CN116656077A - ABS material for high interlayer adhesion 3D printing and preparation method thereof - Google Patents
ABS material for high interlayer adhesion 3D printing and preparation method thereof Download PDFInfo
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- CN116656077A CN116656077A CN202310625956.XA CN202310625956A CN116656077A CN 116656077 A CN116656077 A CN 116656077A CN 202310625956 A CN202310625956 A CN 202310625956A CN 116656077 A CN116656077 A CN 116656077A
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- interlayer adhesion
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- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000011229 interlayer Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- -1 methyl tetramethylene Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- GIATZHZBSIMOEE-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C GIATZHZBSIMOEE-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 claims description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 2
- MTUBBMSQXXJFQP-UHFFFAOYSA-N OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O Chemical compound OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O MTUBBMSQXXJFQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- HLXGBWBZPNMJJQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dioctadecyl phosphite Chemical compound P(OCCCCCCCCCCCCCCCCCC)(OCCCCCCCCCCCCCCCCCC)OCC(CO)(CO)CO HLXGBWBZPNMJJQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 229910052570 clay Inorganic materials 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 6
- 229920007019 PC/ABS Polymers 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
-
- 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
- C08K3/34—Silicon-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention relates to the technical field of 3D printing materials, in particular to an ABS material for 3D printing with high interlayer adhesion and a preparation method thereof. The ABS material for 3D printing comprises the following components in parts by weight: 50 to 95 parts of ABS, 0.1 to 20 parts of inorganic filler, 0.1 to 1 part of antioxidant, 0.5 to 3 parts of cross-linking agent, 0.1 to 0.7 part of initiator, 0.1 to 0.5 part of catalyst and 0.1 to 1.0 part of lubricant. According to the invention, the ABS is blended with the inorganic filler, the cross-linking agent, the initiator, the catalyst and the like, so that the inorganic filler, the cross-linking agent and the initiator are uniformly distributed in the ABS, the cross-linking reaction is completed in the subsequent use process, the ABS after cross-linking has a more stable three-dimensional structure, the number of bonding points between printing layers and the bonding strength of the bonding points are improved, the warping degree of an ABS material printing product is reduced, the product quality is improved, and the ABS is widely applied in the 3D printing industry.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to an ABS material for 3D printing with high interlayer adhesion and a preparation method thereof.
Background
The 3D printing technology is a rapid prototyping technology, expands product originality and originality space, can realize design and manufacturing integration without a die, greatly reduces product research and development cost, shortens product development period, improves new product production success rate, enhances process realization capability, and has been widely applied to industries such as aerospace, automobiles, medical treatment and the like.
ABS materials have good strength, flexibility and machining properties, excellent wear resistance and impact absorption capacity, and are the most commonly used thermoplastics for nonmetallic 3D printing.
The invention discloses an ABS-like resin for 3D printing and a preparation method thereof, wherein the ABS-like resin comprises the following raw materials in parts by weight: 5 to 15 parts of ABS-like oligomer, 25 to 60 parts of active monomer, 0.01 to 0.2 part of polymerization inhibitor, 1 to 5 parts of fiber, 1 to 10 parts of photoinitiator, 0.02 to 1 part of defoamer, 0.02 to 1 part of flatting agent, 0.03 to 2 parts of pigment and 2 to 5 parts of filler; the preparation method comprises the following steps: the ABS resin for 3D printing is prepared by mixing the above raw materials in proportion, performing ultrasonic treatment for 45-55min at 35-45 ℃ by using an ultrasonic cleaner, and then placing the mixture in a homogenizer for uniform stirring. The ABS resin for 3D printing, which is prepared by the invention, is applied to the field of 3D printing, 3D printing and curing are carried out on the ABS resin for 3D printing, the shrinkage rate of the 3D printing material obtained by shaping and curing is 0.4% -0.9%, and the elastic modulus value is 2-2.8Gpa.
For example, CN202211487231.0 relates to an ABS material for high-speed 3D printing, which comprises the following components in percentage by weight: 80-90 parts of ABS resin; 0.5 to 1 part of monoglyceride; 5-12 parts of flow modifier; 1-3 parts of plasticizer; 1-3 parts of an antioxidant; 0.5 to 1 portion of cross-linking agent. The invention adopts the fluidity agent to make the ABS into the ultra-high flow plastic, which can improve the speed of the ABS printing material from the original 60-90MM/S to 260MM/S.
