CN106633373A - Composite carbon nanotube/polypropylene powder material for SLS (selective laser sintering) and preparation method thereof - Google Patents
Composite carbon nanotube/polypropylene powder material for SLS (selective laser sintering) and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 116
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 91
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000110 selective laser sintering Methods 0.000 title abstract description 8
- -1 polypropylene Polymers 0.000 claims abstract description 60
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000000527 sonication Methods 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical class CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 238000000149 argon plasma sintering Methods 0.000 abstract 1
- 206010067739 Shrinking lung syndrome Diseases 0.000 description 42
- 206010048676 Sjogren-Larsson Syndrome Diseases 0.000 description 42
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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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Abstract
The invention discloses a composite carbon nanotube/polypropylene powder material for SLS (selective laser sintering) and a preparation method thereof. The composite carbon nano tube/polypropylene powder material comprises polypropylene, carbon nanotubes, an initiating agent and antioxidant. The preparation method includes the steps of grafting the carbon nanotubes to maleic anhydride for treatment, compositing polypropylene powder with the carbon nanotubes, and mixing the composite carbon nanotube/polypropylene powder with the initiating agent and the antioxidant. The composite carbon nanotube/polypropylene powder material has the advantages that high laser absorptivity and high thermal conductivity are obtained, and laser sintering performance of the polypropylene powder is improved remarkably; the preparation method has the advantages that uniform dispersion and excellent interface bonding of the carbon nanotubes in a polypropylene matrix are achieved, and overall performance of SLS workpieces are improved effectively.
Description
Technical field
The invention belongs to high molecule nano composite material field, more particularly, to a kind of CNT for SLS/
Polypropylene composite materials dusty material and preparation method.
Background technology
Selective laser sintering (Selective Laser Sintering, SLS) is by means of computer-aided design and system
Make, be Three-dimensional Entity Components by pressed powder direct forming using Layered manufacturing principle of stacking.Macromolecular material is due to having into
The advantages of shape temperature is low, laser power needed for sintering is little, becoming apply at present most, most successful SLS materials.With SLS skills
Art can only be shaped prototype development and can directly be manufactured function part till now by initial, at present existing SLS macromolecules material
The species and performance of material far can not meet the demand of most products.Therefore, more high-performance, the macromolecule of multi items are developed
And its composite material becomes the key for promoting the development of SLS technologies and applying.
Polypropylene with nontoxic, tasteless, light weight, impact strength height, is electrically insulated as one of five big commodity polymer materials
Property well wait good characteristic, all have a wide range of applications at aspects such as household electrical appliance, electronics, auto industrys.However, general poly- third
Alkene compound with regular structure, degree of crystallinity is high, and excessive dimensional contraction is easily caused during SLS, causes part buckling deformation；The opposing party
Face, though the toughness of polypropylene material is good, intensity still belongs to relatively low in macromolecular material.2 points of the above limits it in SLS side
The application in face.
At present, SLS macromolecular materials are strengthened by adding nano-sized filler, it is to improve to form nano composite material
The important channel of its performance.CNT (Carbon nanotube, CNT) has many abnormal mechanics, electricity and chemical
Can, such as its tensile strength reaches 50～200GPa, is 100 times of steel, and density but only has the 1/6 of steel, is widely used in many
Field.If CNT and polypropylene are made into composite powder material, polyacrylic shrinkage factor not only can be reduced, improve its laser and burn
Knot performance, moreover it is possible to improve the performance of the aspects such as polyacrylic mechanics, electricity, calorifics, for SLS a kind of new sinterable height is provided
Molecular material.
