CN114479402A - Polycarbonate composition for 3D printing and preparation method and application thereof - Google Patents
Polycarbonate composition for 3D printing and preparation method and application thereof Download PDFInfo
- Publication number
- CN114479402A CN114479402A CN202011148863.5A CN202011148863A CN114479402A CN 114479402 A CN114479402 A CN 114479402A CN 202011148863 A CN202011148863 A CN 202011148863A CN 114479402 A CN114479402 A CN 114479402A
- Authority
- CN
- China
- Prior art keywords
- polycarbonate composition
- polycarbonate
- aliphatic
- printing
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 83
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000010146 3D printing Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 229920001634 Copolyester Polymers 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- -1 aliphatic diols Chemical class 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000013538 functional additive Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012745 toughening agent Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 16
- 238000001125 extrusion Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 16
- 229920001896 polybutyrate Polymers 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 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 8
- 239000000155 melt Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229920001748 polybutylene Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polycarbonate composition for 3D printing and a preparation method and application thereof. The polycarbonate composition for 3D printing provided by the invention comprises polycarbonate, aliphatic aromatic copolyester, graphene dispersion liquid and optional functional auxiliary agent. The polycarbonate composition for 3D printing provided by the invention can reduce the temperature of a printing nozzle and a soleplate and has higher printing size precision.
Description
Technical Field
The invention relates to a polycarbonate composition for 3D printing and a preparation method and application thereof.
Background
Graphene (Graphene) is a novel two-dimensional single-layer sheet-like nano carbon material composed of sp2 hybridized carbon atoms, has been paid attention to its excellent properties, and is expected to cause revolutionary changes in a variety of fields such as photoelectric products, energy technologies, functional composites, microelectronic devices, and biological medicines.
The principle is that firstly, a digitalized three-dimensional model is obtained through computer modeling or direct scanning of a prototype, then, software is used for cutting the model into two-dimensional section data according to a certain coordinate axis, and a 3D printer is used for printing layer by layer and stacking the section data to form an entity. Through the recent 30 years of development, 3D printing technology has been considered as one of the core technologies that may change the way laboratory and industrial production. The additive manufacturing technology can save materials, shorten the research and development period and reduce the cost, and has great potential application in the aspects of mold manufacturing, product design, medical treatment, education, aerospace and the like.
At present, a 3D printing molding method mainly includes: fused Deposition Modeling (FDM), Stereolithography (SLA), and Selective Laser Sintering (SLS), among others. The FDM technology does not need laser, is simple in use and maintenance, low in cost and widely applied. The technical principle is that a thermoplastic polymer is heated and melted, then extruded out through a spray head, cooled and solidified to form a thin layer with an outline shape, and then overlapped and stacked layer by layer to finally form a product. Therefore, the thermoplastic polymer for FDM 3D printing is required to have excellent fluidity and fast curing rate, and the FDM 3D printing consumables commonly used in the market at present are mainly ABS (acrylonitrile-butadiene-styrene terpolymer) and PLA (polylactic acid), and in addition, a small amount of PC (polycarbonate), TPU (thermoplastic polyurethane), PA (nylon), and the like.
PC is a high molecular polymer containing a carbonate group in its molecular chain, and is classified into various types such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Among them, aromatic, especially bisphenol A type PC, is excellent in mechanical properties and is widely used in the fields of glass assembly industry, automobile industry, electronic and electric appliance industry, etc. Bisphenol A type PC is used as a common transparent engineering plastic, is tasteless, nontoxic, low in molding shrinkage rate and good in flame retardance, and has excellent mechanical properties which are not possessed by other transparent high polymer materials (such as PMMA and PS). PCs have been successfully developed for 3D printed materials. However, compared with common 3D printing high polymer materials such as ABS and PLA, in the fused deposition 3D printing technology, the PC has the problems of overhigh printing temperature, serious warping and the like. This is mainly related to the thermal stress caused by the fluidity and thermal properties of the PC itself, and although the warpage can be alleviated by increasing the nozzle temperature and the hot bed temperature, this problem cannot be completely solved. In order to reduce the nozzle temperature and the soleplate temperature required by PC during printing, Polycaprolactone (PCL) [ CN 108034217A ], polyethylene terephthalate-1, 4-cyclohexane dimethanol ester (PETG) [ CN 104672880A ], polylactic acid (PLA) [ CN 106543672A ] and polybutylene terephthalate (PBT) [ CN 105419260A ] are added. Although the print nozzle temperature and the soleplate temperature can be reduced by adding polymers, the impact strength of the blend is significantly reduced. Aiming at the problem that the impact strength is obviously reduced after PC and PBT are blended, a plurality of toughening agents are developed and used to effectively improve the impact strength of the blend (Yaojun, Schacher, spring, etc.; plastics industry, 2008) (Xudaoqiang, Lubobo, plastics industry, 2005), but the warpage of the blend during 3D printing is still obvious. In view of the above problem, there is a need to invent a technology for preparing a novel modified polycarbonate/aliphatic aromatic copolyester composition, which can reduce the temperature of a nozzle and the temperature of a soleplate during 3D printing and simultaneously improve the dimensional accuracy of a product.