Such as CN202110710487.2, relates to a PC/ABS alloy material for 3D printing and a preparation method thereof. The PC/ABS alloy material for 3D printing is prepared from PC, ABS and an auxiliary agent, wherein the PC and the ABS are used as main materials, the weight ratio of the PC to the ABS is 15-35:65-85, the auxiliary agent comprises maleic anhydride grafted ABS, nitrile rubber, styrene-maleic anhydride copolymer (SMA) and an inorganic filling material, and the weight ratio of the maleic anhydride grafted ABS, the nitrile rubber, the styrene-maleic anhydride copolymer, the inorganic filling material to the main materials is 1-20: 1 to 10: 1-20: 1 to 10:100. compared with the prior art, the PC/ABS alloy material provided by the invention has the characteristics of being low in Vicat softening temperature, good in fluidity and high in elongation, so that the material can work at a low nozzle temperature when being applied to three-dimensional printing.
The ABS material is adopted as the main component in the above patent, and the common defect is that the printed product is obviously deformed after cooling, the contact part of the printed product and the 3D printing substrate is easy to warp, and the deformation is particularly obvious for printing large-size products, so that the problem to be solved is urgently needed for 3D printing by adopting the ABS material.
Disclosure of Invention
Aiming at the technical problem of deformation of the existing printed product, the invention provides the ABS material for 3D printing with high interlayer adhesion and the preparation method thereof, which improves the number of bonding points between printing layers and the bonding strength thereof, reduces the warping degree of the printed product of the ABS material, overcomes the defect of deformation of the printed product after cooling, and improves the product quality.
In a first aspect, the invention provides an ABS material for high interlayer adhesion 3D printing, which comprises the following components in parts by weight: 50 to 95 parts of ABS, 0.1 to 20 parts of inorganic filler, 0.1 to 1 part of antioxidant, 0.5 to 3 parts of cross-linking agent, 0.1 to 0.7 part of initiator, 0.1 to 0.5 part of catalyst and 0.1 to 1.0 part of lubricant.
Further, the inorganic filler is one or more of glass microspheres, calcium carbonate, talcum powder, barium sulfate or clay.
Further, the antioxidant is one or more of bis (2, 4-di-tert-butylphenyl) pentaerythritol bisphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, dioctadecyl tetraol bisphosphite, pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), methyl tetramethylene (3, 5-di-tert-butyl-4-hydroxyphenyl propionate) and pentaerythritol distearyl phosphite.
Further, the cross-linking agent is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane and gamma-ureido propyl triethoxysilane.
Further, the initiator is one or more of dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide or di-tert-butyl peroxide.
Further, the catalyst is one or more of dibutyl tin dilaurate, DMEA, N' -lutidine, toluene sulfonic acid, ziegler-natta catalyst.
Further, the lubricant is one or more of ethylene bisstearamide, oleamide, butyl stearate, glycerol trihydroxystearate, polyethylene wax and oxidized polyethylene wax.
In a second aspect, the invention provides a preparation method of an ABS material for high interlayer adhesion 3D printing, comprising the following steps:
s1, placing ABS in an oven, and drying at 80-120 ℃ for at least 3 hours;
s2, weighing ABS, inorganic filler, antioxidant, cross-linking agent, initiator, catalyst and lubricant according to the weight proportion, adding into a high-speed mixer, and stirring for 10-15 min at the temperature of 10-30 ℃ and the rotating speed of 800-1000 r/min to obtain a premix;
and S3, adding the premix obtained in the step S2 into a charging barrel of a double-screw extruder for heating and melting, extruding, air-cooling, air-drying and granulating to obtain a finished product.
Further, in step S3, the twin screw extruder comprises eight heating zones, each zone temperature being set to: 180-200 ℃ in the first area, 200-220 ℃ in the second area, 210-230 ℃ in the third area, 210-240 ℃ in the fourth area, 210-240 ℃ in the fifth area, 210-240 ℃ in the sixth area, 210-240 ℃ in the seventh area, and 190-210 ℃ in the eighth area.
Further, in the step S3, the screw speed of the double-screw extruder is 100-250 r/min, and the torque of the double-screw extruder is 60-80%.
The ABS material for high interlayer adhesion 3D printing has the beneficial effects that the ABS is blended with the inorganic filler, the cross-linking agent, the initiator, the catalyst and the like, so that the inorganic filler, the cross-linking agent and the initiator are uniformly distributed in the ABS, the cross-linking reaction is completed in the subsequent use process, the ABS after cross-linking has a more stable three-dimensional structure, the number of bonding points between printing layers and the bonding strength of the bonding points are improved, the warping degree of a printing product of the ABS material is reduced, the product quality is improved, and the ABS can be widely applied to the 3D printing industry.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
ABS is placed in an oven and dried for 4 hours at 80 ℃. 82 parts of ABS, 15 parts of glass microspheres, 0.5 part of bis (2, 4-di-tert-butylphenyl) pentaerythritol bisphosphite, 1 part of vinyltriethoxysilane, 0.3 part of dicumyl peroxide, 0.2 part of dibutyltin dilaurate and 1 part of oxidized polyethylene wax are weighed and added into a high-speed mixer, the mixing condition is 30 ℃, the rotating speed is 800r/min, stirring is carried out for 10min, after uniform mixing, the mixture is added into a charging barrel of a double-screw extruder, the rotating speed of the screw is 150r/min, the torque of the double-screw extruder is 70%, and the heating temperature of each zone is as follows: 180 ℃, two areas: 200 ℃, three regions: 210 ℃, four regions: 210 ℃, five regions: 220 ℃, six regions: 240 ℃, seven regions: 220 ℃, eight regions: 190 ℃. And after heating and melting, the ABS material for high interlayer adhesion 3D printing is obtained through an extrusion process, an air cooling and drying process and a granulating process (the rotating speed is 1 m/min).
Example 2
ABS is placed in an oven and dried for 4 hours at 100 ℃. 50 parts of ABS, 0.1 part of calcium carbonate, 0.1 part of tris (2, 4-di-tert-butylphenyl) phosphite, 0.5 part of vinyltrimethoxysilane, 0.5 part of cumene hydroperoxide, 0.1 part of DMEA and 0.8 part of polyethylene wax are weighed and added into a high-speed mixer, the mixing condition is 20 ℃, the rotating speed is 900r/min, stirring is carried out for 15min, after uniform mixing, the mixture is added into a charging barrel of a double-screw extruder, the rotating speed of a screw is 100r/min, the torque of the double-screw extruder is 60%, the heating temperature of each zone is as follows: 200 ℃, two areas: 200 ℃, three regions: 220 ℃, four regions: 220 ℃, five regions: 210 ℃, six regions: 210 ℃, seven regions: 210 ℃, eight regions: 200 ℃. And after heating and melting, the ABS material for high interlayer adhesion 3D printing is obtained through an extrusion process, an air cooling and drying process and a granulating process (the rotating speed is 1 m/min).
Example 3
ABS is placed in an oven and dried for 3 hours at 120 ℃. Weighing 95 parts of ABS, 20 parts of talcum powder, 1 part of pentaerythritol tetra (beta- (3, 5-di-tert-butyl 4-hydroxyphenyl) propionate), 3 parts of vinyltri (beta-methoxyethoxy) silane, 0.7 part of tert-butyl hydroperoxide, 0.5 part of N, N' -lutidine and 0.1 part of ethylene bis-stearamide, adding into a high-speed mixer, stirring for 10 minutes at the temperature of 10 ℃ and the rotating speed of 1000r/min, adding into a charging barrel of a double-screw extruder after uniformly mixing, and the rotating speed of a screw is 250r/min, wherein the torque of the double-screw extruder is 80%, and the heating temperature of each zone is as follows: 180 ℃, two areas: 220 ℃, three regions: 230 ℃, four regions: 220 ℃, five regions: 240 ℃, six regions: 220 ℃, seven regions: 240 ℃, eight regions: 210 ℃. And after heating and melting, the ABS material for high interlayer adhesion 3D printing is obtained through an extrusion process, an air cooling and drying process and a granulating process (the rotating speed is 1 m/min).
Comparative example 1
Comparative example 1 differs from example 1 in that the component of comparative example 1 does not contain dibutyltin dilaurate as a catalyst.
Comparative example 2
Comparative example 2 differs from example 1 in that the component of comparative example 2 does not contain the crosslinking agent vinyltriethoxysilane.
Comparative example 3
Comparative example 3 differs from example 1 in that the component of comparative example 3 does not contain the initiator dicumyl peroxide.
Test and performance test
The ABS materials for 3D printing prepared in examples 1 to 3 and comparative examples 1 to 3 were extruded in a single screw extruder, respectively, to satisfy the wire rod for 3D printing equipment, and sample printing was performed using a fused deposition 3D printing equipment, the size of the printed sample was 50×50×100mm, and after the printing was completed in water, the four corners of the test sample were tilted away from the height of the substrate, and the tensile strength of the sample was measured according to the type I sample requirement in GB/T1040.2, and the test results are shown in table 1.
Table 1 sample performance test data printed with ABS material for 3D printing prepared using examples and comparative examples
As can be seen from table 1, the embodiment of the present invention improves the high interlayer adhesion of the printed product compared with the comparative example, thereby improving the tensile strength of the printed product, reducing the warpage of the printed product, and improving the adhesion strength of the printed product and the printed substrate.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (10)
1. The ABS material for high interlayer adhesion 3D printing is characterized by comprising the following components in parts by weight: 50 to 95 parts of ABS, 0.1 to 20 parts of inorganic filler, 0.1 to 1 part of antioxidant, 0.5 to 3 parts of cross-linking agent, 0.1 to 0.7 part of initiator, 0.1 to 0.5 part of catalyst and 0.1 to 1.0 part of lubricant.
2. The ABS material for high interlayer adhesion 3D printing of claim 1 wherein the inorganic filler is one or more of glass microspheres, calcium carbonate, talc, barium sulfate or clay.
3. The ABS material for high interlayer adhesion 3D printing of claim 1, wherein the antioxidant is one or more of bis (2, 4-di-t-butylphenyl) pentaerythritol bisphosphite, tris (2, 4-di-t-butylphenyl) phosphite, dioctadecyl tetraol bisphosphite, pentaerythritol tetrakis (. Beta. -3, 5-di-t-butyl-4-hydroxyphenyl) propionate, methyl tetramethylene (3, 5-di-t-butyl-4-hydroxyphenyl propionate), pentaerythritol distearyl phosphite.
4. The ABS material for high interlayer adhesion 3D printing of claim 1 wherein the cross-linking agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, γ -ureidopropyltriethoxysilane.
5. The ABS material for high interlayer adhesion 3D printing of claim 1 wherein the initiator is one or more of dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide or di-t-butyl peroxide.
6. The ABS material for high interlayer adhesion 3D printing of claim 1 wherein the catalyst is one or more of dibutyltin dilaurate, DMEA, N' -dimethylpyridine, toluene sulfonic acid, ziegler-natta catalyst.
7. The ABS material for high interlayer adhesion 3D printing of claim 1 wherein the lubricant is one or more of ethylene bisstearamide, oleamide, butyl stearate, glycerol trihydroxystearate, polyethylene wax, oxidized polyethylene wax.
8. A method for producing the ABS material for high interlayer adhesion 3D printing according to any one of claims 1 to 7, comprising the steps of:
s1, placing ABS in an oven, and drying at 80-120 ℃ for at least 3 hours;
s2, weighing ABS, inorganic filler, antioxidant, cross-linking agent, initiator, catalyst and lubricant according to the weight proportion, adding into a high-speed mixer, and stirring for 10-15 min at the temperature of 10-30 ℃ and the rotating speed of 800-1000 r/min to obtain a premix;
and S3, adding the premix obtained in the step S2 into a charging barrel of a double-screw extruder for heating and melting, extruding, air-cooling, air-drying and granulating to obtain a finished product.
9. The method for producing ABS material for high interlayer adhesion 3D printing according to claim 8 wherein in step S3, the twin screw extruder comprises eight heating zones, each zone temperature being set to: 180-200 ℃ in the first area, 200-220 ℃ in the second area, 210-230 ℃ in the third area, 210-240 ℃ in the fourth area, 210-240 ℃ in the fifth area, 210-240 ℃ in the sixth area, 210-240 ℃ in the seventh area, and 190-210 ℃ in the eighth area.
10. The method for preparing an ABS material for 3D printing with high interlayer adhesion according to claim 8 wherein in step S3, the screw speed of the twin screw extruder is 100 to 250r/min and the torque of the twin screw extruder is 60 to 80%.
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