Mainly there are following methods to can be used to prepare SLS carbon nanotube/polypropylene composite powders in presently disclosed data：
1) mechanical mixing (application number 201410129572.X), i.e., by the way that polymeric powder is pinched with Nano filling in ball milling, three-dimensional
Mechanical mixture is carried out in conjunction machine or other mixing apparatus.The method has process is simple, low cost and other advantages, but cannot be by nanometer
It is dispersed in macromolecule matrix to uniform filling；2) melting extrusion+low-temperature grinding method (application number 201410544610.8), will
Polymeric particles are mixed according to a certain percentage with Nano filling, Jing twin-screw extrusions, and then pelletize crushes at low temperature again.Should
Method can be dispersed in nano material in macromolecule matrix, but resulting composite powder pattern is irregular, affect
The performance of SLS products.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of carbon nano-tube/poly for SLS
Propylene composite powder material and preparation method, using maleic anhydride as compatilizer, it can in the presence of initiator for the method
There is melting graft reaction in situ with polypropylene, realize the bridge joint between CNT and polypropylene, prepared by the present invention compound
Both can guarantee that CNT was uniformly dispersed in powder, and the good pattern of former powder can have been kept, can have been manufactured with higher by SLS
The high performance such as mechanical property, conduction, heat conduction or multi-functional product.
For achieving the above object, according to one aspect of the present invention, it is proposed that a kind of carbon nano-tube/poly third for SLS
The preparation method of alkene composite powder material, comprises the steps：
(1) CNT grafted maleic anhydride is processed：
Hydroxylated CNT, ethyl acetate, maleic anhydride and perchloric acid are pressed into 0.1g：100mL：1g：The ratio of 10mL
Example is put in there-necked flask, ultrasonic disperse 40min, and condensing reflux 4h is then stirred at 60 DEG C, product is filtered, is washed, and
Constant weight state is dried under vacuum at 50 DEG C, the CNT of grafted maleic anhydride is obtained；
(2) polypropylene powder is combined with CNT：
The CNT of above-mentioned grafted maleic anhydride is dispersed in dehydrated alcohol, it is then that polypropylene powder is slow
In pouring above-mentioned scattered carbon nano-tube solution into, while homogeneous mixed with CNT to form polypropylene by quick stirring
Close liquid；Then above-mentioned mixed liquor is heated to into 80～100 DEG C, and quickly stirring makes ethanol evaporation；Finally the powder for obtaining is gathered
Collective's drying is sieved, and obtains polypropylene with carbon nano-tube composite powder end；
(3) initiator and antioxidant are mixed into：
Proportionally initiator and antioxidant powder are added in above-mentioned polypropylene and carbon nano-tube composite powder end, mixing
It is uniform obtaining the carbon nanotube/polypropylene composite powder material for SLS.
The method of the present invention can realize dispersed and good interface cohesion of the CNT in polypropylene matrix,
It is effectively improved the combination property of SLS products.
As it is further preferred that the concrete technology of ultrasonic disperse is in step (1)：Using ultrasonic disperser, water-bath
Ultrasonic disperse 40min, 40～120W of power, mixing speed is 100～300rpm.
As it is further preferred that the CNT of grafted maleic anhydride is scattered in the concentration of dehydrated alcohol in step (2)
For 1：0.5～5g/L, the speed that polypropylene powder is poured in scattered carbon nano-tube solution be 2～6g/s, the speed of stirring
For 300～600rpm.
As it is further preferred that the CNT of grafted maleic anhydride is dispersed in using the mode of supersound process
Dehydrated alcohol, the concrete technology of supersound process is that, using ultrasound wave separating apparatus, power is 100～200W, and sonication treatment time is
30min。
As it is further preferred that in step (3) by the powder aggregates for obtaining drying sieve specific technique be must
To powder aggregates be put in 80 DEG C of baking ovens, dry to constant weight state, 200 mesh sub-sieves are then crossed on oscillating sieving machine.
As it is further preferred that the particle diameter of polypropylene powder is 10-150 μm, granule-morphology for spherical or subsphaeroidal,
190 DEG C, under the test condition of 2.16Kg, melt flow index is 5～50g/10min.
As it is further preferred that polypropylene, CNT, initiator and antioxidant content difference 92.5～
99.7wt%, 0.1～5wt%, 0.1～2wt% and 0.1～0.5wt%.
