CN104479349A - Flame-retardant composite material for 3D printing and preparation method thereof - Google Patents
Flame-retardant composite material for 3D printing and preparation method thereof Download PDFInfo
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- CN104479349A CN104479349A CN201410796193.6A CN201410796193A CN104479349A CN 104479349 A CN104479349 A CN 104479349A CN 201410796193 A CN201410796193 A CN 201410796193A CN 104479349 A CN104479349 A CN 104479349A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
The invention provides a flame-retardant composite material for 3D printing, which comprises the following raw materials in parts by weight: 60-95 parts of nylon resin, 5-40 parts of ABS (acrylonitrile-butadiene-styrene) resin, 0.3-2 parts of lubricant, 5-20 parts of compatilizer, 0.2-1 part of antioxidant and 5-30 parts of amorphous red phosphorus. The flame-retardant composite material for 3D printing is free of halogen, and can not pollute the environment in the material combustion and use process; and under the interactions among the amorphous red phosphorus, ABS resin and other raw materials, the flame retardancy and toughness of the material are enhanced. The added lubricant lowers the friction factor of the composite material, improves the free mobility of the composite material, avoids the material decomposition caused by local overheating and enhances the appearance quality and surface smoothness of the product. When the flame-retardant composite material for 3D printing is used for 3D printing, the wire sprayed by the sprayer is smooth, and the printed product has high precision and favorable surface quality.
Description
Technical field
The invention belongs to 3D printing technique field, be specifically related to a kind of flame-proof composite material for 3D printing and preparation method thereof.
Background technology
It is the popular appellation increasing material manufacturing technology that 3D prints, and is superposed by continuous print physical layer, successively increases the technology that 3D solid produced by material.Different from traditional removal materials processing technology, 3D printing technique is without the need to proembryo and mould, just can directly according to computer graphics data, the object of any shape is produced by the method increasing material, effectively can simplify the manufacturing course of product, shorten the lead time of product, raise the efficiency and reduce costs.3D printing technique is the field such as widespread use and product prototype, Making mold, artistic creation, jewelry-making, biotechnology and medicine, building, clothes.Fused glass pellet (FDM) is a kind of 3D printing type common in the market, and the innovation and development of its machine is very fast, but its consumptive material development that can use is limited.
The consumptive material for 3D printing common in the market has poly(lactic acid) (PLA), acrylonitrile-butadiene-styrene copolymer (ABS) and polyvinyl alcohol (PVA) etc.But the mechanical property of PLA is poor, and non-refractory; ABS print procedure has peculiar smell, and mechanical property is general, also non-refractory; PVA is commonly used for a kind of propping material, but non-refractory.Therefore, the shortcoming that above-mentioned consumptive material also exists limits their range of application.
Nylon (PA) be develop the earliest, most widely used thermoplastic engineering plastic, there is the performance that high-strength, high temperature resistant, wear-resisting, shock-resistant, corrosion-resistant, antifatigue, oil resistant, self-lubricating etc. are excellent, being widely used in the fields such as trolley part, electronic apparatus, petrochemical complex, aerospace, is the macromolecular material that in five large-engineering plastics, output is maximum, purposes is the widest, kind is maximum.Nylon is as most important kind maximum in engineering plastics, there is very strong vitality, mainly be that it modifiedly realizes high performance, next is that self of the industries such as automobile, electrical equipment, communication, electronics, machinery is more and more stronger to the high performance requirement of product, the develop rapidly of related industries, facilitate the process of engineering plastics high performance, future developing trend is various modification of nylon.