Graphene modified ABS (WEI X., LI D., WEI J., et al.3D precursor graphene com. scientific Reports,2015, 11181-. However, these technologies either use graphene oxide or graphene nanoplatelets, which cannot exert the performance characteristics of graphene, or easily form holes during the process of preparing composite wires, which affects the printing effect, or the product is easily warped when the thermal stress is not uniform.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a polycarbonate composition for 3D printing, which can effectively reduce the temperature of a printing nozzle and the temperature of a bottom plate and has higher printing size precision.
The first aspect of the invention provides a polycarbonate composition for 3D printing, which comprises polycarbonate, aliphatic aromatic copolyester, graphene dispersion liquid and optional functional auxiliary agents.
According to some embodiments of the invention, the polycarbonate composition comprises, in parts by mass:
(a)50 to 99 parts of a polycarbonate;
(b)1 to 50 parts of an aliphatic aromatic copolyester;
(c)0.01 to 5 parts of a graphene dispersion; and optionally
(d)0.5 to 5 parts of functional auxiliary agent.
According to a preferred embodiment of the present invention, the polycarbonate composition comprises, in parts by mass:
(a)60-90 parts of polycarbonate;
(b)10-40 parts of aliphatic aromatic copolyester;
(c)0.5-3 parts of graphene dispersion liquid; and optionally
(d)0.5 to 5 parts of functional auxiliary agent.
According to a further preferred embodiment of the present invention, the polycarbonate composition comprises 1 to 3 parts by mass of the graphene dispersion.
According to some embodiments of the invention, the polycarbonate is obtained by melt polycondensation of bisphenol a and diphenyl carbonate and/or by direct esterification polymerization of bisphenol a and phosgene.
According to some embodiments of the invention, the number of graphene layers in the graphene dispersion is not higher than 10.
According to some embodiments of the invention, the graphene has a surface functional group selected from at least one of a carboxyl group, an acid anhydride, a hydroxyl group, an amine group, an amide group, and an imide and derivatives thereof.
According to some embodiments of the invention, the solvent of the graphene dispersion is selected from at least one of mineral oil, silicone oil, ethylene glycol and glycerol and derivatives thereof.
According to some embodiments of the invention, the graphene dispersion liquid has a graphene mass concentration of 0.1% to 10%.
According to some embodiments of the invention, the aliphatic aromatic copolyester is selected from a copolyester of an alpha, omega-aliphatic diacid or a derivative thereof and an aromatic diacid or a derivative thereof condensed with an aliphatic diol.
According to some embodiments of the invention, the aliphatic aromatic copolyester comprises a chain-extended copolyester.
According to some embodiments of the invention, the α, ω -aliphatic diacid is selected from substituted or unsubstituted α, ω -aliphatic diacids containing from 2 to 22 backbone carbon atoms.
According to some embodiments of the invention, the substituted α, ω -aliphatic diacid is selected from the group consisting of α, ω -aliphatic diacids substituted with at least one substituent selected from the group consisting of C1-C6 linear alkyl, C3-C6 branched alkyl, C3-C6 alkyl, and C2-C6 unsaturated alkyl.
According to some embodiments of the invention, the derivative of the α, ω -aliphatic diacid includes the anhydride, ester, acid halide, etc. of the corresponding acid of the α, ω -aliphatic diacid.