As it is further preferred that CNT be hydroxylated multi-walled carbon nano-tubes, hydroxy radical content be 1～5wt%, it is pure
Degree>95%.
Used as it is further preferred that the initiator is peroxide initiator, preferably cumyl peroxide powder resists
Oxygen agent is Hinered phenols and/or phosphite antioxidant powder.
It is another aspect of this invention to provide that there is provided a kind of carbon nano-tube/poly third for SLS prepared by methods described
Alkene composite powder material, the composite powder material includes CNT, initiator and the antioxygen that polypropylene, maleic anhydride are grafted
Agent, wherein, the CNT of maleic anhydride grafting accounts for 0.1～5wt% of gross mass, and initiator accounts for 0.1～2wt%, antioxidation
Agent accounts for 0.1～0.5wt%, and remaining is polypropylene.
Carbon nanotube/polypropylene composite powder prepared by the inventive method has good laser absorption rate and thermal conductivity,
So as to substantially improve the laser sintered performance of polypropylene powder.
In general, possess following compared with prior art, mainly by the contemplated above technical scheme of the present invention
Technological merit：
(1) present invention provide SLS with carbon nanotube/polypropylene composite powder material, due to the addition of CNT
The laser absorption rate and thermal conductivity of matrix polymeric powder are improve, during laser sintered, can preferably by laser spoke
The energy penetrated is converted to efficient heat, and good heat transfer is formed between powder, and the laser for substantially increasing powder burns
Knot performance.
(2) in preparation methoies of the SLS that the present invention is provided with carbon nanotube/polypropylene composite powder material, can be in liquid
The dispersed of CNT is realized in phase, and forms the homogeneous mixed liquor of polypropylene powder and CNT on this basis；
And during later stage solvent volatilizees, this good dispersity can be kept, make CNT uniformly cladding or
In being dispersed in polypropylene powder.
(3) maleic anhydride is adopted in the present invention as compatilizer, during laser sintered, can be in the presence of initiator
There is melting graft reaction in situ with polypropylene, realize the bridge joint between CNT and polypropylene, exist CNT is improved
While dispersing uniformity in SLS products, moreover it is possible to strengthen the interface bond strength with polypropylene matrix.
(4) present invention is also by the time to each parameter in preparation method and each composition such as supersound process, the particle diameter of powder
And initiator and antioxidant consumption it is isoparametric it is further research with design, so as to get composite be more beneficial for SLS
Powdering and shaping, part performance further improves.
Description of the drawings
Fig. 1 is the FB(flow block) of preparation method of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Not constituting conflict each other just can be mutually combined.
It is a kind of for the selective laser sintering preparation method of carbon nanotube/polypropylene composite powder that the present invention is provided,
Comprise the following steps：
1) CNT grafted maleic anhydride is processed
Hydroxylated CNT, solvent ethyl acetate, maleic anhydride and catalyst perchloric acid are pressed into 0.1g：100mL：
1g：The ratio of 10mL is put in there-necked flask, using ultrasonic disperser such as bath types, water bath sonicator dispersion 40min, power
40～120W, then stirs condensing reflux 4h at 60 DEG C, and mixing speed is 100～300rpm, and product is filtered, and uses deionization
Water washing is dried under vacuum to constant weight state to neutrality at 50 DEG C.
Above-mentioned CNT be hydroxylated multi-walled carbon nano-tubes, hydroxy radical content be 1～5wt%, purity>95%.
