CN105504749A - Polycarbonate composite material for 3D printing and preparation method thereof - Google Patents
Polycarbonate composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN105504749A CN105504749A CN201511010669.XA CN201511010669A CN105504749A CN 105504749 A CN105504749 A CN 105504749A CN 201511010669 A CN201511010669 A CN 201511010669A CN 105504749 A CN105504749 A CN 105504749A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000010146 3D printing Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HQMFNPIXATUHGM-UHFFFAOYSA-N boric acid;magnesium Chemical compound [Mg].OB(O)O HQMFNPIXATUHGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- GBLIGNUYGOFIKS-UHFFFAOYSA-N 4-[2-(3,5-dioxopiperazin-1-yl)ethyl]piperazine-2,6-dione Chemical compound C1C(=O)NC(=O)CN1CCN1CC(=O)NC(=O)C1 GBLIGNUYGOFIKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 claims description 2
- UKVYVZLTGQVOPX-UHFFFAOYSA-N 3-aminobut-2-enoic acid Chemical compound CC(N)=CC(O)=O UKVYVZLTGQVOPX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000004593 Epoxy Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 styrenic toughner Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polycarbonate composite material for 3D printing and a preparation method thereof. Magnesium borate whiskers and graphene oxide are introduced into polycarbonate, so that not only is the polycarbonate strengthened, but also carboxyl, hydroxyl and epoxy functional groups can be promoted to be connected with the polycarbonate and to be uniformly dispersed, the thermal superconductivity of the graphene oxide allows powder in the polycarbonate to be uniformly heated and solidified, thereby reducing the thermal shrinkage of a product during 3D printing. Further, by virtue of polyelectrolytes, the polycarbonate powder is subjected to surface modification at a fluidized bed, so that the surface of the polycarbonate powder is more in a spherical shape, the mobility of the polycarbonate is greatly improved, the powder agglomeration is effectively prevented, and the polycarbonate is suitable for a 3D printing material.
Description
Technical field
Invention relates to a kind of polycarbonate composite material and preparation method thereof, in particular, the present invention relates to a kind of 3D printing polycarbonate composite material powder and preparation method thereof, belongs to 3D printed material field.
Background technology
3D prints, the i.e. one of rapid shaping technique, it is a kind of based on digital model file, use powdery metal or plastics etc. can jointing material, carried out the technology of constructed object by the mode successively printed, increase material manufacture also known as work, it manufactures fast, 3-D effect can be reproduced completely, product design and die production synchronously be carried out, realizes integrated manufacturing system (IMS).The material category that can be used for 3D printing device uses is extensive, comprises metallic substance, inorganic powder material, stupalith, macromolecular material, wax, paper etc.
At present, the 3D printing device technology used for macromolecular material rapid shaping mainly contains: fusion stacking forming technique (FDM), and it is for thread hot-melt plastic; Precinct laser sintering technology (SLS), it is for the rapid shaping of dusty material, is a kind of 3D printing technique that suitable material is maximum; Stereolithography apparatus technology (SLA), it is mainly used in the shaping of photosensitive resin, and raw material is liquid resin.
SLS technology is a kind of 3D printing technique that suitable material is maximum, and has the advantages that tooling cost is low, the time is short, is most widely used a kind of 3D technology.SLS technology and equipment adopt transmitting focusing in the laser of the energy of target area.At the effect lower part melting of the energy launched by laser or softening powdered material in the target area of that manufactures parts.During operation powder connect irradiated laser energy quantity should be enough to quick forming member thin slice, thus target sublimity must be heated before enforcement laser radiation, powder is preheating to slightly lower than the temperature of its fusing point, then under the effect striking off rod, powder is paved; Laser beam sinters selectively according to layering cross section information under the control of the computer, carries out lower one deck sintering again after one deck completes, and removes unnecessary powder, then can obtain a part sintered after all having sintered.
