CN110724378B - 3D laser printing material and preparation method thereof - Google Patents
3D laser printing material and preparation method thereof Download PDFInfo
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- CN110724378B CN110724378B CN201910873281.4A CN201910873281A CN110724378B CN 110724378 B CN110724378 B CN 110724378B CN 201910873281 A CN201910873281 A CN 201910873281A CN 110724378 B CN110724378 B CN 110724378B
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000007648 laser printing Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 23
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 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 6
- 239000008187 granular material Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 238000004383 yellowing Methods 0.000 abstract description 7
- 239000004677 Nylon Substances 0.000 abstract description 6
- 229920001778 nylon Polymers 0.000 abstract description 6
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 11
- 229920000299 Nylon 12 Polymers 0.000 description 11
- 238000010146 3D printing Methods 0.000 description 9
- 238000012423 maintenance Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000000149 argon plasma sintering Methods 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
Abstract
The application relates to a 3D laser printing material and a preparation method thereof, wherein the material is prepared by synthesizing nylon resin from pentanediamine, sebacic acid or dodecanedioic acid with a branched chain, modifying by an extrusion modification process, and preparing the 3D laser printing material by a chemical powder preparation process. The 3D laser printing material has the advantages of moderate melting point, high toughness, low thermal shrinkage rate, yellowing resistance, easiness in construction and the like.
Description
Technical Field
The invention belongs to the technical field of materials for 3D printing, and particularly relates to a 3D laser printing material and a preparation method thereof.
Background
The existing 3D laser printing material mainly uses nylon 12 as a main material, but has a high melting point and a large thermal shrinkage rate, and after multiple laser sintering, the defects of poor powder performance and toughness, easy yellowing and the like are obvious, so that the utilization rate of 3D laser printing raw materials is obviously influenced, and great waste is caused, thereby the cost of 3D laser printing is also improved, and the popularization and application of 3D laser printing are not facilitated.
Chinese patent CN201611013029.9 discloses a graphene 3D printing material, which belongs to the technical field of material preparation for 3D printing, and the graphene 3D printing material comprises the following raw materials in parts by weight: 5-8 parts of graphene, 26-32 parts of garbage plastic, 32-42 parts of polylactic acid, 16-25 parts of sodium tripolyphosphate, 20-26 parts of butyl acetate, 12-20 parts of a specific synthetic agent and 5-10 parts of a starch synthetic agent. The graphene 3D printing material prepared by the invention has the characteristics of high tensile strength, bending strength, notch impact strength, high thermal deformation temperature, high melt index and the like, but the defects of high melting point, no yellowing resistance, high thermal shrinkage and the like are considered, so that the prior art is slightly insufficient.
Chinese patent CN 201611012959.2 discloses a graphene printing material, which belongs to the technical field of material preparation for 3D printing, and comprises the following raw materials in parts by weight: 5.5-7.6 parts of graphene, 24.6-30.4 parts of waste plastic, 34.2-38.2 parts of polylactic acid, 11.6-22.7 parts of potassium tripolyphosphate, 18.3-24.5 parts of adipate, 9.2-17.3 parts of specific synthetic agent and 5.2-9.5 parts of starch synthetic agent. The graphene printing material prepared by the invention has the characteristics of high tensile strength, bending strength, notch impact strength, high thermal deformation temperature, high melt index and the like, but the defects of high melting point, no yellowing resistance, no recycling and the like are considered, so that the prior art is slightly deficient.
Chinese patent CN 201710160803.7 discloses a 3D printing material capable of being polished to be in a metal appearance, which comprises the following components in percentage by mass: 14-40% of high-fluidity high polymer plastic; 5-15% of a toughening agent; 50-80% of metal powder subjected to surface treatment; 0.3-1% of antioxidant; 0.5-2% of a lubricant; meanwhile, a preparation method and an application method of the 3D printing material capable of being polished to be in a metal appearance are also disclosed, but the prior art is slightly insufficient in consideration of the defects of poor toughness, easy yellowing and the like.
Chinese patent CN 201510852655.6 discloses a carbon fiber reinforced polylactic acid 3D printing material and a preparation method thereof, wherein the material is composed of the following raw materials in parts by weight: 60-80 parts of polylactic acid, 5-15 parts of a toughening agent, 2-10 parts of a compatilizer, 5-25 parts of modified carbon fiber, 0.1-2 parts of an antioxidant, 0.5-2 parts of an anti-hydrolysis agent, 0.05-1 part of a crystallization nucleating agent, 0.5-3 parts of a fluidity regulator and 0.2-2 parts of a melt fusion reinforcing agent.