Current fire-retardant nylon has been widely used in the field such as electronic apparatus, traffic communication, and typical application has industrial circuit breaker, plug, socket and other electrical connectors.The nylon with flame retardant properties is also more and more widely used in 3D printing technique field.Its flame retardant properties of the nylon of non-modified is poor, and its vertical combustion can only reach UL94V-2 level, and oxygen index is about 24, and produces drippage in combustion, belongs to inflammable material, in use very easily initiation fire.Especially at electronics field, the fire caused because of nylon is countless, cause damage larger, but some important nylon resins are as PA6, PA66, PA11, PA12 etc., although have certain self-extinguishing, but in most of the cases, in order to meet the requirement of the flame retardant properties such as electrical equipment and traffic communication equipment, still needing to add fire retardant and carrying out flame-retardant modified to nylon.But the fire retardant added in general fire-retardant nylon is mostly halogen-system fire retardant, although this fire retardant can play good fire retardation, a large amount of acid smog can be produced during material combustion, thus cause secondary to endanger.Meanwhile, the 3D print temperature of nylon material is higher, and halogen system fire-retardant nylon, in 3D print procedure, can cause part halogen flame to discharge objectionable impurities, causes environmental pollution and threaten HUMAN HEALTH.Further, current general fire-retardant nylon toughness is low, and be not suitable for as 3D printing consumables, consumptive material easily causes brittle rupture in print procedure, interrupt 3D printing shaping process, the many defects of goods that the 3D completed reluctantly prints, easy to crack, performance is low, and dimensional stability is low, does not meet actual user demand.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of flame-proof composite material for 3D printing and preparation method thereof, and flame-proof composite material provided by the present invention can not cause environmental pollution, and has good toughness and flame retardant properties.
The invention provides a kind of flame-proof composite material printed for 3D, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The ABS resin of 5 ~ 40 weight parts;
The lubricant of 0.3 ~ 2 weight part;
The compatilizer of 5 ~ 20 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The unformed red phosphorus of 5 ~ 30 weight parts.
Preferably, described nylon resin be in PA6, PA66, PA11, PA12 and PA1010 one or more.
Preferably, described compatilizer is styrene-maleic anhydride copolymer, ABS grafted maleic anhydride, Maleic Anhydride Grafted Ethylene Butyl Acrylate Copolymer or Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
Preferably; described oxidation inhibitor is 3; 5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine, tricresyl phosphite (2; 4-di-tert-butyl phenolic ester), four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N; N'-pair-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, copper halide, potassiumiodide, 1; 3; 5-trimethylammonium-2; one or more in 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene and 2 '-bis-(4-methyl-6-tert butyl-phenol) methane.
Preferably, described lubricant is one or more in ultra-high molecular weight polysiloxane, stearic acid, palmitinic acid, ethylene bis stearamide, stearic acid pentaerythritol ester, polyethylene wax and Zinic stearas.
Present invention also offers a kind of preparation method of the flame-proof composite material for 3D printing, it is characterized in that, comprise the following steps:
Nylon resin, ABS resin, fire retardant, compatilizer, oxidation inhibitor and mix lubricant are stirred and obtains mixture; By described mixture successively by melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
Preferably, before described mix and blend, also comprise and nylon resin and ABS resin are carried out drying.
Preferably, the rotating speed of described mix and blend is 700-1500r/min, and the mix and blend time is 1-5min.
Preferably, the 6 sections of temperature melt extruded described in 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.
Preferably, the rotating speed melt extruded described in is 80 ~ 180r/min.
Compared with prior art, the invention provides a kind of flame-proof composite material printed for 3D, comprise the raw material of following weight part: the nylon resin of 60 ~ 95 weight parts; The ABS resin of 5 ~ 40 weight parts; The lubricant of 0.3 ~ 2 weight part; The compatilizer of 5 ~ 20 weight parts; The oxidation inhibitor of 0.2 ~ 1 weight part; The unformed red phosphorus of 5 ~ 30 weight parts.Not halogen-containing in flame-proof composite material for 3D printing provided by the invention, can not to environment in material combustion and use procedure, further, by the interaction of unformed red phosphorus, ABS resin and other raw materials, improve flame retardant properties and the toughness of material.In addition, due to adding of lubricant, reduce the frictional coefficient of matrix material, improve the free-flowing property of matrix material, avoid the material caused due to local superheating to decompose, improve visual appearance and the surface smoothness of goods.Contribute to that the goods precision that is smooth and easy, that print of shower nozzle wire vent when 3D prints is high, surface quality good.
Result shows, the flame retardant rating of the flame-proof composite material for 3D printing provided by the present invention is V-0, unnotched impact strength >=774J/m, tensile strength > 38MPa, elastic modulus G reatT.GreaT.GT 881MPa.
Embodiment
The invention provides a kind of flame-proof composite material printed for 3D, it is characterized in that, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The ABS resin of 5 ~ 40 weight parts;
The lubricant of 0.3 ~ 2 weight part;
The compatilizer of 5 ~ 20 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The unformed red phosphorus of 5 ~ 30 weight parts.
