CN111320869A - High-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing and preparation method thereof - Google Patents
High-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing and preparation method thereof Download PDFInfo
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- CN111320869A CN111320869A CN202010309363.9A CN202010309363A CN111320869A CN 111320869 A CN111320869 A CN 111320869A CN 202010309363 A CN202010309363 A CN 202010309363A CN 111320869 A CN111320869 A CN 111320869A
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- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 title claims abstract description 84
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 238000010146 3D printing Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 7
- 230000007613 environmental effect Effects 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims description 20
- 239000004677 Nylon Substances 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 18
- 229920001778 nylon Polymers 0.000 claims description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- -1 amine stearate Chemical class 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 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 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005491 wire drawing Methods 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 235000021355 Stearic acid Nutrition 0.000 claims 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 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 239000012796 inorganic flame retardant Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 150000003902 salicylic acid esters Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 21
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 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 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 229940088990 ammonium stearate Drugs 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
- B29B13/065—Conditioning or physical treatment of the material to be shaped by drying of powder or pellets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical 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 discloses a 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable and a preparation method thereof. According to the invention, based on the research and development of 3D printing consumables, the 3D printing nylon 6T consumables are prepared by mixing materials through a double-screw extruder and drawing wires through a single-screw extruder. The feed comprises the following raw materials in parts by weight: 40-70 parts of nylon 6T; 0-5 parts of a compatilizer; 0-40 parts of glass fiber; 5-15 parts of a halogen-free flame retardant; 0.1-1 part of antioxidant; 1-5 parts of a lubricant; 0-0.5 part of anti-ultraviolet agent; 5-15 parts of a toughening agent; 0-1.5 parts of toner. The invention takes nylon 6T resin as a base material, utilizes compatilizer, glass fiber, antioxidant, lubricant, uvioresistant agent, toughening agent, halogen-free flame retardant and the like to modify the nylon 6T resin, and adjusts the synergistic effect among the components with different proportions, so that the consumable material has the characteristics of high temperature resistance up to more than 300 ℃ without deformation, high strength, low shrinkage, low warpage, high molding precision, halogen-free environmental protection, easy removal of support and the like.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing and a preparation method thereof.
Background
3D printing, also known as additive manufacturing, refers to a technique for manufacturing three-dimensional entities by layer-by-layer superimposition of materials, based on digital model files. Compared with traditional material reduction manufacturing, the 3D printing technology has the following outstanding advantages: (1) the structure information of the product is converted into a data file through a computer, so that digital intelligent manufacturing can be realized; (2) the production process is simplified, the manufacturing period is shortened, and the rapid molding is realized; (3) a cutter or a die in the traditional process is not needed, and a workpiece with a very complex structure can be formed; (4) the near-net forming can be realized, and the waste of raw materials and the pollution to the environment are reduced; (5) the processing mode of the 3D printing layer-by-layer superposition is beneficial to preparing a non-homogeneous functional gradient material; (6) the product can be customized individually, and can respond to market demands quickly. In recent years, 3D printing technology has been rapidly developed and is used in various fields such as medical treatment, aerospace, construction, art, food, and the like. Among them, the most widely used technique is the FDM printing technique, i.e., the fused deposition technique, and in the fused deposition molding process, the printing material is a key factor that affects the process development and the performance of the finished product. Common printing materials are polylactic acid (PLA), acrylonitrile-butadiene-styrene copolymer (ABS), Polycarbonate (PC), polyethylene terephthalate-1, 4-cyclohexane dimethanol ester (PETG), nylon (PA), and the like. These printing materials have their own drawbacks that limit their application. The PLA material is very brittle and does not resist high temperature; ABS has poor solvent resistance and easy warping in printing; the PC has high glass transition temperature, so that the printed layer has poor bonding performance and is easy to warp, and the PC generally contains bisphenol A which is a carcinogen. The nylon material has a plurality of excellent performances in engineering plastics, and the modified PA6T has the following advantages: (1) excellent solder resistance: PA6T has a high melting point (310 ℃ C.), and a high heat distortion temperature (about 300 ℃ C.), and therefore exhibits excellent solder resistance. The excellent solder resistance makes PA6T particularly suitable for use in electronic connectors for Surface Mount Technology (SMT). (2) Excellent high-temperature rigidity: PA6T maintained a relatively high modulus at elevated temperatures, for example 55% of the