Disclosure of Invention
The technical problem to be solved is as follows: the application mainly provides a 3D laser printing material and a preparation method thereof, and the technical problems of poor powder performance toughness, easy yellowing and the like in the prior art are solved.
The technical scheme is as follows:
A3D laser printing material comprises the following raw materials in parts by weight: 1 part of branched pentanediamine, 1.0-3.8 parts of diacid and 0.1-0.3 part of water.
As a preferred technical scheme of the invention: the diacid is one or two mixed acids of sebacic acid and dodecanedioic acid.
As a preferred technical scheme of the invention: when the diacid is sebacic acid, the 3D laser printing material comprises 1 part of branched pentanediamine, 1.7-1.8 parts of sebacic acid and 0.1-0.3 part of water according to the mass part ratio; when the diacid is dodecanedioic acid, the 3D laser printing material comprises, by mass, 1 part of branched pentanediamine, 1.0-2.0 parts of dodecanedioic acid, and 0.1-0.3 part of water.
As a preferred technical scheme of the invention: the pentanediamine with the branched chain is 2-methyl pentanediamine.
As a preferred technical scheme of the invention: the raw materials of the 3D laser printing material also contain additives, and the additives comprise a compound antioxidant and/or a molecular weight regulator.
As a preferred technical scheme of the invention: the compound antioxidant is prepared by compounding phosphorous acid, an antioxidant 1098 and an antioxidant 168, and the weight ratio is that the phosphorous acid: antioxidant 1098: antioxidant 168= (0.2-0.5): (2-3) and (1-1.5), wherein the addition amount of the antioxidant is 1-3% of the total weight of the feed.
As a preferred technical scheme of the invention: the water is distilled water or softened water.
As a preferred technical scheme of the invention: the raw materials of the 3D laser printing material also comprise a toughening modifier, wherein the toughening modifier is preferably a polyolefin toughening agent subjected to maleic anhydride grafting modification.
As a preferred technical scheme of the invention: the raw materials of the 3D laser printing material also comprise an antioxidant B225.
The invention also discloses a preparation method of the 3D laser printing material, which comprises the following steps:
the first step is as follows: weighing pentanediamine with a branched chain, diacid and water according to the weight part ratio, and uniformly mixing the weighed raw materials;
the second step is that: adding a compound antioxidant accounting for 1-3% of the total weight of the raw materials into the raw materials, and uniformly mixing to obtain a mixture;
the third step: putting the mixture into a high-pressure reaction kettle, sealing, heating, simultaneously opening an emptying valve and a stirring device, closing the emptying valve when the temperature of the material rises to 100 ℃, stopping stirring, continuing heating, starting heat preservation and pressure maintaining when the temperature of the material is higher than 200 ℃ and the pressure reaches 1.2MPa, and preserving heat and pressure for 2 hours;
the fourth step: after heat preservation and pressure maintaining, uniformly releasing the pressure to the normal pressure within 2 hours, and preserving the heat for 2 hours at the normal pressure;
the fifth step: introducing nitrogen to 0.2MPa, opening a discharge valve, cutting the materials into granules by a tape injection head, a cold water tank and a granulator, and then drying in vacuum to obtain resin particles;
and a sixth step: the synthetic resin particles, the toughening modifier and the antioxidant B225 are mixed according to the weight ratio of 1 (0.06-0.15): (0.005-0.02) carrying out extrusion modification, wherein the toughening modifier is a polyolefin toughening agent subjected to maleic anhydride grafting modification;
the seventh step: carrying out chemical solvent powder preparation on the extruded and modified resin, taking absolute ethyl alcohol as a main solvent and water as an auxiliary solvent, and weighing the extruded and modified resin according to the weight ratio: anhydrous ethanol: and (0.02-0.05), putting the weighed resin subjected to extrusion modification, absolute ethyl alcohol and water into a reaction kettle, sealing, heating, starting stirring, keeping the temperature for 1 hour after the temperature of the material rises to 120 ℃, introducing cooling water, cooling the material to 50 ℃, putting the material into a crystallization tank, standing for crystallization, performing centrifugal separation after the solid-liquid separation of the material is complete, distilling the absolute ethyl alcohol for recycling, performing vacuum drying treatment on the powder, and screening to obtain a finished product of the 3D laser printing material.