Polycarbonate (PC) refers to the general name of the base polymer containing carbonate group in molecular chain, and because synthesis of bisphenol A type PC output is maximum, purposes is the widest, generally alleged polycarbonate is bisphenol A polycarbonate.Due to the singularity on polycarbonate structure, now become the general engineering plastic that in five large-engineering plastics, rate of growth is the fastest.Polycarbonate is a kind of thermoplastic engineering plastic of high comprehensive performance, has outstanding impelling strength, the transparency and dimensional stability, excellent mechanical strength, electrical insulating property, use temperature wide ranges, good creep resistant, weathering resistance and self-extinguishing.At present, polycarbonate relies on the performance of its excellence to be widely used in the fields such as electronics, electrical equipment, automobile, optical material.But polycarbonate also has powerful and influential shortcoming, as contained a large amount of phenyl ring in its molecular chain, molecular rigidity is large, and molecule space steric hindrance is large, causes its melt temperature high, and melt viscosity is large, and processing fluidity is poor; It easily produces stress cracking to notch sensitive; Fatigue resistance, solvent resistance and wear no resistance; In addition, to exist water and heat all than more sensitive carbonic acid ester bond in its molecular chain, make it easily degrade under high temperature aerobic and wet environment, have a strong impact on material property, significantly limit the application & development of polycarbonate.
Patent 200910074854.3 provides the rapid laser sintering molding material based on polycarbonate powder, that pulverize at low temperature becomes polycarbonate powder material by polycarbonate, styrenic toughner, ABS resin and phenylethylene/maleic anhydride copolymer, ABS graft copolymer mixing granulation; Sulphonic acids tensio-active agent and silane coupling agent are dissolved in dehydrated alcohol; Evenly be sprayed onto polycarbonate powder material surface, base-material made by removing dehydrated alcohol; In base-material, add benzophenone light absorber, nano carborundum powder, non-ionic antistatic agent and mineral-type filler, mix, make the rapid laser sintering molding material based on polycarbonate powder.Resin is first pulverized laggard row surface treatment by the present invention, and due to the higher easy reunion of fine powder surface energy, dispersion difficulty is large, therefore may cause the situation that surface treatment is insufficient, affect powder overall performance; This material preparation method complex process, operational difficulty, is not easy to industrial production.
Summary of the invention
For 3D printing technique to the requirement of polycarbonate powder body material, and defect, a kind of 3D printing of the present invention polycarbonate composite material and preparation method thereof such as at present polycarbonate powder is easily reunited, poor fluidity, contraction are serious.
Technical scheme of the present invention is as follows:
A kind of 3D printing polycarbonate composite material, it is characterized in that matrix material is the spherical powder material comprising magnesium borate crystal whisker and graphene oxide, feed composition comprises by weight:
Polycarbonate 50 ~ 80 weight part,
Magnesium borate crystal whisker 10 ~ 20 weight part,
Graphene oxide 3-5 part,
Coupling agent 0.2 ~ 0.5 weight part,
Thermo-stabilizer 0.1 ~ 0.5 weight part;
Wherein, described polycarbonate number-average molecular weight is 14000 ~ 30000, moisture content≤0.02%; Described magnesium borate crystal whisker diameter is 0.5 ~ 2 μm, and length is 20 ~ 40 μm; Described graphene oxide particle diameter is between 1-10 μm.
Described coupling agent is silane coupling agent.
Described thermo-stabilizer is one or both couplings in two (beta-amino butenoic acid) ester of BDO, tricresyl phosphite (nonyl phenyl) ester.
A preparation method for 3D printing polycarbonate composite material, is characterized in that: preparation method comprises the following steps:
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 10 ~ 20 part by weight of boric acid magnesium whiskers, 3-5 part graphene oxide and water, ultrasonic disperse process 3 ~ 5 minutes, is mixed with suspension; 0.2 ~ 0.5 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 20 ~ 40 minutes obtain material modified;
2) by step 1) material modified and 50 ~ 80 weight part polycarbonates that obtain, 0.1 ~ 0.5 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixing 10 ~ 20 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
4) composite material granular obtained for step 3) is pulverized the powder obtaining 50 ~ 100 μm, powder is immersed the polyelectrolyte aqueous solution, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material, described polyelectrolyte solution is the poly diallyldimethylammonium chloride of concentration 0.05-0.1mol/L or the poly-ethyliminum aqueous solution.