According to some embodiments of the invention, the α, ω -aliphatic diacid is selected from at least one of 1, 4-succinic acid, 1, 6-adipic acid and 1, 8-suberic acid.
According to some embodiments of the invention, the aromatic diacid is selected from substituted or unsubstituted aromatic diacids containing 8 to 22 backbone carbon atoms.
According to some embodiments of the invention, the substituted aromatic diacid is selected from aromatic diacids substituted with at least one substituent selected from the group consisting of C1-C6 linear alkyl, C3-C6 branched alkyl, C3-C6 alkyl, and C2-C6 unsaturated alkyl.
According to some embodiments of the invention, the derivative of the aromatic diacid includes the corresponding anhydride, ester, acid halide, etc. of the aromatic diacid.
According to some embodiments of the invention, the aromatic diacid is selected from at least one of terephthalic acid and 2, 6-naphthalene diacid.
According to some embodiments of the invention, the derivative of an aromatic diacid is selected from dimethyl terephthalate.
According to some embodiments of the invention, the aliphatic diol is selected from diols containing 2 to 10 carbon atoms.
According to some embodiments of the invention, the aliphatic diol is selected from at least one of 1, 4-butanediol, 1, 6-hexanediol, and 1, 8-octanediol.
According to some embodiments of the invention, the functional adjuvant is selected from at least one of a compatibilizing agent, an inorganic filler, an antioxidant, a lubricant, a colorant, and a flame retardant.
The second aspect of the present invention provides a method for preparing the polycarbonate composition according to the first aspect, which comprises mixing the polycarbonate, the aliphatic aromatic copolyester, the graphene dispersion liquid and optional functional additives in a molten state, and performing extrusion granulation to obtain the polycarbonate composition.
According to some embodiments of the invention, the polycarbonate composition is prepared by a melt blending process.
According to some embodiments of the invention, the melt blending process employs a twin screw continuous extrusion process.
According to some embodiments of the present invention, the melt blending method comprises mixing the polycarbonate, the aliphatic aromatic copolyester, the graphene dispersion liquid and the optional functional additives uniformly according to a required ratio, and then performing continuous extrusion granulation to obtain the polycarbonate composition.
According to some embodiments of the present invention, the melt blending method comprises separately metering the polycarbonate, the aliphatic aromatic copolyester and the toughening agent into a twin-screw extruder according to certain feeding proportions, and performing extrusion granulation to obtain the polycarbonate composition.
According to some embodiments of the invention, in the melt blending process, the screw speed is from 50rpm to 1500 rpm.
According to some embodiments of the invention, the melt blending process is at a temperature of 160 ℃ to 260 ℃.
A third aspect of the invention provides a use of the polycarbonate composition according to the first aspect or the polycarbonate composition obtained by the preparation method according to the second aspect in 3D printing.
The fourth aspect of the present invention provides a method for preparing a 3D printing material, which comprises melt-extruding the polycarbonate composition according to the first aspect or the polycarbonate composition obtained by the preparation method according to the second aspect, cooling, and orienting and drawing to obtain the 3D printing material.
According to some embodiments of the present invention, the polycarbonate composition after extrusion granulation is further subjected to melt extrusion to cool the polycarbonate composition melt and simultaneously perform drawing and winding to form a line, preferably a single screw extrusion method, wherein the polycarbonate composition particles are subjected to melt extrusion through a single screw extruder, and are cooled through two water baths with different temperatures and simultaneously drawn and wound to form a 3D printing line.
According to the invention, the graphene functional group interacts with the matrix resin, so that the dispersion state of graphene is improved, and the thermal stress of a printed product is reduced due to the heat conduction effect of the graphene functional group. This combines with graphite alkene size stabilization effect, has improved printed matter size precision. Meanwhile, the graphene is oriented or the polymer random coil is inhibited from loosening in the extrusion printing process, so that the viscosity is reduced, the printing temperature and the hot bed temperature are reduced, and a better technical effect is achieved. The polycarbonate composition for 3D printing provided by the invention can reduce the temperature of a printing nozzle and a soleplate and has higher printing size precision.