Flame-proof composite material for 3D printing provided by the present invention comprises nylon resin, and nylon is the one in engineering plastics, and have the characteristics such as intensity is high, wear-resisting, self-lubricating, its mechanical property is apparently higher than the mechanical property of ABS and PLA printed for 3D.Described nylon resin to be selected from PA6, PA66, PA11, PA12 and PA1010 one or more.In described matrix material, the content of nylon resin is 60 ~ 95 weight parts, is preferably 75 ~ 90 weight parts, is more preferably 80 ~ 85 weight parts.
In the present invention, described flame-proof composite material also comprises ABS resin, and the content of described ABS resin is 5 ~ 40 weight parts, is preferably 10 ~ 35 weight parts, is more preferably 15 ~ 30 weight parts.The toughness that ABS resin can improve material is added in described matrix material.
Described flame-proof composite material also comprises lubricant, described lubricant is one or more in ultra-high molecular weight polysiloxane, stearic acid, palmitinic acid, ethylene bis stearamide, stearic acid pentaerythritol ester, polyethylene wax and Zinic stearas, is preferably ultra-high molecular weight polysiloxane.Described flame-proof composite material comprises the lubricant of 0.3 ~ 2 weight part, is preferably 0.5 ~ 1.5 weight part, is more preferably 0.7 ~ 1.0 weight part.
Also comprise compatilizer in flame-proof composite material provided by the present invention, described compatilizer is selected from styrene-maleic anhydride copolymer, ABS grafted maleic anhydride, Maleic Anhydride Grafted Ethylene Butyl Acrylate Copolymer or Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer; Be preferably the acrylonitrile-butadiene-styrene copolymer of maleic anhydride graft.Described flame-proof composite material comprises the compatilizer of 5 ~ 20 weight parts, is preferably 10 ~ 15 weight parts.In the present invention, compatilizer is dispersed in nylon based composites system, and when material is subject to impacting, its microtexture can produce a large amount of crazings, and branching around, absorb a large amount of striking energys, thus improve the shock strength of material.
Also oxidation inhibitor is comprised in described flame-proof composite material, described oxidation inhibitor is selected from 3, 5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine, tricresyl phosphite (2, 4-di-tert-butyl phenolic ester), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N'-pair-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, copper halide, potassiumiodide, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene and 2 '-bis-(4-methyl-6-tert butyl-phenol) methane, be preferably four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.Described flame-proof composite material comprises the oxidation inhibitor of 0.2 ~ 1 weight part, is preferably 0.5 ~ 0.8 weight part.
Unformed red phosphorus is also comprised in described flame-proof composite material, at 400-450 DEG C, red phosphorus depolymerization forms white phosphorus, the latter is oxidized to the oxygen acid of the phosphorus of viscosity under aqueous vapor exists, and this kind of material both can be covered in by the surface of fire retardant material, can accelerate dehydration carbonization on the surface of material again, the oxygen of outside, volatile combustible and heat and inner superpolymer matrix then can separate and contribute to flameout by the liquid film of formation and layer of charcoal.Described flame-proof composite material comprises the unformed red phosphorus of 5 ~ 30 weight parts, is preferably 10 ~ 25 weight parts, is more preferably 15 ~ 20 weight parts.
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, oxidation inhibitor and mix lubricant are stirred and obtains mixture; By described mixture successively by melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
First each raw material mixes by the present invention, and before combination, preferably nylon resin and ABS resin are carried out pre-treatment, concrete grammar is:
Nylon resin and ABS resin are placed in loft drier and carry out drying, wherein, drying temperature is 90 ~ 110 DEG C, and time of drying is 4 ~ 8h.
By the nylon resin after drying and ABS resin mixing, obtain hybrid resin.In hybrid resin, add lubricant, compatilizer, oxidation inhibitor and unformed red phosphorus again stir, obtain mixture.Wherein, the rotating speed of described stirring is 700-1500r/min, and the rotating speed of described stirring is 1-5min, blending and stirring 3 times.
After mixing terminates, described mixture is melt extruded.In the present invention, preferably adopt screw extrusion press to melt extrude, 6 sections of temperature of described melt extruder are for being 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 melt extruded is carried out wire-drawing shape, and obtain the flame-proof composite material printed for 3D, wherein, the string diameter of the matrix material of wire-drawing shape has 1.75mm and 3mm two kinds of specifications, and the precision of matrix material is ± 0.03mm, and circularity is ± 0.03mm.