modulus at 120 ℃ at 23 ℃. That is, PA6T can maintain a stable and excellent rigidity over a wide temperature range. (3) Excellent chemical resistance. (4) The water absorption rate is low: for nylon resins, the water absorption of PA6T is quite low, only 1/4 to 1/3 for nylon 66. Therefore, the change in physical properties due to water absorption of PA6T is relatively small. (5) Excellent dimensional stability: the water absorption of PA6T is relatively low and the dimensional change due to water absorption is relatively small. The coefficient of thermal expansion of PA6T is fairly stable, remaining at a fairly low level in the high temperature range, and therefore dimensional stability to temperature changes is good. In addition, PA6T has little warpage due to the molding process. That is to say PA6T has excellent dimensional stability. (6) PA6T has good melt flow and is easily processed by injection molding. In addition, PA6T has excellent thin-wall formability, so that the forming die is suitable for processing and forming small parts. (7) Difficult burr during the shaping: PA6T also has a characteristic inherent in nylon and is less prone to raising during injection molding. (8) Halogen-free environment-friendly
Disclosure of Invention
In order to make up the limitation of application of common 3D printing consumables, the invention aims to provide a high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing, which has the excellent characteristics of excellent welding resistance, excellent high-temperature rigidity, excellent chemical resistance, low water absorption, excellent dimensional stability, excellent fluidity, difficult edge fluffing during molding, halogen-free environment friendliness and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the purpose of the invention is realized by the following technical scheme: A3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable is prepared from the following components in parts by weight:
40-70 parts of nylon 6T;
1-5 parts of a compatilizer;
1-40 parts of high-temperature resistant glass fiber;
5-15 parts of a halogen-free flame retardant;
0.1-1 part of antioxidant;
1-5 parts of a lubricant;
0.1-0.5 part of anti-ultraviolet agent;
5-15 parts of a toughening agent;
preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the density of the nylon 6T is 1.75g/cm3(ii) a The water absorption rate is 0.2 percent; molding shrinkage rate: 0.3 percent; notched impact strength of 75KJ/m3(ii) a The tensile strength is 180 MPa.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the compatilizer is at least one of a maleic anhydride graft, a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the heat-resistant temperature of the high-temperature-resistant glass fiber is higher than 350 ℃.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the flame retardant is at least one of a halogen-free flame retardant (such as aluminum diethylphosphinate, red phosphorus and the like), a nitrogen-based flame retardant and an inorganic flame retardant (such as magnesium hydroxide and the like).
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the antioxidant is at least one of antioxidant 1010, antioxidant 1098, antioxidant 425, antioxidant 264, antioxidant 168 and antioxidant TNPP.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the lubricant is one or a mixture of barium stearate, ammonium stearate, stearic acid, calcium stearate, and zinc stearate.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable, the anti-ultraviolet agent is at least one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, triazines, and hindered amines.
Preferably, in the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable material, the toughening agent is at least one of POE, grafted POE, EPDM, PBE, SEBS, SBS, SIS, SEPS, SOE, ABS high rubber powder, ASA high rubber powder, MBS, ACR, EMA, silicone rubber, ethylene-methyl acrylate-glycidyl methacrylate random copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride and acrylate bifunctional ethylene elastomer, EVA, PU, TPO, TPE, TPV, TPU, TPEE, TPR.
The invention uses the melt blending intercalation method to prepare the high temperature resistant nylon wire material for 3D printing, accords with the technical characteristics of 3D printing, enhances the mechanical property and the thermal deformation temperature of the material, achieves the aim of modification enhancement, and successfully solves the defects of poor dimensional stability and low thermal deformation temperature of the nylon material.
According to the invention, the high-strength nylon 6T resin is used as a base material, the nylon resin is physically modified by utilizing high-temperature-resistant glass fiber, an antioxidant, a lubricant and the like, the shrinkage of the nylon resin is improved and the thermal denaturation temperature is increased by adjusting the synergistic effect among the components in different proportions, and the high-temperature-resistant nylon wire material for 3D printing is obtained, and has the advantages of high strength, low shrinkage, low warping deformation degree, high molding precision, high temperature resistance and easiness in support removal.
The high-temperature-resistant nylon wire prepared by adopting the nylon 6T resin keeps the original excellent mechanical property and molding processability of nylon, has the characteristics of high temperature resistance, high roundness and the like, and can well meet the requirements of fused deposition molding on materials.
The other purpose of the invention is realized by the following technical scheme: a preparation method of a high-temperature-resistant nylon wire for 3D printing comprises the following steps:
(1) drying nylon 6T resin;
(2) adding the compatilizer, the glass fiber, the antioxidant, the lubricant, the anti-ultraviolet agent, the toughening agent and the halogen-free flame retardant into nylon 6T resin, uniformly mixing, melting and blending in a double-screw extruder, extruding and granulating to obtain granules;
(3) drying the granulated granules;
(4) and adding the dried granules into a single-screw extruder for melt extrusion, and carrying out wire drawing forming to obtain the high-temperature-resistant nylon wire.