Detailed Description
The materials and preparation methods used in the present invention are briefly described below:
1. polycarbonate (PC)
In the present invention, PC is a high molecular polymer having a carbonate group in the molecular chain, and is generally obtained by melt polycondensation of bisphenol A and diphenyl carbonate or direct esterification of bisphenol A and phosgene.
2. Aliphatic aromatic copolyester
The aliphatic aromatic copolyester of the present invention is a copolyester obtained by condensing an aromatic diacid or a derivative thereof, an alpha, omega-aliphatic diacid or a derivative thereof, and at least one aliphatic diol. Including but not limited to poly (ethylene-co-oxalate terephthalate), poly (ethylene-co-malonate), poly (ethylene-co-succinate terephthalate), poly (ethylene-co-glutarate), poly (ethylene-co-adipate), poly (ethylene-co-suberate), poly (trimethylene-co-oxalate), poly (trimethylene-co-malonate), poly (trimethylene-co-succinate), poly (trimethylene-co-glutarate), poly (trimethylene-co-adipate), poly (trimethylene-co-suberate), poly (trimethylene-co-adipate), Polytrimethylene terephthalate-co-sebacate, polybutylene terephthalate-co-oxalate, polybutylene terephthalate-co-malonate, polybutylene terephthalate-co-succinate, polybutylene terephthalate-co-glutarate, polybutylene terephthalate-co-adipate, polybutylene terephthalate-co-octanedioate, polyhexamethylene terephthalate-co-oxalate, polyhexamethylene terephthalate-co-malonate, polyhexamethylene terephthalate-co-succinate, polyhexamethylene terephthalate-co-glutarate, polyhexamethylene terephthalate-co-adipate, or polyhexamethylene terephthalate-co-octanedioate, and the like.
3. Graphene
The graphene is modified by a physical or chemical method, and carboxyl, hydroxyl, carboxyl, acid anhydride, hydroxyl, amido, imide, derivative groups thereof and the like are introduced on the graphene. Preferred graphene includes graphene modified with carboxyl, hydroxyl and derivatives thereof. The modified graphene forms a uniform dispersion in an organic solvent, and the solvent is preferably mineral oil, silicone oil, glycerol and derivatives thereof.
4. Method for preparing polycarbonate composition for 3D printing
The method for preparing the polycarbonate composition comprises the steps of uniformly mixing the required amount of PC, the required amount of aliphatic aromatic copolyester and the required amount of graphene dispersion liquid in a molten state in a continuous process, and extruding and granulating. According to the continuous melting preparation method, the PC particles, the aliphatic aromatic copolyester particles and the graphene dispersion liquid are uniformly mixed according to a certain proportion, and then the mixture is added into a feeding port of a double-screw extruder by a feeding machine according to a certain feeding rate. The feeder can be a weight loss feeder or a volume feeder. And the other concrete embodiment is that a plurality of feeders are adopted to respectively meter and add the PC particles, the aliphatic aromatic copolyester particles and the graphene dispersion liquid into a double-screw extruder according to a certain feeding proportion for reaction and extrusion, and extruded sample bars are cut into granules through a water tank or underwater to prepare the blend particles. The extrudate can also be air cooled by an anhydrous process and then pelletized.
Extrusion temperatures suitable for the present invention are preferably 160 ℃ to the low thermal decomposition temperature of PC and aliphatic aromatic copolyester, more preferably 180 ℃ to 240 ℃; the rotational speed of the extruder is 50rpm to 1500rpm, preferably 100rpm to 400 rpm.
Melt blending devices suitable for use in the present invention include a variety of mixers, Farrel continuous mixers, Banbury mixers, single screw extruders, twin screw extruders, multiple screw extruders (more than two screws), reciprocating single screw extruders such as Buss Ko-kneaders (Buss Ko-kneaders), and the like. Preferred processes are continuous melt blending extrusion processes including twin screw extrusion processes. Continuous twin-screw extruders suitable for use in the present invention include twin-screw extruders of different designs, such as the ZSK Mcc manufactured by Coperion, Germany18Co-rotating parallel twin screw extruders and the like.