Has the advantages that: compared with the prior art, the 3D laser printing material and the preparation method thereof adopt the technical scheme, and have the following technical effects:
1. the 3D laser printing material has the advantages of moderate melting point, high toughness, low thermal shrinkage rate, yellowing resistance, easiness in construction and the like.
2. The 3D laser printing material has Shore hardness: 68-70, can be recycled, and is beneficial to the application and popularization of 3D laser printing.
3. The melting point of the product is 160-164 ℃, and the melt index (230 ℃, 2.16 kg): 20 g/10 min, high toughness, and continuous folding of the sample strips.
4. The molding material can be repeatedly used for 12 times, the molded part still keeps good mechanical property and whiteness, the thermal shrinkage rate is low, and the elongation at break is as follows: 500 percent.
5. The preheating temperature range of 145-155 ℃ is obviously widened, the control of the laser sintering process is facilitated, and experiments show that the warping phenomenon that the preheating temperature of the nylon 12 powder is too low and the powder agglomeration phenomenon of the nylon 12 powder when the preheating temperature is too high do not occur in the range.
6. The laser sintering power is controlled to be 6-8W, so that a satisfactory effect can be obtained, and the mechanical property of the material cannot be reduced.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a 3D laser printing material comprises the following steps:
the first step is as follows: 109 kg of 2-methyl pentanediamine, 191 kg of sebacic acid, 30 kg of distilled water and 4.7 kg of compound antioxidant are weighed according to the mass part ratio, and the compound antioxidant is prepared by compounding 200 g of phosphorous acid, 3 kg of antioxidant 1098 and 1.5 kg of antioxidant 168;
the second step: putting the materials into a high-pressure reaction kettle according to the proportion, sealing, heating, simultaneously opening an emptying valve and a stirring device, closing the emptying valve when the temperature of the materials rises to 100 ℃, stopping stirring, continuing heating, starting heat preservation and pressure maintenance when the temperature of the materials rises to more than 200 ℃, starting heat preservation and pressure maintenance when the pressure reaches 1.2MPa, wherein the heat preservation and pressure maintenance time is 2 hours, uniformly releasing the pressure to the normal pressure within 2 hours after heat preservation and pressure maintenance, preserving heat for 2 hours at the normal pressure, then filling nitrogen to 0.2MPa, opening a discharge valve, cutting the materials into granules by a tape injection head, a cold water tank and a granulator, and carrying out vacuum drying to obtain the resin granules. The product indexes are as follows:
melting point: 164 deg.C
Melt index (230 ℃, 2.16 kg): 20 g/10 min
Hardness (shore): 70
Elongation at break: 500 percent
Toughness: the sample strips are continuously folded;
the third step: mixing the synthesized resin particles, the toughening modifier and the antioxidant B225 in a weight ratio of 1: 0.06: 0.008, carrying out extrusion modification by using a double-screw extruder, wherein the toughening modifier is a polyolefin toughening agent subjected to maleic anhydride grafting modification;
the fourth step: putting 300 kg of modified resin, 900 kg of absolute ethyl alcohol and 9 kg of distilled water into a reaction kettle, sealing, heating, starting stirring, keeping the temperature for 1 hour when the temperature of the material rises to 120 ℃, introducing cooling water, cooling the material to 50 ℃, putting the material into a crystallization tank, standing for crystallization, performing centrifugal separation after the solid-liquid separation of the material is thorough, recovering and reusing the absolute ethyl alcohol after distillation, performing vacuum drying treatment on the powder, and screening to obtain the 3D laser printing material.