According to the preparation method, the nylon resin, the antioxidant and the lubricant are mixed, and then the high-temperature-resistant nylon wire material which can be directly applied to 3D printing is prepared through the process technologies of double-screw extrusion, granulation, single-screw extruder wire drawing and the like, and the formed piece obtained through FDM printing and forming has excellent mechanical properties and higher use temperature.
The preparation method of the invention utilizes the single-screw extruder to extrude, draw and draw the device to adjust the diameter of the wire, overcomes the defects of unstable control of the diameter of the wire and larger loss of the wire in the traditional method, improves the utilization rate of raw materials and reduces the cost.
The preparation method has the advantages of simple steps, low deformation degree, low forming precision, high temperature resistance and easy removal of the support.
The high-temperature resistant nylon wire material disclosed by the invention keeps single, is convenient to operate and control, has stable quality, high production efficiency and low production cost, and can be industrially produced on a large scale.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T master batch: 50 parts of nylon 6T; 5 parts of high-temperature resistant glass fiber (the heat resistance is higher than 350 ℃); 5 parts of maleic anhydride graft; 10 parts of aluminum diethylphosphinate; 1680.1 parts of an antioxidant; 1 part of amine stearate; 3600.2 parts of UV (ultraviolet); 15 parts of POE grafted maleic anhydride. Adding into a high-speed mixer, and mixing uniformly at a stirring speed of 600r/min for 2 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 250 rpm;
(2) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 110 ℃ for drying treatment for 1h, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Example 2
(1) Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T master batch: 60 parts of nylon 6T; 20 parts of high-temperature resistant glass fiber (the heat resistance is higher than 350 ℃); 5 parts of titanate coupling agent; 5 parts of aluminum diethylphosphinate; 10980.1 parts of an antioxidant; 1 part of amine stearate; 3600.2 parts of UV (ultraviolet); 10 parts of POE grafted maleic anhydride; uniformly mixing by a high-speed mixer, wherein the stirring speed is 600r/min, and the mixing time is 10 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃; the rotating speed of the double-screw main machine is 500 rpm;
(2) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 100 ℃ for drying treatment for 1h, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Example 3
(1) Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumables: weighing 50 parts of dried nylon 6T; 15 parts of high-temperature resistant glass fiber (the heat resistance is higher than 350 ℃), 3 parts of maleic anhydride graft, 5 parts of macromolecular quaternary ammonium salt grafted nano silicon dioxide, 0.1 part of 5, 7-bis- (2, 2-dimethylethyl) -3- (3, 4-dimethylphenyl) -2-3 hydrogen-benzofuranone, 2640.4 parts of antioxidant and 0.5 part of zinc stearate; uniformly mixing by a high-speed mixer, wherein the stirring speed is 600r/min, and the mixing time is 5 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 300 rpm;
(2) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 110 ℃ for drying treatment for 2 hours, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Example 4
(1) Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T master batch: 50 parts of nylon 6T; 30 parts of high-temperature resistant glass fiber (resistant to heat higher than 350 ℃); 5 parts of a silane coupling agent; 6 parts of aluminum diethylphosphinate; 0.1 part of antioxidant TNPP; 1 part of calcium stearate; 3600.2 parts of UV (ultraviolet); 10 parts of ASA high-rubber powder; uniformly mixing by a high-speed mixer, wherein the stirring speed is 600r/min, and the mixing time is 8 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 350 rpm;
(3) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 110 ℃ for drying treatment for 2 hours, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Example 5
(1) Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T master batch: 40 parts of nylon 6T and 40 parts of high-temperature resistant glass fiber (the heat resistance is higher than 350 ℃); 5 parts of maleic anhydride graft; 5 parts of magnesium hydroxide; 1680.1 parts of an antioxidant; 1 part of amine stearate; 3600.2 parts of UV (ultraviolet); 5 parts of POE grafted maleic anhydride; uniformly mixing by a high-speed mixer, wherein the stirring speed is 600r/min, and the mixing time is 8 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 400 rpm;
(3) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 110 ℃ for drying treatment for 2 hours, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Comparative example 1
Drying nylon 6T resin at 110 ℃ for 1 h; preparing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T master batch: 50 parts of nylon 6T; 5 parts of maleic anhydride graft; 10 parts of aluminum diethylphosphinate; 1680.1 parts of an antioxidant; 1 part of amine stearate; 3600.2 parts of UV (ultraviolet); 15 parts of POE grafted maleic anhydride. Adding into a high-speed mixer, and mixing uniformly at a stirring speed of 600r/min for 2 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 250 rpm;
(2) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T granules are placed at 110 ℃ for drying treatment for 1h, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Comparative example 2