5. Method for preparing 3D printing material
The invention provides a 3D printing material (3D printing line) which is obtained by melting and extruding the polycarbonate composition prepared by the continuous melting, extruding and blending method in a screw extruder, cooling and simultaneously drawing and rolling into a line.
The invention provides a 3D printing line method which is a single-screw extrusion method. In the method, a blend prepared in advance is added into a single-screw extruder, the single-screw extruder is generally divided into three stages on the effective length, the first stage is a conveying section, and the blend is preheated and extruded at the first stage; the second section is a compression section, the depth of the thread groove is reduced from large to small, and the melt temperature reaches the degree of plasticizing and melting the polycarbonate composition; the third section is a metering section, and the blend melt is conveyed to a 3D printing line die according to a certain melt flow under the rotation of a screw. The die is provided with one or more circular small holes, and the circular holes can be selected to have different diameters according to the requirements of a printer, and the diameter is generally 1.75mm or 3.00 mm. And cooling and drafting the extruded printing line, and rolling after detection. There are various methods of cooling, including water cooling or air cooling.
The extrusion temperature of the 3D printed line of the blend is from 100 ℃ to 260 ℃, preferably from 200 ℃ to 240 ℃. The number of revolutions of the single-screw extruder is 10 to 200rpm, preferably 25 to 100 rpm.
The 3D printing line can be used for preparing 3D printing products by Fused Deposition Modeling (FDM), and has lower printing temperature and lower bottom plate temperature and better impact strength.
The invention carries out performance measurement according to the following method:
and (3) testing impact strength: the measurement was carried out according to ISO 179/1eA using a model 6957 materials tester from CEAST.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
In the following examples, Polycarbonate (PC) was used as HF1130 from SABIC;
the aliphatic aromatic copolyester adopts BASF company C1200(PBAT, polybutylene adipate terephthalate);
graphene is a GRN2000 mineral oil dispersion (graphene concentration 5%) from royal new energy technology (shanghai) ltd.
Comparative example 1
Weighing the following raw materials in proportion: the mass portion of PC is 80 portions, and the mass portion of PBAT is 20 portions. Uniformly mixing PC and PBAT, feeding through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out grain cutting, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-220 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
Comparative example 2
Weighing the following raw materials in proportion: 80 parts of PC, 20 parts of PBAT, 0.6 part of graphene nanoplatelets and 0.08 part of antioxidant. Uniformly mixing PC, PBAT, graphene microchip and antioxidant, feeding through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, drawing strips, cooling in a water bath, and then pelletizing, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-220 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
Comparative example 3
Weighing the following raw materials in proportion: 80 parts of PC, 20 parts of PBAT, 0.03 part of graphene oxide (oxygen content: 40%), 0.08 part of antioxidant and 0.57 part of white oil. Uniformly mixing PC, PBAT, graphene oxide, an antioxidant and white oil, feeding through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, cooling a brace in a water bath, and then cutting into granules, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-fold and 220 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
[ example 1 ]
Weighing the following raw materials in proportion: 80 parts of PC, 20 parts of PBAT, 0.6 part of graphene dispersion liquid (the mass concentration of graphene is 5%, the oxygen content in graphene is 10%) and 0.08 part of antioxidant. Uniformly mixing PC, PBAT, graphene dispersion liquid and an antioxidant, feeding through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out particle cutting, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
[ example 2 ]
Weighing the following raw materials in proportion: 80 parts of PC, 20 parts of PBAT, 1 part of graphene dispersion liquid and 0.08 part of antioxidant. Uniformly mixing PC, PBAT, graphene dispersion liquid and an antioxidant, feeding through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out particle cutting, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
[ example 3 ] A method for producing a polycarbonate
Weighing the following raw materials in proportion: 80 parts of PC, 20 parts of PBAT, 2 parts of graphene dispersion liquid and 0.08 part of antioxidant. Uniformly mixing the PC, the PBAT and the graphene dispersion liquid, feeding the mixture through a hopper at the first section of a double-screw extruder, carrying out melt extrusion, carrying out water bath cooling on a brace, and then carrying out granulation, wherein the rotating speed of a screw is 200r/min, the feeding speed is 1kg/h, and the temperature of each section of the extruder is 180-class 220 ℃. The collected particles are dried for 4 hours at 85 ℃ and then packaged for standby.