Example 2
A preparation method of a 3D laser printing material comprises the following steps:
the first step is as follows: weighing 101 kg of 2-methyl pentanediamine, 199 kg of dodecanedioic acid, 15 kg of water and 3.5 kg of compound antioxidant according to the mass part ratio, wherein the compound antioxidant is prepared by compounding 500 g of phosphorous acid, 2 kg of antioxidant 1098 and 1 kg of antioxidant 168;
the second step is that: putting the materials into a high-pressure reaction kettle according to the proportion, sealing, heating, simultaneously opening an emptying valve and a stirring device, closing the emptying valve when the temperature of the materials rises to 100 ℃, stopping stirring, continuing heating, starting heat preservation and pressure maintenance when the temperature of the materials rises to more than 200 ℃, starting heat preservation and pressure maintenance when the pressure reaches 1.2MPa, wherein the heat preservation and pressure maintenance time is 2 hours, uniformly releasing the pressure to the normal pressure within 2 hours after heat preservation and pressure maintenance, preserving heat for 2 hours at the normal pressure, then filling nitrogen to 0.2MPa, opening a discharge valve, cutting the materials into granules by a tape injection head, a cold water tank and a granulator, and carrying out vacuum drying to obtain the resin granules. The product indexes are as follows:
melting point: 160 deg.C
Melt index (230 ℃, 2.16 kg): 20 g/10 min
Hardness (shore hardness): 68
Elongation at break: 500 percent
Toughness: the sample strips are continuously folded;
the third step: carrying out extrusion modification on the synthesized resin particles, the toughening modifier and the antioxidant B225 by using a double-screw extruder according to the weight ratio of 1: 0.15:0.01, wherein the toughening modifier is a polyolefin toughening agent grafted and modified by maleic anhydride;
the fourth step: putting 300 kg of modified resin, 900 kg of absolute ethyl alcohol and 9 kg of distilled water into a reaction kettle, sealing, heating, starting stirring, keeping the temperature for 1 hour when the temperature of the material rises to 120 ℃, introducing cooling water, cooling the material to 50 ℃, putting the material into a crystallization tank, standing for crystallization, carrying out centrifugal separation after complete solid-liquid separation of the material, recovering and reusing the absolute ethyl alcohol after distillation, carrying out vacuum drying treatment on the powder, and screening to obtain the 3D laser printing material.
The difference of this application and the nylon 12 that current 3D laser printing material adopted lies in:
first, preheat temperature differentiation
The preheating temperature of the nylon 12 is 168-169 DEG C
The preheating temperature of the invention is 145-155 DEG C
The preheating temperature range is obviously widened, the control of the laser sintering process is facilitated, and experiments show that in the range, the warping phenomenon caused by too low preheating temperature of the nylon 12 powder does not occur, and the powder agglomeration phenomenon caused by the nylon 12 powder when the preheating temperature is too high does not occur.
Selection of laser power
When the carbon dioxide power is lower, the tensile strength and the impact strength of the nylon powder material formed part are increased along with the increase of the carbon dioxide laser power, and when the laser power is more than 10W, the surface temperature of the nylon 12 powder coating is too high due to too high energy, so that oxidative degradation is caused, and the mechanical property of the material is reduced to be sharply reduced. Currently, the laser sintering power of nylon 12 is generally controlled to be 8-10W.
The melting point of the product obtained by the invention is lower than that of nylon 12 by about 14-18 ℃, so that the satisfactory effect can be obtained by controlling the laser sintering power to be 6-8W.
Third, the number of times of using the powder
Because the nylon powder is subjected to laser sintering, the nylon powder can be gradually oxidized, yellowed and embrittled at high temperature, and the recycling frequency of the nylon powder can be influenced, at present, the conventional nylon 12 powder can not be used after being used for 6 times and only can be discarded.
The product obtained by the invention has low melting point and the processing temperature far lower than the thermal decomposition temperature of nylon, and is repeatedly proved by a plurality of experiments, and the formed part still keeps good mechanical property and whiteness after 12 times of repeated use.
The above examples only illustrate some of the raw material ratios in this patent, and they are not illustrated herein. Modifications and substitutions to methods, steps or conditions of the present application are intended to be within the scope of the present application without departing from the spirit and substance of the present application.