A kind of 3D printing of the present invention polycarbonate composite material and preparation method thereof, by introducing magnesium borate crystal whisker and graphene oxide in polycarbonate, not only reinforced polycarbonate, and the carboxyl of graphene oxide, hydroxyl, epoxy functionality are impelled and to be connected with polycarbonate and dispersed, the superior heat conductivity of graphene oxide makes powder in poly-carbonic acid be heated evenly, solidifies evenly, thus reduces the heat-shrinkable of goods when 3D prints.Further, make polycarbonate powder carry out surface modification at fluidized-bed by polyelectrolyte, its surface more trends towards spherical, significantly promotes the mobility of polycarbonate, effectively prevents powder reuniting.
A kind of 3D printing of the present invention polycarbonate composite material and preparation method thereof, compared with prior art, its outstanding feature and excellent effect are:
1, the present invention introduces graphene oxide and magnesium borate crystal whisker in polycarbonate composition, and magnesium borate crystal whisker length-to-diameter ratio is high, has excellent mechanical property, and graphene oxide changes the thermal characteristics of polycarbonate, makes polycarbonate powder be heated evenly, shrink reduction.Meet 3D and print SLS technology to the requirement of material.
2, the present invention is by soaking polyelectrolyte by polycarbonate powder, and obtains spherical powder through fluidized-bed, improves the mobility of polycarbonate powder, prevents from reuniting.
3, preparation technology of the present invention is easily controlled, and production technique is brief, with low cost, is applicable to large-scale production.
Specific embodiments
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 10 part by weight of boric acid magnesium whiskers, 3 parts of graphene oxides and water, ultrasonic disperse process 3 minutes, is mixed with suspension; 0.2 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 20 minutes obtain material modified;
2) by step 1) material modified and 50 weight part polycarbonates that obtain, 0.1 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixes 10 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
4) composite material granular obtained for step 3) is pulverized the powder obtaining 50 ~ 100 μm, powder is immersed the poly diallyldimethylammonium chloride polyelectrolyte aqueous solution of concentration 0.05mol/L, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material.
embodiment 2
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 20 part by weight of boric acid magnesium whiskers, 5 parts of graphene oxides and water, ultrasonic disperse process 5 minutes, is mixed with suspension; 0.5 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 40 minutes obtain material modified;
2) by step 1) material modified and 60 weight part polycarbonates that obtain, 0.5 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixes 15 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
4) composite material granular obtained for step 3) is pulverized the powder obtaining 50 ~ 100 μm, powder is immersed the poly-ethyliminum polyelectrolyte aqueous solution of concentration 0.1mol/L, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material.
embodiment 3
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 20 part by weight of boric acid magnesium whiskers, 4 parts of graphene oxides and water, ultrasonic disperse process 3 minutes, is mixed with suspension; 0.2 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 20 minutes obtain material modified;
2) by step 1) material modified and 70 weight part polycarbonates that obtain, 0.1 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixes 20 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
4) composite material granular obtained for step 3) is pulverized the powder obtaining 50 ~ 100 μm, powder is immersed the poly diallyldimethylammonium chloride polyelectrolyte aqueous solution of concentration 0.1mol/L, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material.
embodiment 4
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 10 part by weight of boric acid magnesium whiskers, 5 parts of graphene oxides and water, ultrasonic disperse process 3 minutes, is mixed with suspension; 0.4 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 25 minutes obtain material modified;
2) by step 1) material modified and 80 weight part polycarbonates that obtain, 0.5 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixes 20 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
4) composite material granular obtained for step 3) is pulverized the powder obtaining 50 ~ 100 μm, powder is immersed the poly-ethyliminum polyelectrolyte aqueous solution of concentration 0.05mol/L, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material.
Claims (4)
1. a 3D printing polycarbonate composite material, it is characterized in that matrix material is the spherical powder material comprising magnesium borate crystal whisker and graphene oxide, feed composition comprises by weight:
Polycarbonate 50 ~ 80 weight part,
Magnesium borate crystal whisker 10 ~ 20 weight part,
Graphene oxide 3-5 part,
Coupling agent 0.2 ~ 0.5 weight part,
Thermo-stabilizer 0.1 ~ 0.5 weight part;
Wherein, described polycarbonate number-average molecular weight is 14000 ~ 30000, moisture content≤0.02%; Described magnesium borate crystal whisker diameter is 0.5 ~ 2 μm, and length is 20 ~ 40 μm; Described graphene oxide particle diameter is between 1-10 μm.