[ PREPARATION EXAMPLE 1 ]
The 6 blend particles in the examples 1-3 and the comparative examples 1-3 are fed by a hopper at the first section of a single-screw extruder, melted and extruded, a brace is cooled by two sections of water baths with different temperatures, and the blend particles are coiled into a wire after the wire diameter is qualified through a drawing test, the screw rotating speed is 15r/min, the temperature of each section of the extruder is 200 and 230 ℃, and the drawing speed is adjusted in real time according to the tested wire diameter so as to ensure that the wire diameter is about 1.75mm or 3.00 mm.
[ test example 1 ]
The wire rod manufactured in preparation example 1 was printed on a copier 2X printer of Makerbot corporation, and different temperatures were selected for printing, and appropriate printing temperature conditions were determined.
The results of the bar testing of the 6 blends prepared in examples 1 to 3 and comparative examples 1 to 3 according to test example 1 are shown in Table 1. From the result can obviously see, add graphite alkene etc. and all can promote the size precision who prints the finished piece, reduce 3D and print the temperature. Wherein the addition of the graphene dispersion in an amount exceeding 1 part can reduce the dimensional error to within the error range of test bars specified by the standard. Meanwhile, the 3D printing temperature is reduced from 280 ℃ to 250 ℃, so that the material is easier to print.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A polycarbonate composition for 3D printing comprises polycarbonate, aliphatic aromatic copolyester, graphene dispersion liquid and optional functional auxiliary agents.
2. The polycarbonate composition according to claim 1, wherein the polycarbonate composition comprises, in parts by mass:
(a)50 to 99 parts of a polycarbonate;
(b)1 to 50 parts of an aliphatic aromatic copolyester;
(c)0.01-5 parts of graphene dispersion liquid; and optionally
(d)0.5 to 5 parts of functional auxiliary agent.
3. The polycarbonate composition according to claim 1 or 2, wherein the polycarbonate is obtained by melt polycondensation of bisphenol a with diphenyl carbonate and/or by direct esterification polymerization of bisphenol a with phosgene.
4. The polycarbonate composition according to any one of claims 1 to 3, wherein the graphene dispersion has no more than 10 layers, preferably the graphene has a surface functional group selected from at least one of a carboxyl group, an acid anhydride, a hydroxyl group, an amine group, an amide group, and an imide and a derivative thereof; and/or the solvent of the graphene dispersion is at least one selected from mineral oil, silicone oil, ethylene glycol and glycerol and derivatives thereof.
5. The polycarbonate composition according to any one of claims 1 to 4, wherein the graphene dispersion liquid has a graphene mass concentration of 0.1% to 10%.
6. The polycarbonate composition according to any of claims 1-5, wherein the aliphatic aromatic copolyester is selected from copolyesters of alpha, omega-aliphatic diacids or derivatives thereof and aromatic diacids or derivatives thereof condensed with aliphatic diols, preferably the aliphatic aromatic copolyester comprises a chain-extended copolyester; more preferably still, the first and second liquid crystal compositions are,
the alpha, omega-aliphatic diacid is selected from substituted or unsubstituted alpha, omega-aliphatic diacids containing 2 to 22 main chain carbon atoms, and is preferably selected from at least one of 1, 4-succinic acid, 1, 6-adipic acid and 1, 8-suberic acid; and/or
The aromatic diacid is selected from substituted or unsubstituted aromatic diacid containing 8 to 22 main chain carbon atoms, preferably at least one selected from terephthalic acid and 2, 6-naphthalene diacid; and/or
The aliphatic diol is selected from diols having 2 to 10 carbon atoms, preferably at least one selected from 1, 4-butanediol, 1, 6-hexanediol and 1, 8-octanediol.
7. The polycarbonate composition of any of claims 1-6, wherein the functional additives are selected from at least one of compatibilizing agents, inorganic fillers, antioxidants, lubricants, colorants, and flame retardants.
8. A method for preparing the polycarbonate composition of any one of claims 1-7, comprising mixing the polycarbonate, the aliphatic aromatic copolyester, the toughening agent and optionally a functional aid in a molten state, and extruding for granulation to obtain the polycarbonate composition.