Claims (3)
1. The 3D laser printing material is characterized in that: the 3D laser printing material comprises the following raw materials in parts by weight: 1 part of 2-methyl pentanediamine, 1.0-3.8 parts of diacid and 0.1-0.3 part of water; the diacid is one or two mixed acids of sebacic acid and dodecanedioic acid; the raw materials of the 3D laser printing material also contain additives, and the additives comprise a compound antioxidant and/or a molecular weight regulator; the compound antioxidant is prepared by compounding phosphorous acid, an antioxidant 1098 and an antioxidant 168, and the weight ratio is that the phosphorous acid: antioxidant 1098: antioxidant 168= (0.2-0.5): (2-3) and (1-1.5), wherein the addition amount of the antioxidant is 1-3% of the total weight of the feed; the raw materials of the 3D laser printing material also comprise a toughening modifier, wherein the toughening modifier is a polyolefin toughening agent grafted and modified by maleic anhydride; the raw materials of the 3D laser printing material also comprise an antioxidant B225;
the preparation method of the 3D laser printing material comprises the following steps:
the first step is as follows: weighing 2-methylpentamethylenediamine, diacid and water according to the weight part ratio, and uniformly mixing the weighed raw materials;
the second step: adding a compound antioxidant accounting for 1-3% of the total weight of the raw materials into the raw materials, and uniformly mixing to obtain a mixture;
the third step: putting the mixture into a high-pressure reaction kettle, sealing, heating, simultaneously opening an emptying valve and a stirring device, closing the emptying valve when the temperature of the material rises to 100 ℃, stopping stirring, continuing heating, starting heat preservation and pressure maintaining when the temperature of the material is higher than 200 ℃ and the pressure reaches 1.2MPa, and preserving heat and pressure for 2 hours;
the fourth step: after heat preservation and pressure maintaining, uniformly releasing the pressure to the normal pressure within 2 hours, and preserving the heat for 2 hours at the normal pressure;
the fifth step: introducing nitrogen to 0.2MPa, opening a discharge valve, cutting the materials into granules by a tape injection head, a cold water tank and a granulator, and then drying in vacuum to obtain resin particles;
and a sixth step: the synthetic resin particles, the toughening modifier and the antioxidant B225 are mixed according to the weight ratio of 1 (0.06-0.15): (0.005-0.02) carrying out extrusion modification, wherein the toughening modifier is a polyolefin toughening agent subjected to maleic anhydride grafting modification;
the seventh step: carrying out chemical solvent powder preparation on the extruded and modified resin, taking absolute ethyl alcohol as a main solvent and water as an auxiliary solvent, and weighing the extruded and modified resin according to the weight ratio: anhydrous ethanol: and (0.02-0.05), putting the weighed resin subjected to extrusion modification, absolute ethyl alcohol and water into a reaction kettle, sealing, heating, starting stirring, keeping the temperature for 1 hour after the temperature of the material rises to 120 ℃, introducing cooling water, cooling the material to 50 ℃, putting the material into a crystallization tank, standing for crystallization, performing centrifugal separation after the solid-liquid separation of the material is complete, distilling the absolute ethyl alcohol for recycling, performing vacuum drying treatment on the powder, and screening to obtain a finished product of the 3D laser printing material.
2. The 3D laser printed material according to claim 1, wherein: when the diacid is sebacic acid, the 3D laser printing material comprises 1 part of 2-methyl pentanediamine, 1.7-1.8 parts of sebacic acid and 0.1-0.3 part of water according to the mass part ratio; when the diacid is dodecanedioic acid, the 3D laser printing material comprises, by mass, 1 part of 2-methylpentanediamine, 1.0-2.0 parts of dodecanedioic acid, and 0.1-0.3 part of water.
3. The 3D laser printed material according to claim 1, wherein: the water is distilled water or softened water.
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| CN113416411B (en) * | 2021-07-21 | 2022-08-12 | 贵州森远增材制造科技有限公司 | Selective laser printing method for recycling and reusing four-stage nylon 12 residual powder |
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| CN107304292A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | nylon resin powder for selective laser sintering and preparation method thereof |
| CN110229328A (en) * | 2019-06-06 | 2019-09-13 | 南京工程学院 | A kind of preparation method and application of nylon powder |
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| CN107304292A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | nylon resin powder for selective laser sintering and preparation method thereof |
| CN110229328A (en) * | 2019-06-06 | 2019-09-13 | 南京工程学院 | A kind of preparation method and application of nylon powder |
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Application publication date: 20200124 Assignee: Yiyuan Technology (Nanjing) Co.,Ltd. Assignor: NANJING INSTITUTE OF TECHNOLOGY Contract record no.: X2023980035286 Denomination of invention: A 3D laser printing material and its preparation method Granted publication date: 20220913 License type: Common License Record date: 20230508 Application publication date: 20200124 Assignee: Jiangsu Yongbei Engineering Technology Co.,Ltd. Assignor: NANJING INSTITUTE OF TECHNOLOGY Contract record no.: X2023980035191 Denomination of invention: A 3D laser printing material and its preparation method Granted publication date: 20220913 License type: Common License Record date: 20230505 |
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