2) polypropylene powder is combined with CNT
First, above-mentioned CNT is dispersed in dehydrated alcohol using ultrasound wave separating apparatus such as Tip types, carbon is received
Concentration of the mitron in ethanol solution is 1：0.5～5g/L, sonication treatment time is 30min, and power is 100～200W；
Then polypropylene powder is poured in scattered carbon nano-tube solution with the speed of 2～6g/s, while using mechanical agitator
Quick stirring, mixing speed is 300～600rpm, is allowed to form the homogeneous mixed liquor of polypropylene and CNT；Again will be above-mentioned
Mixed liquor is heated to 80～100 DEG C, keeps quick stirring to make ethanol rapid evaporation, and mixing speed is 300～600rpm,；Finally
The powder aggregates for obtaining drying is sieved, polypropylene is obtained with carbon nano-tube composite powder end.Specifically, the powder for obtaining is gathered
Collective is put in 80 DEG C of baking ovens, is dried to constant weight state, and 200 mesh sub-sieves are then crossed on oscillating sieving machine, obtains polypropylene
With carbon nano-tube composite powder end
Wherein, polypropylene powder is the powder with appropriate particle size and granule-morphology, and wherein powder diameter is 10-150 μm,
Granule-morphology is spherical or subsphaeroidal；At 190 DEG C, under the test condition of 2.16Kg, melt flow index is 5～50g/10min.
3) initiator and antioxidant are mixed into
Initiator and antioxidant powder are added in above-mentioned polypropylene and carbon nano-tube composite powder end, several persons mixing is equal
It is even that SLS carbon nanotube/polypropylene composite powders are obtained；Wherein, CNT accounts for 0.1～5wt% of gross mass, causes
Agent accounts for 0.1～2wt%, and antioxidant accounts for 0.1～0.5wt%, and remaining is polypropylene.
The effect of above-mentioned initiator be during laser sintered, initiation grafting maleic anhydride on the carbon nanotubes and
Polyacrylic graft reaction, so as to improve the interfacial combined function between CNT and polypropylene, initiator is peroxidating initiation
Agent, preferably cumyl peroxide powder.Above-mentioned antioxidant is Hinered phenols and/or phosphite antioxidant powder.
Invention is further elaborated with reference to embodiment：
Embodiment 1：(carbon nanotube mass fraction is the carbon nanotube/polypropylene composite powder of 0.1wt%)
1) it is hydroxylated CNT (1g), solvent ethyl acetate (1000mL), maleic anhydride (10g) and catalyst is high
Chloric acid (100mL) is put into there-necked flask, using ultrasonic disperser (bath types), water bath sonicator dispersion 40min, power 40W；So
Stir condensing reflux 4h at 60 DEG C afterwards, mixing speed is 100rpm, and product is filtered, and is washed with deionized, at 50 DEG C
It is dried under vacuum to constant weight state.
2) above-mentioned 1g nanotubes are dispersed in dehydrated alcohol using ultrasound wave separating apparatus (Tip types), CNT
Concentration be 1：5g/L, power is 100W, and sonication treatment time is 30min；By polypropylene powder that 993g particle diameters are 10 μm with
The speed of 6g/s is poured slowly in scattered carbon nano-tube solution, while quickly being stirred using mechanical agitator, the speed of stirring
Spend for 300rpm；Again above-mentioned mixed liquor is heated to into 100 DEG C, keeps quick stirring to make ethanol rapid evaporation；By the powder for obtaining
Aggregation is put in 80 DEG C of baking ovens, is dried to constant weight state, and 200 mesh sub-sieves are then crossed on oscillating sieving machine, obtains poly- third
Alkene and carbon nano-tube composite powder end；
3) polypropylene for preparing is added in three-dimensional kneader with carbon nano-tube composite powder end, is blended into 1g initiator peroxides
Change diisopropylbenzene (DIPB) powder and 5g antioxidant 1010s, you can obtain the SLS carbon nanotube/polypropylene composite powder materials of 0.1wt%
Material.
4) above-mentioned powder is shaped on SLS equipment HK320, preheating temperature is set to 105 DEG C, and sweep span is 0.15mm,
Laser power 9W, thickness in monolayer 0.1mm, scanning speed is 2000mm/s；By the test block of gained according to GB GB/T1040-
2006 are tested.