In the present invention, also consumptive material can be prepared into particulate state or Powdered.Concrete, the preparation method of particulate state consumptive material is: the consumptive material after wire drawing is introduced dicing machine, carries out granulation, and granular size is determined, generally between 0.5mm-5mm by the silk material diameter and granulate equipment extruding wire drawing.
The preparation method of powder material is: the consumptive material after particulate state consumptive material or wire drawing is carried out chilling fragmentation or dissolution with solvents precipitation, the diameter of powder material is at 10-100 micron.
Not halogen-containing in flame-proof composite material for 3D printing provided by the invention, can not to environment in material combustion and use procedure, further, by the interaction of unformed red phosphorus, ABS resin and other raw materials, improve flame retardant properties and the toughness of material.In addition, due to adding of lubricant, reduce the frictional coefficient of matrix material, improve the free-flowing property of matrix material, avoid the material caused due to local superheating to decompose, improve visual appearance and the surface smoothness of goods.Contribute to that the goods precision that is smooth and easy, that print of shower nozzle wire vent when 3D prints is high, surface quality good.
Result shows, the flame retardant rating of the flame-proof composite material for 3D printing provided by the present invention is V-0, unnotched impact strength > 774J/m, tensile strength > 38MPa, elastic modulus G reatT.GreaT.GT 881MPa.
In order to understand the present invention further, be described flame-proof composite material for 3D printing provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Take Nylon 6 1000g, ABS resin 400g, unformed red phosphorus 128g, the acrylonitrile-butadiene-styrene copolymer 200g of maleic anhydride graft, four [β-(3 respectively, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 5.4g, ultra-high molecular weight polysiloxane 18g, put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 200 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, and screw speed is 80 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
Measure resistance to impact shock and the flame retardant properties of the flame-proof composite material for 3D printing obtained, the results are shown in Table 1, the performance of the flame-proof composite material for 3D printing that table 1 provides for embodiment 1 ~ 3.
Embodiment 2
Take Nylon 6 1000g, ABS resin 300g, unformed red phosphorus 145g, styrene-maleic anhydride copolymer 150g, N respectively; N'-couple-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester 4.4g, stearic acid 14.5g puts into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237 DEG C, 245 DEG C, and screw speed is 80 revs/min.The silk material of extrusion moulding carries out granulation process via granulate equipment, and its particle size is adjustable, and determined by the diameter of precursor and the parameter of granulate equipment, general diameter is at 1-3mm, and length is between 0.5mm-5mm.
Measure resistance to impact shock and the flame retardant properties of the flame-proof composite material for 3D printing obtained, the results are shown in Table 1, the performance of the flame-proof composite material for 3D printing that table 1 provides for embodiment 1 ~ 3.
Embodiment 3
Take Nylon 66 1000g, ABS resin 300g respectively, 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-phenyl] phosphorous acid ester 4.5g, stearic acid 15g put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 240 DEG C, 250 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 270 DEG C, and screw speed is 100 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
Measure resistance to impact shock and the flame retardant properties of the flame-proof composite material for 3D printing obtained, the results are shown in Table 1, the performance of the flame-proof composite material for 3D printing that table 1 provides for embodiment 1 ~ 3.
Embodiment 4
Take Nylon 6 800g respectively, nylon 12 resin 200g, 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-phenyl] phosphorous acid ester 4.5g, stearic acid 15g put into high-speed mixer mixing 5min.Then extrude with screw extrusion press, shaping via wire-drawing shape equipment.The 6 sections of temperature melt extruded are respectively 200 DEG C, 220 DEG C, 225 DEG C, 232 DEG C, 237 DEG C, 240 DEG C, and screw speed is 100 revs/min.Be coiled into the consumptive material of volume through vacuum-drying, sealing is preserved.
The performance of the flame-proof composite material for 3D printing that table 1 embodiment 1 ~ 3 provides
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1., for the flame-proof composite material that 3D prints, it is characterized in that, comprise the raw material of following weight part:
The nylon resin of 60 ~ 95 weight parts;
The ABS resin of 5 ~ 40 weight parts;
The lubricant of 0.3 ~ 2 weight part;
The compatilizer of 5 ~ 20 weight parts;
The oxidation inhibitor of 0.2 ~ 1 weight part;
The unformed red phosphorus of 5 ~ 30 weight parts.
2. matrix material according to claim 1, is characterized in that, described nylon resin be in PA6, PA66, PA11, PA12 and PA1010 one or more.
