi-wall carbon nano-tube
Pipe/nano silver antibacterial material, wherein, described multi-walled carbon nano-tubes is 2:5 with the mass ratio of nanometer silver.
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