2. polycarbonate composite material according to claim 1, is characterized in that: described coupling agent is silane coupling agent.
3. polycarbonate composite material according to claim 1, is characterized in that: described thermo-stabilizer is one or both couplings in two (beta-amino butenoic acid) ester of BDO, tricresyl phosphite (nonyl phenyl) ester.
4. the preparation method of the 3D printing polycarbonate composite material described in any one of claim 1 ~ 3, is characterized in that: preparation method comprises the following steps:
1) magnesium borate crystal whisker and surface of graphene oxide modification: add in container by 10 ~ 20 part by weight of boric acid magnesium whiskers, 3-5 part graphene oxide and water, ultrasonic disperse process 3 ~ 5 minutes, is mixed with suspension; 0.2 ~ 0.5 weight part coupling agent is dissolved in ethanol, is mixed with the solution that coupling agent mass content is 20%; Mixed with coupling agent solution by suspension, be heated to 40 ~ 60 DEG C, stir process filtration, vacuum-drying in 20 ~ 40 minutes obtain material modified;
2) by step 1) material modified and 50 ~ 80 weight part polycarbonates that obtain, 0.1 ~ 0.5 weight part thermo-stabilizer, join in high-speed mixer, high-speed stirring mixing 10 ~ 20 minutes, send into meshing co rotating twin screw extrusion fusion plastification, shear modification, extrude pelletizing, obtained polycarbonate composite material particle;
3) by step 2) obtained composite material granular pulverizes the powder obtaining 50 ~ 100 μm, powder is immersed the polyelectrolyte aqueous solution, make powder surface modifications by fluidized-bed, drying obtains spherical polycarbonate composite material, described polyelectrolyte solution is the poly diallyldimethylammonium chloride of concentration 0.05-0.1mol/L or the poly-ethyliminum aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511010669.XA CN105504749B (en) | 2015-12-30 | 2015-12-30 | A kind of 3D printing polycarbonate composite material and preparation method thereof |
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| CN201511010669.XA CN105504749B (en) | 2015-12-30 | 2015-12-30 | A kind of 3D printing polycarbonate composite material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN105504749A true CN105504749A (en) | 2016-04-20 |
| CN105504749B CN105504749B (en) | 2017-06-23 |
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| KR20200049766A (en) * | 2017-09-04 | 2020-05-08 | 오츠카 가가쿠 가부시키가이샤 | Sculpture and its manufacturing method |
| CN107648675A (en) * | 2017-09-16 | 2018-02-02 | 常州富思通管道有限公司 | A kind of preparation method of high-strength bone internal fixation material |
| CN109897356B (en) * | 2017-12-08 | 2021-07-23 | 万华化学集团股份有限公司 | High-heat-resistance polycarbonate composition and preparation method thereof |
| CN109897356A (en) * | 2017-12-08 | 2019-06-18 | 万华化学集团股份有限公司 | A kind of polycarbonate compositions of high heat resistance and preparation method thereof |
| CN109593340A (en) * | 2018-12-27 | 2019-04-09 | 苏州荣昌复合材料有限公司 | A kind of PC material with high thermal conductivity and high reflection |
| CN110698838A (en) * | 2019-10-30 | 2020-01-17 | 濮阳市盛通聚源新材料有限公司 | Flexible conductive film based on polycarbonate and preparation method thereof |
| CN110698838B (en) * | 2019-10-30 | 2021-11-02 | 濮阳市盛通聚源新材料有限公司 | Flexible conductive film based on polycarbonate and preparation method thereof |
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Effective date of registration: 20170527 Address after: 523000 Guangdong Province, Dongguan City Dalingshan Town Water Lang village Yongjun Road No. 333 Applicant after: DONGGUAN YINGHE PRECISION PLASTIC CO.,LTD. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Applicant before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20170527 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Applicant after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Applicant before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
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Denomination of invention: A polycarbonate composite material for 3D printing and its preparation method Granted publication date: 20170623 Pledgee: Agricultural Bank of China Limited Dongguan Dalingshan Sub branch Pledgor: DONGGUAN YINGHE PRECISION PLASTIC CO.,LTD. Registration number: Y2024980021308 |