3. matrix material according to claim 1, it is characterized in that, described compatilizer is styrene-maleic anhydride copolymer, ABS grafted maleic anhydride, Maleic Anhydride Grafted Ethylene Butyl Acrylate Copolymer or Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
4. matrix material according to claim 1, it is characterized in that, described oxidation inhibitor is 3, 5-di-t-butyl-4-hydroxybenzene propionyl-hexanediamine, tricresyl phosphite (2, 4-di-tert-butyl phenolic ester), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N'-pair-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, copper halide, potassiumiodide, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene and 2 '-bis-(4-methyl-6-tert butyl-phenol) methane.
5. matrix material according to claim 1, is characterized in that, described lubricant is one or more in ultra-high molecular weight polysiloxane, stearic acid, palmitinic acid, ethylene bis stearamide, stearic acid pentaerythritol ester, polyethylene wax and Zinic stearas.
6., for a preparation method for the flame-proof composite material of 3D printing, it is characterized in that, comprise the following steps:
Nylon resin, ABS resin, fire retardant, compatilizer, oxidation inhibitor and mix lubricant are stirred and obtains mixture; By described mixture successively by melt extruding the flame-proof composite material obtaining with wire-drawing shape printing for 3D.
7. preparation method according to claim 6, is characterized in that, before described mix and blend, also comprises and nylon resin and ABS resin are carried out drying.
8. preparation method according to claim 6, its feature exists, and the rotating speed of described mix and blend is 700-1500r/min, and the mix and blend time is 1-5min.
9. preparation method according to claim 6, is characterized in that, described in 6 sections of temperature melt extruding 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.
10. preparation method according to claim 6, is characterized in that, described in the rotating speed that melt extrudes be 80 ~ 180r/min.
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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 |
| CN106832906A (en) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | 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 |
| 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 |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5924752A (en) * | 1982-08-02 | 1984-02-08 | Kanebo Ltd | Method for making thermoplastic resin flame-retardant |
| JP2001011266A (en) * | 1999-04-30 | 2001-01-16 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| CN1379061A (en) * | 2002-04-26 | 2002-11-13 | 北京北方恒利科技发展有限公司 | Nylon powder used for high-speed laser sintered products |
| CN103756301A (en) * | 2013-12-20 | 2014-04-30 | 安徽孟凌精密电子有限公司 | Halogen-free expansive flame retardant PA12 composite material for nylon gasket |
| CN103897386A (en) * | 2014-04-02 | 2014-07-02 | 苏州大业三维打印技术有限公司 | Reinforcing material applied in selective laser sintering |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
| WO2014186769A1 (en) * | 2013-05-17 | 2014-11-20 | Uram Stuart | Molds for ceramic casting |
-
2014
- 2014-12-18 CN CN201410796193.6A patent/CN104479349B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5924752A (en) * | 1982-08-02 | 1984-02-08 | Kanebo Ltd | Method for making thermoplastic resin flame-retardant |
| JP2001011266A (en) * | 1999-04-30 | 2001-01-16 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| CN1379061A (en) * | 2002-04-26 | 2002-11-13 | 北京北方恒利科技发展有限公司 | Nylon powder used for high-speed laser sintered products |
| WO2014186769A1 (en) * | 2013-05-17 | 2014-11-20 | Uram Stuart | Molds for ceramic casting |
| CN103756301A (en) * | 2013-12-20 | 2014-04-30 | 安徽孟凌精密电子有限公司 | Halogen-free expansive flame retardant PA12 composite material for nylon gasket |
| CN103897386A (en) * | 2014-04-02 | 2014-07-02 | 苏州大业三维打印技术有限公司 | Reinforcing material applied in selective laser sintering |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
Non-Patent Citations (4)
| Title |
|---|
| 吴智华: "《高分子材料加工工程实验教程》", 30 September 2004, 化学工业出版社 * |
| 徐德林 等: "《表面活性剂合成及应用》", 31 August 1995, 河南科学技术出版社 * |
| 杨永强 等: "《制造改变设计-3D打印直接制造技术》", 30 June 2014, 中国科学技术出版社 * |
| 杨鸣波 等: "《高分子材料手册[上]》", 31 July 2009, 化学工业出版社 * |
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| 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 |
| CN106832906A (en) * | 2017-03-02 | 2017-06-13 | 张家港市五湖新材料技术开发有限公司 | A kind of high flame retardant nylon composite materials for 3D printing |
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