Embodiment 2：(carbon nanotube mass fraction is the carbon nanotube/polypropylene composite powder of 1wt%)
1) by hydroxylated CNT (10g), solvent ethyl acetate (10000mL), maleic anhydride (100g) and catalysis
Agent perchloric acid (1000mL) is put into there-necked flask, using ultrasonic disperser (bath types), water bath sonicator dispersion 40min, power
80W；Then condensing reflux 4h is stirred at 60 DEG C, mixing speed is 200rpm, and product is filtered, and is washed with deionized,
It is vacuum dried at 50 DEG C；
2) the above-mentioned CNTs of 10g are dispersed in dehydrated alcohol using ultrasound wave separating apparatus (Tip types), carbon nanometer
The concentration of pipe is 1：2.5g/L, power is 150W, and sonication treatment time is 30min；By the polypropylene powder that 982g particle diameters are 90 μm
End is poured slowly in scattered carbon nano-tube solution with the speed of 4g/s, while quickly being stirred using mechanical agitator, is stirred
Speed be 450rpm；Again above-mentioned mixed liquor is heated to into 80 DEG C, keeps quick stirring to make ethanol rapid evaporation；By the powder for obtaining
Last aggregation drying is sieved, and the powder aggregates for obtaining are put in 80 DEG C of baking ovens, is dried to constant weight state, then in vibrosieve
200 mesh sub-sieves are crossed on powder machine, polypropylene is obtained with carbon nano-tube composite powder end；
3) polypropylene for preparing is added in three-dimensional kneader with carbon nano-tube composite powder end, is blended into 5g initiator peroxides
Change the compound antioxidant of diisopropylbenzene (DIPB) powder and 3g 1010 and 168, you can obtain the SLS carbon nanotube/polypropylenes of 1wt%
Composite powder material.
4) above-mentioned powder is shaped on SLS equipment HK320, preheating temperature is set to 104 DEG C, and sweep span is 0.15mm,
Laser power 8.5W, thickness in monolayer 0.1mm, scanning speed is 2000mm/s；By the test block of gained according to GB GB/T1040-
2006 are tested.
Embodiment 3：(carbon nanotube mass fraction is the carbon nanotube/polypropylene composite powder of 2wt%)
1) by hydroxylated CNT (20g), solvent ethyl acetate (20000mL), maleic anhydride (200g) and catalysis
Agent perchloric acid (2000mL) is put into there-necked flask, using ultrasonic disperser (bath types), water bath sonicator dispersion 40min, power
100W；Then condensing reflux 4h is stirred at 60 DEG C, mixing speed is 250rpm, and product is filtered, and is washed with deionized,
It is vacuum dried at 50 DEG C.
2) the above-mentioned CNTs of 20g are dispersed in dehydrated alcohol using ultrasound wave separating apparatus (Tip types), carbon nanometer
The concentration of pipe is 1：1.5g/L, power is 180W, and sonication treatment time is 30min；By the polypropylene powder that 968g particle diameters are 100 μm
End is poured slowly in scattered carbon nano-tube solution with the speed of 3g/s, while quickly being stirred using mechanical agitator, is stirred
Speed be 600rpm；It is allowed to form the homogeneous mixed liquor of polypropylene and CNT, then above-mentioned mixed liquor is heated to into 85 DEG C,
Quick stirring is kept to make ethanol rapid evaporation；The powder aggregates for obtaining are put in 80 DEG C of baking ovens, are dried to constant weight state, then
200 mesh sub-sieves are crossed on oscillating sieving machine, polypropylene is obtained with carbon nano-tube composite powder end.
3) polypropylene for preparing is added in three-dimensional kneader with carbon nano-tube composite powder end, is blended into 10g initiator mistakes
Oxidation diisopropylbenzene (DIPB) powder and 2g irgasfos 168s, you can obtain the SLS carbon nanotube/polypropylene composite powder materials of 2wt%
Material.
4) above-mentioned powder is shaped on SLS equipment HK320, preheating temperature is set to 103 DEG C, and sweep span is 0.15mm,
Laser power 8.5W, thickness in monolayer 0.1mm, scanning speed is 2000mm/s；By the test block of gained according to GB GB/T1040-
2006 are tested.