9. Use of the polycarbonate composition according to any of claims 1 to 7 or obtained according to the preparation process of claim 8 in 3D printing.
10. A method for preparing a 3D printing material, comprising melt extruding, cooling, and orientation drawing the polycarbonate composition according to any one of claims 1 to 7 or the polycarbonate composition obtained by the preparation method according to claim 8 to obtain the 3D printing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011148863.5A CN114479402A (en) | 2020-10-23 | 2020-10-23 | Polycarbonate composition for 3D printing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011148863.5A CN114479402A (en) | 2020-10-23 | 2020-10-23 | Polycarbonate composition for 3D printing and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114479402A true CN114479402A (en) | 2022-05-13 |
Family
ID=81470601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011148863.5A Pending CN114479402A (en) | 2020-10-23 | 2020-10-23 | Polycarbonate composition for 3D printing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479402A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751587A (en) * | 2016-12-28 | 2017-05-31 | 深圳市明鑫高分子技术有限公司 | Graphene 3D printing material and preparation method thereof |
| CN109666276A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | 3D printing modification material of polycarbonate, printing silk thread and preparation method thereof |
| CN111087780A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified polycarbonate/aliphatic aromatic copolyester composition, preparation method and application |
-
2020
- 2020-10-23 CN CN202011148863.5A patent/CN114479402A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751587A (en) * | 2016-12-28 | 2017-05-31 | 深圳市明鑫高分子技术有限公司 | Graphene 3D printing material and preparation method thereof |
| CN109666276A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | 3D printing modification material of polycarbonate, printing silk thread and preparation method thereof |
| CN111087780A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Modified polycarbonate/aliphatic aromatic copolyester composition, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113088055A (en) | High-performance polyvinyl alcohol-based composite material and preparation method thereof | |
| JP4572516B2 (en) | Method for producing resin composition | |
| TW201602211A (en) | Modification of engineering plastics using olefin-maleic anhydride copolymers | |
| WO2006123824A1 (en) | Process for producing resin composition containing fibrous filler in high concentration and resin composition pellet | |
| CN107108901B (en) | Shaped polylactic acid articles and method for making same | |
| CN109666272B (en) | Polylactic acid modified material for 3D printing, printing silk thread and preparation method thereof | |
| CN113185810B (en) | Renewable high-barrier polyester packaging material and preparation method thereof | |
| CN109666276B (en) | Polycarbonate modified material for 3D printing, printing silk thread and preparation method thereof | |
| CN106543622A (en) | Polyester is as flow improver additive in the purposes for improving enhancing ASA composition glossiness | |
| CN111087780B (en) | Modified polycarbonate/aliphatic aromatic copolyester composition, preparation method and application | |
| CN109721786B (en) | Polyethylene composite material and preparation method thereof | |
| CN111171541A (en) | Modified PC/ABS composition for 3D printing and preparation method thereof | |
| JP6263428B2 (en) | Thermoplastic polyester resin pellet blend, method for producing pellet blend and molded product | |
| CN112159588A (en) | Low-warpage 3D printing PA/PPO alloy consumable and preparation method thereof | |
| CN114479402A (en) | Polycarbonate composition for 3D printing and preparation method and application thereof | |
| WO2019189328A1 (en) | Resin composition and filament-like molded body formed from same | |
| KR20180007179A (en) | Biodegradable filament composition for 3D printer containing metal powder and filament for 3D printer using the same | |
| CN114507429A (en) | Polycarbonate composition for 3D printing and preparation method and application thereof | |
| JPH0525903B2 (en) | ||
| CN111320869A (en) | High-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing and preparation method thereof | |
| CN111592755B (en) | Enhanced bio-based polyamide 56 composition and preparation method thereof | |
| CN107163523A (en) | A kind of fused glass pellet polyhydroxyalkanoate material and preparation method thereof | |
| CN108017903A (en) | A kind of chopped glass fiber enhancing nylon consumptive material and preparation method thereof | |
| CN116063833A (en) | Biodegradable super-tough 3D printing material and preparation method thereof | |
| CN116003982A (en) | Glass fiber composite polycarbonate modified material for 3D printing, preparation method thereof and printing wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |