CN104479349B - A kind of flame-proof composite material for 3D printing and preparation method thereof - Google Patents
A kind of flame-proof composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN104479349B CN104479349B CN201410796193.6A CN201410796193A CN104479349B CN 104479349 B CN104479349 B CN 104479349B CN 201410796193 A CN201410796193 A CN 201410796193A CN 104479349 B CN104479349 B CN 104479349B
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- -1 pentaerythritol ester Chemical class 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005491 wire drawing Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 235000019260 propionic acid Nutrition 0.000 claims description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 5
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 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 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 abstract description 28
- 229920001778 nylon Polymers 0.000 abstract description 28
- 239000000314 lubricant Substances 0.000 abstract description 13
- 239000003963 antioxidant agent Substances 0.000 abstract description 11
- 230000003078 antioxidant effect Effects 0.000 abstract description 11
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 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 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 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 group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 3
- 229920006659 PA12 Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 2
- 229920006152 PA1010 Polymers 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 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 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-(1,1-dimethylethyl)-phenol Natural products CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical group CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001960 triggered effect Effects 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of flame-proof composite material for 3D printing, include the raw material of following parts by weight：The nylon resin of 60~95 parts by weight；The ABS resin of 5~40 parts by weight；The lubricant of 0.3~2 parts by weight；The compatilizer of 5~20 parts by weight；The antioxidant of 0.2~1 parts by weight；The unformed red phosphorus of 5~30 parts by weight.Provided by the present invention for being free of halogen in the flame-proof composite material of 3D printing, environment will not be polluted during material combustion and use, by the interaction of unformed red phosphorus, ABS resin and other raw materials, improve the fire resistance and toughness of material.Further, since the addition of lubricant, reduces the coefficient of friction of composite, improves the free mobility of composite, avoid the material caused by hot-spot from decomposing, improve the presentation quality and surface smoothness of product.Contribute to during 3D printing shower nozzle wire vent is smooth, prints product precision height, surface quality good.
Description
Technical field
The invention belongs to 3D printing technique field, and in particular to a kind of flame-proof composite material and its preparation for 3D printing
Method.
Background technology
3D printing is the popular appellation of increases material manufacturing technology, is superimposed by continuous physical layer, successively increases material
Produce the technology of 3D solid.Different from traditional removal materials processing technology, 3D printing technique is without proembryo and mould, with regard to energy
Directly according to computer graphics data, the method by increasing material produces the object of any shape, can effectively simplify product
Fabrication schedule, shorten lead time of product, improving efficiency simultaneously reduces cost.3D printing technique has been widely used former with product
The field such as type, Making mold, artistic creation, jewelry-making, bioengineering and medicine, building, clothes.Fused glass pellet
(FDM) it is a kind of 3D printing method common in the market, the innovation and development of its machine is very fast, but its consumptive material that can use
Develop limited.
Being commonly used in the consumptive material of 3D printing in the market has PLA (PLA), acrylonitrile-butadiene-styrene (ABS) common
Polymers (ABS) and polyvinyl alcohol (PVA) etc..But PLA mechanical property is poor, and non-refractory；ABS print procedures have different
Taste, mechanical property is general, also non-refractory；PVA is commonly used for a kind of backing material, but non-refractory.Therefore, above-mentioned consumptive material is deposited
The shortcomings that limit their application.
Nylon (PA) is earliest, the most widely used thermoplastic engineering plastic of development, has high-strength, high temperature resistant, wear-resisting, resistance to
The excellent performance such as impact, corrosion-resistant, endurance, oil resistant, self-lubricating, is widely used in automobile component, electronic apparatus, oil
The fields such as work, Aero-Space, it is the high polymer material that yield is maximum, purposes is most wide, kind is most in five large-engineering plastics.Nylon
As maximum most important kind in engineering plastics, there is very strong vitality, essentially consist in it is modified realize high performance,
Next to that itself requirement high performance to product of the industry such as automobile, electrical equipment, communication, electronics, machinery is more and more stronger, correlation production
The rapid development of industry, promotes the process of engineering plastics high performance, and future developing trend is various modification of nylon.