Embodiment 4：(carbon nanotube mass fraction is the carbon nanotube/polypropylene composite powder of 5wt%)
1) by hydroxylated CNT (50g), solvent ethyl acetate (50000mL), maleic anhydride (500g) and catalysis
Agent perchloric acid (5000mL) is put into there-necked flask, using ultrasonic disperser (bath types), water bath sonicator dispersion 40min, power
120W, then stirs condensing reflux 4h at 60 DEG C with the mixing speed of 300rpm, and product is filtered, and is washed with deionized,
It is vacuum dried at 50 DEG C；
2) the above-mentioned CNTs of 50g are dispersed in dehydrated alcohol first with ultrasound wave separating apparatus (Tip types), carbon
The concentration of nanotube is 1：0.5g/L, power is 200W, and sonication treatment time is 30min；Then it is 150 μm by 929g particle diameters
Polypropylene powder is poured slowly in scattered carbon nano-tube solution with the speed of 2g/s, while quickly being stirred using mechanical agitator
Mix, the speed of stirring is 600rpm, is allowed to form the homogeneous mixed liquor of polypropylene and CNT；Above-mentioned mixed liquor is heated again
To 90 DEG C, quick stirring is kept to make ethanol rapid evaporation；The powder aggregates for obtaining are put in 80 DEG C of baking ovens, are dried to constant weight shape
State, then crosses 200 mesh sub-sieves on oscillating sieving machine, obtains polypropylene with carbon nano-tube composite powder end；
3) polypropylene for preparing is added in three-dimensional kneader with carbon nano-tube composite powder end, is blended into 20g initiator mistakes
Oxidation diisopropylbenzene (DIPB) powder and 1g irgasfos 168s, you can obtain the SLS carbon nanotube/polypropylene composite powder materials of 5wt%
Material.
4) above-mentioned powder is shaped on SLS equipment HK320, preheating temperature is set to 101 DEG C, and sweep span is 0.15mm,
Laser power 8W, thickness in monolayer 0.1mm, scanning speed is 2000mm/s；By the test block of gained according to GB GB/T1040-
2006 are tested.
By the carbon nanotube/polypropylene composite materials SLS drip moldings obtained in embodiment 1-4, with virgin pp SLS shapings
Part is contrasted, as a result as shown in table 1.
The SLS product mechanical property contrast tables of table 1
As it can be seen from table 1 the tensile strength of composite, toughness and elongation at break are with CNT addition
Increase and presenting first increases the trend for reducing afterwards, when content of carbon nanotubes is excessive, performance has then declined；But, it is combined
The elastic modelling quantity of material rises always with the addition of CNT.In addition, SLS shaping optimized parameter in terms of, SLS into
The preheating temperature of shape decreases with the increase of content of carbon nanotubes, and this is conducive to being controlled SLS forming processes, while
Material aging degree is reduced, the addition for illustrating CNT produces impact to the thermal property of polypropylene matrix, affects mainly to come
From in two aspects：1) thermal conductivity of composite powder increases, and Uniformity of Temperature Field is improved；2) becoming occurs in polyacrylic melting characteristic
Change, melt initiation temperature degree is reduced.Secondly, laser power needed for the forming process of SLS also with the addition of increase with CNT and
Reduce, this is because the addition of CNT increased absorbance of the composite powder to laser, so that in relatively low laser energy
Can just make composite powder that molten sintering occurs under amount.By table 1, compared with virgin pp SLS drip moldings, using the present invention
The dusty material of preparation is applied to SLS technologies, and dusty material flowing property prepared by the present invention is good, the SLS initial blanks of shaping
Possess higher intensity and toughness, the good mechanical performance of product.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. are limited, all should be included
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the carbon nanotube/polypropylene composite powder material for SLS, it is characterised in that including as follows
Step：
(1) CNT grafted maleic anhydride is processed：
Hydroxylated CNT, ethyl acetate, maleic anhydride and perchloric acid are pressed into 0.1g：100mL：1g：The ratio of 10mL is put
In entering there-necked flask, then ultrasonic disperse 40min stirs condensing reflux 4h at 60 DEG C, product is filtered, is washed, and 50
Constant weight is dried under vacuum at DEG C, the CNT of grafted maleic anhydride is obtained；
(2) polypropylene powder is combined with CNT：
The CNT of above-mentioned grafted maleic anhydride is dispersed in dehydrated alcohol, is then poured slowly into polypropylene powder
In above-mentioned scattered carbon nano-tube solution, while by quick stirring forming mixing for polypropylene and CNT
Liquid；Then above-mentioned mixed liquor is heated to into 80～100 DEG C, and quickly stirring makes ethanol evaporation；Finally the powder for obtaining is assembled
Body drying is sieved, and obtains polypropylene with carbon nano-tube composite powder end；
(3) initiator and antioxidant are mixed into：
Initiator and antioxidant powder are added in above-mentioned polypropylene and carbon nano-tube composite powder end, mix homogeneously is being used
In the carbon nanotube/polypropylene composite powder material of SLS.
2. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 1
It is that the concrete technology of ultrasonic disperse is in step (1)：Using ultrasonic disperser, water bath sonicator dispersion 40min, power 40
～120W；Mixing speed is 100～300rpm.
3. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 2
It is that the concentration that the CNT of grafted maleic anhydride is scattered in dehydrated alcohol in step (2) is 1：0.5～5g/L, polypropylene
The speed that powder is poured in scattered carbon nano-tube solution is 2～6g/s, and the speed of stirring is 300～600rpm.
4. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 3
It is that the CNT of grafted maleic anhydride is dispersed in into dehydrated alcohol using the mode of supersound process, supersound process
Concrete technology is that, using ultrasound wave separating apparatus, power is 100～200W, and sonication treatment time is 30min.
5. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 4
It is that it is that the powder aggregates that will be obtained are put into 80 that the powder aggregates for obtaining are dried into specific technique of sieving in step (3)
In DEG C baking oven, dry to constant weight state, 200 mesh sub-sieves are then crossed on oscillating sieving machine.
6. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 5
It is that the particle diameter of polypropylene powder is 10-150 μm, and granule-morphology is spherical or subsphaeroidal.
7. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 6
Be, CNT be hydroxylated multi-walled carbon nano-tubes, hydroxy radical content be 1～5wt%, purity>95%.
8. the preparation method of the carbon nanotube/polypropylene composite powder material of SLS, its feature are used for as claimed in claim 7
Be that the initiator is peroxide initiator, preferably cumyl peroxide powder, antioxidant be Hinered phenols and/or
Phosphite antioxidant powder.
9. it is a kind of by any one of claim 1-8 methods described prepare the carbon nanotube/polypropylene composite powder material for SLS
Material, it is characterised in that including polypropylene, the CNT of maleic anhydride grafting, initiator and antioxidant, wherein, maleic anhydride
The CNT of grafting accounts for 0.1～5wt% of gross mass, and initiator accounts for 0.1～2wt%, and antioxidant accounts for 0.1～0.5wt%,
Remaining is polypropylene.
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| US11884763B2 (en) * | 2021-05-17 | 2024-01-30 | Xerox Corporation | Spherical particles comprising carbon nanomaterial-graft-polyolefin and methods of production and uses thereof |
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| CN114573894B (en) * | 2020-12-01 | 2024-03-01 | 中国石油天然气股份有限公司 | Carbon nano tube master batch and preparation method and application thereof |
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| CN112745461B (en) * | 2020-12-31 | 2022-07-29 | 河北科技大学 | High-molecular composite powder for selective laser sintering and preparation method thereof |
| EP4091987A1 (en) * | 2021-05-17 | 2022-11-23 | Xerox Corporation | Spherical particles comprising carbon nano material-graft-polymer and methods of production and uses thereof |
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| US12060461B2 (en) | 2021-05-17 | 2024-08-13 | Xerox Corporation | Spherical particles comprising carbon nanomaterial-graft-polyamide and methods of production and uses thereof |
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