Drying nylon 6 resin at 110 ℃ for 1 h; preparing the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6 master batch: 650 parts of nylon; 5 parts of high-temperature resistant glass fiber (the heat resistance is higher than 350 ℃); 5 parts of maleic anhydride graft; 10 parts of aluminum diethylphosphinate; 1680.1 parts of an antioxidant; 1 part of amine stearate; 3600.2 parts of UV (ultraviolet); 15 parts of POE grafted maleic anhydride. Adding into a high-speed mixer, and mixing uniformly at a stirring speed of 600r/min for 2 min; adding the mixed raw materials into a double-screw extruder, and performing melt extrusion granulation, wherein the temperature of each extrusion section is 270-350 ℃, and the rotating speed of a double-screw host is 250 rpm;
(2) the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6 granules are placed at 110 ℃ for drying treatment for 1h, extruded by a 3D printing material single-screw extruder, processed at 350 ℃, and subjected to one-section constant-temperature cooling at 70 ℃, two-section constant-temperature cooling at 50 ℃, normal-temperature cooling, air drying, bracing and winding to prepare the high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
Table 1 results of performance testing of examples
The following conclusions are drawn from the test data of table 1: in comparative example 1, the high temperature resistant glass fiber is not used for modification, and compared with example 1, all parameters of the mechanical property are reduced, and the thermal deformation temperature is also greatly reduced. In comparative example 2, in which nylon 6 was used as the substrate, the mechanical properties were decreased in each parameter, and the heat distortion temperature was decreased to a small extent, as compared with example 1. The material has high mechanical property and high thermal deformation temperature, so that the prepared 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable material has excellent mechanical property and high use temperature.
The present invention is not limited to the embodiments described herein, and those skilled in the art, having the benefit of this disclosure, will appreciate numerous modifications and variations there from without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The utility model provides a 3D prints high temperature resistant environmental protection and does not have steamed fine reinforcing nylon 6T consumptive material of ripples which characterized in that: the composition is prepared from the following components in parts by weight:
40-70 parts of nylon 6T;
1-5 parts of a compatilizer;
1-40 parts of high-temperature resistant glass fiber;
5-15 parts of a halogen-free flame retardant;
0.1-1 part of antioxidant;
1-5 parts of a lubricant;
0.1-0.5 part of anti-ultraviolet agent;
5-15 parts of a toughening agent.
2. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable according to claim 1, which is characterized in that: the density of the nylon 6T is 1.75g/cm3The water absorption rate is 0.2 percent, and the molding shrinkage rate is as follows: 0.3% and a notched impact strength of 75KJ/m3The tensile strength is 180 MPa.
3. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable according to claim 1, which is characterized in that: the compatilizer is at least one of maleic anhydride graft, silane coupling agent, titanate coupling agent and aluminate coupling agent.
4. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable according to claim 1, which is characterized in that: the temperature resistance of the high-temperature resistant glass fiber is higher than 350 ℃.
5. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable material according to claim 1, wherein the flame retardant is at least one of a halogen-free flame retardant, a nitrogen-based flame retardant and an inorganic flame retardant; the antioxidant is at least one of antioxidant 1010, antioxidant 1098, antioxidant 425, antioxidant 264, antioxidant 168 and antioxidant TNPP.
6. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable according to claim 1, which is characterized in that: the lubricant is one or a mixture of more of barium stearate, amine stearate, stearic acid, calcium stearate and zinc stearate.
7. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable according to claim 1, which is characterized in that: the uvioresistant agent is at least one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile, triazines and hindered amines.
8. The 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable of claim, which is characterized in that: the toughening agent is at least one of POE, grafted POE, EPDM, PBE, SEBS, SBS, SIS, SEPS, SOE, ABS high rubber powder, ASA high rubber powder, MBS, ACR, EMA, silicon rubber, ethylene-methyl acrylate-glycidyl methacrylate random copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, maleic anhydride and acrylate bifunctional ethylene elastomer, EVA, PU, TPO, TPE, TPV, TPU, TPEE and TPR.
9. The preparation method of the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable material according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
(1) drying nylon 6T resin;
(2) adding the compatilizer, the glass fiber, the antioxidant, the lubricant, the anti-ultraviolet agent, the toughening agent and the flame retardant into nylon 6T resin, uniformly mixing, melting and blending in a double-screw extruder, extruding and granulating to obtain granules;
(3) drying the granulated granules;
(4) and adding the dried granules into a single-screw extruder for melt extrusion, and performing wire drawing forming to obtain the 3D printing high-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable.
10. The method of claim 9, wherein: in the step (1) and the step (3), the drying temperature is 80-110 ℃, and the drying time is 1-5 h; in the step (2), the processing temperature of the double-screw extruder is 270-360 ℃; in the step (4), the single-screw extrusion temperature parameters are as follows: the temperature of each section is 270-360 ℃; the diameter of the high-temperature nylon wire is controlled to be 1.75 +/-0.05 mm.
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