Fire-retardant nylon has been widely used in the fields such as electronic apparatus, traffic communication at present, and typical application has industry disconnected
Road device, plug, socket and other electrical connectors.Nylon with fire resistance is also more and more extensive to be applied to 3D printing skill
Art field.Its fire resistance of non-modified nylon is poor, and its vertical combustion can only achieve UL94V-2 levels, and oxygen index (OI) is 24 left
The right side, and drippage is produced in combustion, belong to combustible material, easily trigger fire in use.Especially in electricity
Sub- product scope, the fire triggered by nylon is countless, causes damage larger, but some important nylon resins are such as
PA6, PA66, PA11, PA12 etc., although with certain self-extinguishment, in most cases, in order to meet electrical equipment and traffic
The requirement of the fire resistances such as Communication Equipment, it is still necessary to it is flame-retardant modified to nylon progress to add fire retardant.However, general fire-retardant Buddhist nun
The fire retardant added in dragon is mostly halogen-system fire retardant, although this fire retardant can play good fire retardation,
A large amount of acid smog can be produced when being material combustion, so as to cause secondary hazards.Meanwhile the 3D printing temperature of nylon material compared with
Height, halogen system fire-retardant nylon can cause part halogen flame to discharge harmful substance during 3D printing, cause environment dirty
Contaminate and threaten health.Also, current general fire-retardant nylon toughness is low, is not suitable for as 3D printing consumptive material, consumptive material
Easily cause brittle fracture in print procedure, interrupt 3D printing forming process, the more defects of product for the 3D printing completed reluctantly, easily
Cracking, performance is low, and dimensional stability is low etc., do not meet actual use demand.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of flame-proof composite material for 3D printing and
Its preparation method, flame-proof composite material provided by the present invention will not cause environmental pollution, and have good toughness and resistance
Fire performance.
The invention provides a kind of flame-proof composite material for 3D printing, include the raw material of following parts by weight：
The nylon resin of 60~95 parts by weight；
The ABS resin of 5~40 parts by weight；
The lubricant of 0.3~2 parts by weight；
The compatilizer of 5~20 parts by weight；
The antioxidant of 0.2~1 parts by weight；
The unformed red phosphorus of 5~30 parts by weight.
Preferably, the nylon resin is one or more in PA6, PA66, PA11, PA12 and PA1010.
Preferably, the compatilizer is styrene-maleic anhydride copolymer, ABS grafted maleic anhydrides, maleic anhydride grafting
Ethylene-butyl acrylate copolymer or Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
Preferably, the antioxidant is 3,5- di-t-butyl -4- hydroxy benzenes propionyl-hexamethylene diamine, (2,4- bis- uncles of phosphorous acid three
Butyl benzene phenolic ester), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, N, N'- it is double-[3- (3,5- bis-
Tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, copper halide, KI, 1,3,5- trimethyls -2,4, (3,5- bis- uncles of 6- tri-
Butyl -4- hydroxybenzyls) one or more in benzene and 2 '-bis- (4- methyl-6-terts butyl-phenol) methane.
Preferably, the lubricant be super high molecular weight polysiloxanes, it is stearic acid, palmitic acid, ethylene bis stearamide, hard
One or more in resin acid pentaerythritol ester, Tissuemat E and zinc stearate.
Present invention also offers a kind of preparation method of the flame-proof composite material for 3D printing, it is characterised in that including
Following steps：
Nylon resin, ABS resin, fire retardant, compatilizer, antioxidant and mix lubricant are stirred to obtain mixture；Will
The mixture passes sequentially through melting extrusion and wire-drawing shape obtains the flame-proof composite material for 3D printing.
Preferably, before the mixing, in addition to nylon resin and ABS resin be dried.
Preferably, the rotating speed of the mixing is 700-1500r/min, and the mixing time is 1-5min.
Preferably, 6 sections of temperature of the melting extrusion be respectively 160~240 DEG C, 180~250 DEG C, 190~270 DEG C,
200~275 DEG C, 220~280 DEG C, 230~280 DEG C.
Preferably, the rotating speed of the melting extrusion is 80~180r/min.
Compared with prior art, the invention provides a kind of flame-proof composite material for 3D printing, including following weight
The raw material of part：The nylon resin of 60~95 parts by weight；The ABS resin of 5~40 parts by weight；The lubricant of 0.3~2 parts by weight；5~
The compatilizer of 20 parts by weight；The antioxidant of 0.2~1 parts by weight；The unformed red phosphorus of 5~30 parts by weight.Use provided by the invention
Halogen is free of in the flame-proof composite material of 3D printing, environment will not be polluted during material combustion and use, also,
By the interaction of unformed red phosphorus, ABS resin and other raw materials, the fire resistance and toughness of material are improved.In addition,
Due to the addition of lubricant, the coefficient of friction of composite is reduced, improves the free mobility of composite, avoids due to office
Material caused by portion's overheat decomposes, and improves the presentation quality and surface smoothness of product.Shower nozzle wire vent when contributing to 3D printing
Smooth, printing product precision is high, surface quality is good.
As a result show, the flame retardant rating of the flame-proof composite material provided by the present invention for 3D printing is V-0, non-notch
Impact strength >=774J/m, tensile strength ＞ 38MPa, elastic modulus G T.GT.GT 881MPa.
Embodiment
The invention provides a kind of flame-proof composite material for 3D printing, it is characterised in that including following parts by weight
Raw material：
The nylon resin of 60~95 parts by weight；
The ABS resin of 5~40 parts by weight；
The lubricant of 0.3~2 parts by weight；
The compatilizer of 5~20 parts by weight；
The antioxidant of 0.2~1 parts by weight；
The unformed red phosphorus of 5~30 parts by weight.
Flame-proof composite material provided by the present invention for 3D printing includes nylon resin, and nylon is in engineering plastics
One kind, there is the characteristics such as high, the wear-resisting, self-lubricating of intensity, power of its mechanical property apparently higher than ABS and PLA for 3D printing
Learn performance.The nylon resin is one or more in PA6, PA66, PA11, PA12 and PA1010.In the composite
In, the content of nylon resin is 60~95 parts by weight, preferably 75~90 parts by weight, more preferably 80~85 parts by weight.
In the present invention, the flame-proof composite material also includes ABS resin, and the content of the ABS resin is 5~40 weight
Part, preferably 10~35 parts by weight, more preferably 15~30 parts by weight.ABS resin is added into the composite to be changed
The toughness of kind material.
The flame-proof composite material also includes lubricant, and the lubricant is super high molecular weight polysiloxanes, stearic acid, palm fibre
One or more in palmitic acid acid, ethylene bis stearamide, stearic acid pentaerythritol ester, Tissuemat E and zinc stearate, it is preferably
Super high molecular weight polysiloxanes.The flame-proof composite material includes the lubricant of 0.3~2 parts by weight, preferably 0.5~1.5 weight
Measure part, more preferably 0.7~1.0 parts by weight.
Also include compatilizer in flame-proof composite material provided by the present invention, the compatilizer is selected from styrene-maleic acid
Anhydride copolymer, ABS grafted maleic anhydrides, Maleic Anhydride Grafted Ethylene Butyl Acrylate Copolymer or Ethylene-butyl acrylate-
Glycidyl methacrylate copolymer；The preferably acrylonitrile-butadiene-styrene copolymer of maleic anhydride grafting.Institute
Stating flame-proof composite material includes the compatilizer of 5~20 parts by weight, preferably 10~15 parts by weight.In the present invention, compatilizer
It is dispersed in nylon based composites system, when material is impacted, its microstructure can produce substantial amounts of crazing, and
It is branched around, substantial amounts of impact energy is absorbed, so as to improve the impact strength of material.
Also include antioxidant in the flame-proof composite material, the antioxidant is selected from 3,5- di-t-butyl -4- hydroxy benzenes third
Acyl-hexamethylene diamine, phosphorous acid three (2,4-DTBP ester), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons
Doutrate, N, N'- is double-[3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hexamethylene diamine, copper halide, KI, 1,3,
5- trimethyls -2,4, (3, the 5- di-tert-butyl-4-hydroxyl benzyl) benzene of 6- tri- and 2 '-bis- (4- methyl-6-terts butyl-phenol) methane
In one or more, preferably four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three [2.4- bis-
Tert-butyl-phenyl] phosphite ester.The flame-proof composite material includes the antioxidant of 0.2~1 parts by weight, preferably 0.5~0.8
Parts by weight.
Also include unformed red phosphorus in the flame-proof composite material, at 400-450 DEG C, red phosphorus depolymerization forms white phosphorus, after
Person is oxidized to the oxyacid of the phosphorus of viscosity in the presence of aqueous vapor, and this kind of material can be both covered in by the table of fire proofing
Face, can accelerate dehydration carbonization on the surface of material again, the liquid film and layer of charcoal of formation then can by the oxygen of outside, volatile combustible and
Heat separates with internal high polymer matrix and contributes to flameout.The flame-proof composite material includes the nothing of 5~30 parts by weight
Sizing red phosphorus, more preferably preferably 10~25 parts by weight, 15~20 parts by weight.
Present invention also offers a kind of preparation method of the flame-proof composite material for 3D printing, comprise the following steps：
Nylon resin, ABS resin, fire retardant, compatilizer, antioxidant and mix lubricant are stirred to obtain mixture；Will
The mixture passes sequentially through melting extrusion and wire-drawing shape obtains the flame-proof composite material for 3D printing.
The present invention is first mixed each raw material, before combination, is preferably located nylon resin in advance with ABS resin
Reason, specific method are：
Nylon resin and ABS resin are placed in drying box and are dried, wherein, drying temperature is 90~110 DEG C, is dried
Time is 4~8h.
Nylon resin and ABS resin mixing after will be dry, obtain hybrid resin.Lubrication is added into hybrid resin again
Agent, compatilizer, antioxidant and unformed red phosphorus are stirred, and obtain mixture.Wherein, the rotating speed of the stirring is 700-
1500r/min, the rotating speed of the stirring are 1-5min, blending and stirring 3 times.
After mixing terminates, by the mixture melting extrusion.Squeezed in the present invention, it is preferred to be melted using screw extruder
Go out, 6 sections of temperature of the melt extruder are respectively 160~240 DEG C, 180~250 DEG C, 190~270 DEG C, 200~275
DEG C, 220~280 DEG C, 230~280 DEG C.The engine speed of melt extruder is 80~180r/min.
The mixture of melting extrusion is subjected to wire-drawing shape, obtains the flame-proof composite material for 3D printing, wherein, wire drawing
The string diameter of the composite of shaping has two kinds of specifications of 1.75mm and 3mm, and the precision of composite is ± 0.03mm, circularity for ±
0.03mm。
In the present invention, consumptive material can also be prepared into graininess or powdered.Specifically, the preparation of graininess consumptive material
Method is：Consumptive material after wire drawing is introduced into pelleter, is granulated, granular size is set by the silk material diameter of extrusion wire drawing and pelletizing
It is standby to determine, typically between 0.5mm-5mm.
The preparation method of pulverulent material is：Consumptive material progress chilling after graininess consumptive material or wire drawing is crushed or solvent is molten
Parse, the diameter of pulverulent material is in 10-100 microns.
Provided by the present invention for being free of halogen in the flame-proof composite material of 3D printing, during material combustion and use not
Environment can be polluted, also, by the interaction of unformed red phosphorus, ABS resin and other raw materials, improve material
Fire resistance and toughness.Further, since the addition of lubricant, reduces the coefficient of friction of composite, improves composite
Free mobility, avoid caused by hot-spot material from decomposing, improve the presentation quality and surface smoothness of product.
Contribute to during 3D printing shower nozzle wire vent is smooth, prints product precision height, surface quality good.
As a result show, the flame retardant rating of the flame-proof composite material provided by the present invention for 3D printing is V-0, non-notch
Impact strength ＞ 774J/m, tensile strength ＞ 38MPa, elastic modulus G T.GT.GT 881MPa.
For a further understanding of the present invention, with reference to embodiment to provided by the present invention for the fire-retardant compound of 3D printing
Material and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Nylon 6 resin 1000g, ABS resin 400g, unformed red phosphorus 128g, the propylene of maleic anhydride grafting are weighed respectively
Nitrile-BS 200g, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three
[2.4- di-tert-butyl-phenyls] phosphite ester 5.4g, super high molecular weight polysiloxanes 18g, are put into high-speed mixer and mix
5min.Then extruded with screw extruder, be molded via wire-drawing shape equipment.6 sections of temperature of melting extrusion are respectively 200 DEG C,
220 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, screw speed is 80 revs/min.Around coiled consumptive material by vacuum drying, sealing
Preserve.
The impact strength and fire resistance of the flame-proof composite material for 3D printing obtained by measure, the results are shown in Table 1,
Table 1 is the performance for the flame-proof composite material for 3D printing that embodiment 1~3 provides.
Embodiment 2
Nylon 6 resin 1000g, ABS resin 300g, unformed red phosphorus 145g, styrene-maleic anhydride copolymer are weighed respectively
Thing 150g, N, N'- pairs-[3- (3,5- di-tert-butyl-hydroxy phenyls) propiono] hexamethylene diamine and three [2.4- di-tert-butyls
Base] phosphite ester 4.4g, stearic acid 14.5g be put into high-speed mixer and mix 5min.Then extruded with screw extruder, via
Wire-drawing shape equipment is molded.6 sections of temperature of melting extrusion are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237 DEG C, 245 DEG C,
Screw speed is 80 revs/min.The silk material of extrusion molding carries out granulation processing via granulate equipment, and its particle size is adjustable, by original
The diameter of silk and the parameter of granulate equipment determine that general diameter is in 1-3mm, and length is between 0.5mm-5mm.
The impact strength and fire resistance of the flame-proof composite material for 3D printing obtained by measure, the results are shown in Table 1,
Table 1 is the performance for the flame-proof composite material for 3D printing that embodiment 1~3 provides.
Embodiment 3
It is common that nylon 66 resin 1000g, ABS resin 300g, unformed red phosphorus 120g, phenylethylene-maleic anhydride are weighed respectively
Polymers 200g, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three [2.4- di-tert-butyl-phenyls]
Phosphite ester 4.5g, stearic acid 15g are put into high-speed mixer and mix 5min.Then extruded with screw extruder, via wire drawing
Former is molded.6 sections of temperature of melting extrusion are respectively 240 DEG C, 250 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 270 DEG C, screw rod
Rotating speed is 100 revs/min.Around coiled consumptive material by vacuum drying, it is sealed.
The impact strength and fire resistance of the flame-proof composite material for 3D printing obtained by measure, the results are shown in Table 1,
Table 1 is the performance for the flame-proof composite material for 3D printing that embodiment 1~3 provides.
Embodiment 4
Nylon 6 resin 800g, the resin 200g of nylon 12, ABS resin 300g, unformed red phosphorus 120g, benzene second are weighed respectively
Alkene-copolymer-maleic anhydride 200g, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three [2.4-
Di-tert-butyl-phenyl] phosphite ester 4.5g, stearic acid 15g be put into high-speed mixer and mix 5min.Then screw extruder is used
Extrusion, it is molded via wire-drawing shape equipment.6 sections of temperature of melting extrusion are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237
DEG C, 240 DEG C, screw speed be 100 revs/min.Around coiled consumptive material by vacuum drying, it is sealed.
The performance for the flame-proof composite material for 3D printing that the embodiment 1~3 of table 1 provides
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (1)
1. a kind of flame-proof composite material for 3D printing, it is characterised in that include the raw material of following parts by weight：
Take nylon 66 resin 1000g, ABS resin 300g, unformed red phosphorus 120g, styrene-maleic anhydride copolymer 200g, four
[β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4- di-tert-butyl-phenyls] phosphite esters
4.5g, stearic acid 15g；
The preparation method of the flame-proof composite material for 3D printing is：
Above-mentioned raw materials are put into high-speed mixer and mix 5min, are then extruded with screw extruder, via wire-drawing shape equipment
Shaping, 6 sections of temperature of melting extrusion are respectively 240 DEG C, 250 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 270 DEG C, screw speed 100
Rev/min, around coiled consumptive material by vacuum drying, it is sealed.
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| CN106189048A (en) * | 2016-07-29 | 2016-12-07 | 苏州秉创科技有限公司 | A kind of bio-based 3D printing consumables |
| CN107686627A (en) * | 2016-08-04 | 2018-02-13 | 中国石油化工股份有限公司 | 3D printing composition and 3D printing material and its preparation method and application |
| CN106832906B (en) * | 2017-03-02 | 2019-08-23 | 上海术博新材料技术有限公司 | A kind of high flame retardant nylon composite materials for 3D printing |
| CN107151442A (en) * | 2017-05-26 | 2017-09-12 | 褚建英 | A kind of laser sintering rapid forming nylon composite materials and preparation method thereof |
| CN107674282A (en) * | 2017-10-18 | 2018-02-09 | 安徽天易金属新材料有限公司 | A kind of aluminium pigment for 3D printing high polymer material and preparation method thereof |
| CN110669180A (en) * | 2019-10-15 | 2020-01-10 | 常州增材制造研究院有限公司 | High-performance anti-deformation 3D printing material and preparation method thereof |
| CN111040443A (en) * | 2019-12-27 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Polyamide powder material for selective laser sintering and preparation method thereof |
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| JP2001011266A (en) * | 1999-04-30 | 2001-01-16 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| CN1188464C (en) * | 2002-04-26 | 2005-02-09 | 北京北方恒利科技发展有限公司 | Nylon powder used for high-speed laser sintered products |
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