CN109627716A

CN109627716A - Low smell halogen-free flameproof PLA/PC material and preparation method thereof for 3D printing

Info

Publication number: CN109627716A
Application number: CN201811457048.XA
Authority: CN
Inventors: 潘德群
Original assignee: Guangdong Shunde Youxian Three-Dimension Technology Co Ltd
Current assignee: Guangdong Shunde Youxian Three-Dimension Technology Co Ltd
Priority date: 2018-11-30
Filing date: 2018-11-30
Publication date: 2019-04-16

Abstract

The present invention discloses a kind of low smell halogen-free flameproof PLA/PC material for 3D printing, by mass percentage, including following components, polylactic acid: 33~73.6%, polycarbonate: 10-40%, compatilizer: 1~5%, phosphorus nitrogen composite halogen-free fire retardant: 15-20%, antioxidant: 0.2~1%, lubricant: 0.2~1%.Low smell halogen-free flameproof PLA/PC material provided by the present invention for 3D printing, by using the mixture of coated inorganic hypophosphites and melamine salt as phosphorus nitrogen compound flame retardant, substantially increase flame retardant effect, flame retardant rating can reach V0, the release of odor profiles substance in hypophosphites can be reduced simultaneously, requirement of the 3D printing material to flame retardant effect and smell can be met simultaneously, reduce costs and have good heat resistance, toughness and processability, it is environment-protecting and non-poisonous.Additionally provide the preparation method of PLA/PC material, it is easy to operate, process conditions controllability is strong, it is very suitable for large-scale industrial production.

Description

Low smell halogen-free flameproof PLA/PC material and preparation method thereof for 3D printing

Technical field

The present invention relates to the low smell halogen-free flameproof PLA/PC Material Fields for 3D printing, and in particular to is used for 3D printing Low smell halogen-free flameproof PLA/PC material and preparation method thereof.

Background technique

3D printing technique is to pass through delamination software and numerical control molding system, benefit based on designing a model by Computerized three-dimensional The special materials such as metal powder, ceramic powders, plastics, cell tissue are subjected to layer-by-layer heap with modes such as laser beam, hot melt nozzles Product is cohered, and final superposition molding produces physical product.Polylactic acid (PLA) is used as a kind of novel excellent bioabsorbable polymer material, Have the characteristics that nontoxic, nonirritant, good biocompatibility, intensity are high and biodegradable and absorb, is most to have development at present The biodegradable polymer of future.But the defects of polylactic acid physical property is crisp, poor heat resistance limits beating in 3D for polylactic acid Application in print technology, and polycarbonate (PC) has high rigidity, the features such as high tenacity, temperature tolerance is good, and dimensional stability is excellent are used The toughness and temperature tolerance of polylactic acid can be improved in polycarbonate modified polylactic acid, promotes the Physical Processing performance of poly-lactic acid material.

Simultaneously it is hidden to there is safety because having inflammability in the high molecular materials such as polylactic acid and its modifier in application process Suffer from, need to carry out flame-retarded processing, the burning of high molecular material, which is broadly divided into, to be thermally decomposed, is lighted, acceleration of burning, stablizing combustion Burning, burning decay and five Main Stages such as daughter-in-law is gone out, and addition fire retardant is the most direct effective method of flame retardance of polymer processing, root Halogenated flame retardant, organic phosphorus nitrogen based flame retardant, expansion type flame retardant and inorganic fire retardants can be divided into according to the component difference of fire retardant Deng, halogenated flame retardant, with the promulgation of the relevant laws and regulations such as RoHs and WEEE, its application centainly is restricted, for polylactic acid Halogen-free flame retardants mainly based on additive flame retardant, have at present: graphite, organic phosphine, phosphate, ammonium polyphosphate and its compounding Object, hypophosphites etc..Wherein organic phosphorus nitrogen based flame retardant because high effect nontoxic it is more and more in good graces, and due to print temperature height, The processing fluidity of material is poor and poor heat resistance especially additive flame retardant such as hypophosphites will lead to plastics and print Cheng Zhonghui gives out some smells and limits polylactic acid in the application in 3D printing field.

Summary of the invention

The purpose of the present invention is to provide a kind of good toughness and impact strength height, and heat resistance and processing performance are good and environmentally friendly Low smell halogen-free flameproof PLA/PC material for 3D printing is to solve the deficiency in existing issue.

It is a further object of the present invention to provide a kind of preparations of low smell halogen-free flameproof PLA/PC material for 3D printing Method.

To achieve this purpose, the present invention adopts the following technical scheme:

A kind of low smell halogen-free flameproof PLA/PC material for 3D printing, by mass percentage, including following components, Polylactic acid: 33~73.6%, polycarbonate: 10-40%, compatilizer: 1~5%, phosphorus nitrogen composite halogen-free fire retardant: 15-20%, Antioxidant: 0.2~1%, lubricant: 0.2~1%.

In above-mentioned technical proposal, using the good biocompatibility of polylactic acid, high intensity and biodegradability with And the good toughness of polycarbonate and temperature tolerance, and make compatilizer, phosphorus nitrogen composite halogen-free fire retardant, antioxidant and lubricant plus Enter amount and control the temperature tolerance and toughness for improving composite material greatly in the reasonable scope as 3D printing material, wherein phosphorus nitrogen Composite halogen-free fire retardant is mainly that condensed phase fire retardant mechanism plays a role, and P-N cross-linked structure can be formed in condensed phase Play the role of it is heat-insulated oxygen barrier, avoid inorganic hypophosphites in thermal degradation process be easy with P₂O₅The form volatilization of equal oxides Fire retardation is lost, processing performance of the composite material in print procedure is improved and to reduce smell more environmentally-friendly.

The weight percent of above-mentioned PLA is 33-73.6%, such as 35%, 38%, 40%, 43%, 45%, 48%, 50%, 55%, 58%, 60%, 62%, 65%, 67%, 70% and 72%；The weight percent of above-mentioned PC is 10-40%, example Such as 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38% and 40%；The weight of above-mentioned compatilizer Measuring part is 1~5%, such as 1.2%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.8%, 3.0%, 3.2%, 3.4%, 3.7%, 4.0%, 4.2%, 4.5% and 4.7%；The weight percent of above-mentioned phosphorus nitrogen composite halogen-free fire retardant is 15-20%, example Such as 15.3%, 15.6%, 15.8%, 16.0%, 16.5%, 17.0%, 17.3%, 17.6%, 18%, 18.5%, 19.0%, 19.2% and 19.6%；The weight percent of above-mentioned antioxidant is 0.2~1%, such as 0.4%, 0.5%, 0.6% and 0.8%； The weight percent of above-mentioned lubricant is 0.2~1%, such as 0.3%, 0.5%, 0.7% and 0.9%.

Further, the phosphorus nitrogen composite halogen-free fire retardant is the mixing of coated inorganic hypophosphites and melamine salt Object.

In above-mentioned technical proposal, melamine salt can be played with inorganic hypophosphites and be acted synergistically, and avoid inorganic secondary phosphorus Easily volatilization is in the form of the oxide to its effect of difficult performance in condensed phase for hydrochlorate, and in addition melamine salt is to inorganic hypophosphorous acid Salt, which carries out coating modification, can be improved the stability of inorganic hypophosphites, reinforces the oxidation of phosphorus, delays its volatilization process, and nothing The release of the inert gases such as the ammoniate of nitrogenous compound in combustion after machine hypophosphites cladding can dilute flammable Property gas concentration substantially increases flame retardant effect to play fire retardation, can reach the flame retardant rating of V0.

Further, the mass percent of the coated inorganic hypophosphites and melamine salt be respectively 50-80% and 20-50%, the coated inorganic hypophosphites are melamine cyanurate coated inorganic hypo-aluminum orthophosphate or melamine cyanurea Hydrochlorate coated inorganic calcium hypophosphite.

In above-mentioned technical proposal, by reducing the mantle friction of hypophosphites to inorganic hypophosphites surface coating modification, The release of odor profiles substance in hypophosphites is reduced, while the ratio of hypophosphites can be reduced by compounding melamine salt, Therefore, meet smell fire-retardant, and that hypophosphites can be substantially reduced in a manner of phosphorus nitrogen compounding.

Mass percent of the above-mentioned coated inorganic hypophosphites in phosphorus nitrogen composite halogen-free flame-retardant mixture is 50- 80%, for example, 52%, 55%, 58%, 60%, 63%, 65%, 68%, 70%, 72%, 75% and 78%；It is above-mentioned in phosphorus nitrogen Mass percent in composite halogen-free flame-retardant mixture is 20-50%, such as 25%, 28%, 30%, 33%, 36%, 38%, 40%, 42%, 46% and 48%.The mass percent of coated inorganic hypophosphites and melamine salt is controlled respectively It in reasonable range, that is, can guarantee that the flame retardant effect of composite material can achieve V0, while smell can be reduced again meet environmental protection and want It asks.

Further, the melamine salt is melamine cyanurate (MCA), melamine pyrophosphate (MPP), just Any one or more of melamine phosphate (MMP) or two melamine of orthophosphoric acid (DMPY).These melamine salts as a result, Inert gas is generated by heat absorption in combustion after coating to the surface of inorganic hypophosphites, promotes into charcoal and is mostly swollen The formation of swollen separation layer can capture combustion activity free radical, greatly improve the flame retardant rating of composite material, have good heat-resisting Property and processability, the application in terms of making it be more suitable for 3D printing material.

Further, the melt index MI of the polylactic acid is 8g/10min (190 DEG C of .2.16Kg).Since polylactic acid is molten It is too low to melt index, the big melting viscosity of molecular weight is big, influences extrusion and print speed；Polylactic acid melt index is too high, and molecular weight is low The mechanical properties such as toughness, the intensity of modified material are influenced, therefore select moderate melt index so that modified material has While suitable melting viscosity and extrusion print speed, the mechanical properties such as toughness, intensity needed for guaranteeing 3D printing.

Further, the polycarbonate is bisphenol A-type aromatic copolycarbonate and MI is (300 DEG C of 10g/10min .0.3Kg).Moderate melt index is selected as a result, while containing rigid phenyl ring, phenyl ring in bisphenol A-type aromatic copolycarbonate Upper polar hydroxyl can be reacted with the carboxyl end group of polylactic acid, formed cross-linked network, can be obviously improved composite material Impact resistance, heat resistance and toughness.

Further, the compatilizer is Methyl Methacrylate-Butadiene-Styrene Copolymer, ethene-vinyl acetate Ester copolymer, ethylene-acrylate-any one of glycidyl methacrylate or Ethylene-butyl acrylate or several Kind.Thus, it is possible to improve the interface binding power between polylactic acid and polycarbonate, keep the dispersibility of composite material more preferable, it is modified The mechanical performance of composite material.

Further, the antioxidant is antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant B215 or antioxygen Any one or more of agent B225.Since phenolic antioxidant has toxicity low, non-discolouring and good heat resistance can extend multiple The service life of laminate article.

Further, the lubricant is stearic acid, calcium stearate, magnesium stearate, ethylene bis stearamide or Ji Wusi Any one or more of alcohol stearate.Stearic acid lubricant has good thermal stability and compatibility, squeezes in material The mobility of material can be improved when forming out, improve the adhesion of polymer material and barrel and mold, prevent and reduce retentate.

A kind of preparation method of the low smell halogen-free flameproof PLA/PC material as described above for 3D printing, including it is following Step:

It first weighs polylactic acid and polycarbonate respectively by mass percentage, adds compatilizer, fire retardant, antioxidant and profit Lubrication prescription stirs evenly all raw materials；Draw ratio is used to be granulated for the double screw extruder melting extrusion of 40:1 again, extrusion temperature It is 200 DEG C~230 DEG C, revolving speed 150-350rpm；Then pellet will be squeezed out to be placed in convection oven in 80 DEG C~100 DEG C dryings 4-6h will squeeze out pellet under 220 DEG C~240 DEG C and 40~50Mpa with injection molding machine and be molded into standard testing batten to be used to hinder Combustion test.

It is had the advantage that provided by the present invention for the low smell halogen-free flameproof PLA/PC material of 3D printing

1, PLA and PC is mixed and modified, it is polar on phenyl ring containing rigid phenyl ring in bisphenol A-type aromatic copolycarbonate Hydroxyl can be reacted with the carboxyl end group of PLA, formed cross-linked network, can be obviously improved the impact resistance of composite material, resistance to Hot property and toughness ensure that the mechanical property requirements such as processability required when 3D printing, heat resistance, toughness and intensity, can fit For higher print speed.

2, it is on the one hand adopted using the mixture of coated inorganic hypophosphites and melamine salt as phosphorus nitrogen compound flame retardant The stability that coating modification improves inorganic hypophosphites is carried out to inorganic hypophosphites with melamine salt, reinforces the oxygen of phosphorus Change, avoiding inorganic hypophosphites, easily volatilization substantially increases in the form of the oxide to which hardly possible plays its effect in condensed phase Flame retardant effect can reach the flame retardant rating of V0；Simultaneously because of the table to inorganic hypophosphites surface coating modification reduction hypophosphites Face friction, so that the release of odor profiles substance in hypophosphites is reduced, in addition reducing hypophosphites by compounding melamine salt Ratio, further reduced smell, therefore, selected phosphorus nitrogen compound flame retardant can meet the fire-retardant of 3D printing material simultaneously The requirement that effect is good and smell is small.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.

Unless specific instructions, various raw materials of the invention are commercially available buys, or according to the conventional method of the art It is prepared.

Embodiment 1

The present embodiment use for 3D printing low smell halogen-free flameproof PLA/PC material include by mass percentage, Including following components:

1 embodiment 1- raw material components of table and its mass percent

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 1, add methyl methacrylate-fourth Diene-styrene copolymer, melamine cyanurate coated inorganic calcium hypophosphite, antioxidant 1010, irgasfos 168 and hard Resin acid stirs evenly all raw materials, and wherein polylactic acid is produced by U.S. nature works；Use draw ratio for 40:1's again Double screw extruder melting extrusion is granulated, and extrusion temperature is 200 DEG C, revolving speed 150rpm；Then pellet will be squeezed out and be placed in air blast In 80 DEG C of dry 4h in baking oven, pellet will be squeezed out under 240 DEG C and 50Mpa with injection molding machine and is molded into standard testing batten to be used for Flame retardant test.

Embodiment 2

2 embodiment 2- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	39
PC (trade mark: PC-110)	40
		Methyl Methacrylate-Butadiene-Styrene Copolymer	5
Melamine cyanurate coated inorganic calcium hypophosphite	10
		Melamine cyanurate (MCA)	5
1010	0.5
		168	0.3
Calcium stearate	0.2

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 2, add methyl methacrylate-fourth Diene-styrene copolymer, melamine cyanurate coated inorganic calcium hypophosphite, melamine cyanurate (MCA), antioxidant 1010, irgasfos 168 and calcium stearate stir evenly all raw materials, and wherein polylactic acid is nature works institute, the U.S. It produces；Draw ratio is used to be granulated for the double screw extruder melting extrusion of 40:1 again, extrusion temperature is 210 DEG C, revolving speed 160rpm； Then pellet will be squeezed out to be placed in convection oven in 80 DEG C of dry 5h, pellet note will be squeezed out under 220 DEG C and 45Mpa with injection molding machine Standard testing batten is moulded into for flame retardant test.

Embodiment 3

3 embodiment 3- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	53.5
PC (trade mark: PC-110)	20
		Ethylene-acrylate-glycidyl methacrylate	5
Melamine cyanurate coated inorganic hypo-aluminum orthophosphate	15
		Melamine pyrophosphate (MPP)	5
1076	0.5
		168	0.5
Magnesium stearate	0.5

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 3, add ethylene-acrylate-first Base glycidyl acrylate, melamine pyrophosphate (MPP), resists melamine cyanurate coated inorganic hypo-aluminum orthophosphate Oxygen agent 1076, irgasfos 168 and magnesium stearate stir evenly all raw materials, and wherein polylactic acid is U.S. nature works It is produced；Draw ratio is used to be granulated for the double screw extruder melting extrusion of 40:1 again, extrusion temperature is 200 DEG C, and revolving speed is 280rpm；Then pellet will be squeezed out to be placed in convection oven in 80 DEG C of dry 6h, will be squeezed under 220 DEG C and 40Mpa with injection molding machine Pellet is molded into standard testing batten for flame retardant test out.

Embodiment 4

4 embodiment 4- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	44
PC (trade mark: PC-110)	30
		Ethylene-acrylate-glycidyl methacrylate	5
Melamine cyanurate coated inorganic hypo-aluminum orthophosphate	15
		Orthophosphoric acid melamine (MMP)	5
B215	0.5
		Pentaerythritol stearate	0.5

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 4, add ethylene-acrylate-first Base glycidyl acrylate, melamine cyanurate coated inorganic hypo-aluminum orthophosphate, orthophosphoric acid melamine (MMP), antioxygen Agent B215 and pentaerythritol stearate stir evenly all raw materials, and wherein polylactic acid is nature works institute, the U.S. It produces；Draw ratio is used to be granulated for the double screw extruder melting extrusion of 40:1 again, extrusion temperature is 200 DEG C, revolving speed 350rpm； Then pellet will be squeezed out to be placed in convection oven in 80 DEG C of dry 5h, pellet note will be squeezed out under 220 DEG C and 50Mpa with injection molding machine Standard testing batten is moulded into for flame retardant test.

Embodiment 5

5 embodiment 5- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	44
PC (trade mark: PC-110)	30
		Ethylene-butyl acrylate	5
Melamine cyanurate coated inorganic hypo-aluminum orthophosphate	15
		Two melamine of orthophosphoric acid (DMPY)	5
B225	0.5
		Ethylene bis stearamide	0.5

First weigh polylactic acid and polycarbonate respectively by the mass percent in table 5, add Ethylene-butyl acrylate, Melamine cyanurate coated inorganic hypo-aluminum orthophosphate, two melamine of orthophosphoric acid (DMPY), antioxidant B225 and ethylene are double Stearmide stirs evenly all raw materials, and wherein polylactic acid is produced by U.S. nature works；Use draw ratio for 40 again: 1 double screw extruder melting extrusion is granulated, and extrusion temperature is 210 DEG C, revolving speed 200rpm；Then pellet will be squeezed out and be placed in drum In 100 DEG C of dry 4h in wind baking oven, will be squeezed out under 220 DEG C and 50Mpa with injection molding machine pellet be molded into standard testing batten with For flame retardant test.

Comparative example 1

This comparative example use for 3D printing low smell halogen-free flameproof PLA/PC material include by mass percentage, Including following components:

6 comparative example 1- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	64
PC (trade mark: PC-110)	10
		Methyl Methacrylate-Butadiene-Styrene Copolymer	5
Inorganic calcium hypophosphite	10
		Melamine cyanurate (MCA)	10
1010	0.5
		168	0.3
Stearic acid	0.2

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 6, add methyl methacrylate-fourth Diene-styrene copolymer, inorganic calcium hypophosphite, melamine cyanurate (MCA), antioxidant 1010, irgasfos 168 and hard Resin acid stirs evenly all raw materials, and wherein polylactic acid is produced by U.S. nature works；Use draw ratio for 40:1's again Double screw extruder melting extrusion is granulated, and extrusion temperature is 200 DEG C, revolving speed 200rpm；Then pellet will be squeezed out and be placed in air blast In 80 DEG C of dry 5h in baking oven, pellet will be squeezed out under 220 DEG C and 50Mpa with injection molding machine and is molded into standard testing batten to be used for Flame retardant test.

Comparative example 2

7 comparative example 2- raw material components of table and its mass percent

Raw material	Mass percent (%)
		PLA (trade mark: 3801X)	64
PC (trade mark: PC-110)	10
		Methyl Methacrylate-Butadiene-Styrene Copolymer	5
Inorganic hypo-aluminum orthophosphate	15
		Melamine cyanurate (MCA)	5
1010	0.5
		168	0.3
Stearic acid	0.2

Polylactic acid and polycarbonate are first weighed respectively by the mass percent in table 7, add methyl methacrylate-fourth Diene-styrene copolymer, inorganic hypo-aluminum orthophosphate, melamine cyanurate (MCA), antioxidant 1010, irgasfos 168 and hard Resin acid calcium stirs evenly all raw materials, and wherein polylactic acid is produced by U.S. nature works；Use draw ratio for 40:1 again Double screw extruder melting extrusion be granulated, extrusion temperature be 210 DEG C, revolving speed 150rpm；Then pellet will be squeezed out and be placed in drum In 80 DEG C of dry 5h in wind baking oven, will be squeezed out under 220 DEG C and 45Mpa with injection molding machine pellet be molded into standard testing batten with In flame retardant test.

By embodiment 1-5 and comparative example 1 and the comparative example 2 low smell halogen-free flameproof PLA/ obtained for being used for 3D printing PC material is tested for the property, and anti-flammability is tested according to the test method of UL94V0, and odor profiles test is according to masses VW50180 method is tested: acquired sample being made to the colour table of unified size, is placed in sealing conical beaker, is placed in After toasting 2H in 80 DEG C of baking oven, beaker is opened, comparison is odor profiles, according to: 1, free from extraneous odour；2, slightly smell；3, flavoursome, but It does not stimulate；4, irritating smell；5, strong impulse smell；6, intolerable taste, six grades are divided, are as a result seen Table 8:

8 the performance test results of table

As can be seen from Table 8, material obtained by comparative example 1-2 and Examples 1 to 5 is able to satisfy V0 flame-retardancy requirements, but by There is no coating modifications for inorganic phosphate in the fire retardant that comparative example 1-2 is used, while also without compounding melamine salt, right 1 comparative example 2 of ratio it is odor profiles significantly greater, there is penetrating odor, and the free from extraneous odour of Examples 1 to 5, while having very well Tensile strength and elongation at break, comply fully with requirement of the 3D printing material to smell, fire-retardant and toughness and processing performance.

Above embodiments are only used to illustrate method detailed of the invention, and the invention is not limited to above-mentioned method detaileds, i.e., Do not mean that the invention must rely on the above detailed methods to implement.Person of ordinary skill in the field should be understood that pair Any improvement of the invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode Deng all of which fall within the scope of protection and disclosure of the present invention.

Claims

1. a kind of low smell halogen-free flameproof PLA/PC material for 3D printing, which is characterized in that by mass percentage, including Following components, polylactic acid: 33~73.6%, polycarbonate: 10-40%, compatilizer: 1~5%, phosphorus nitrogen composite halogen-free fire retardant: 15-20%, antioxidant: 0.2~1%, lubricant: 0.2~1%.

2. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described Phosphorus nitrogen composite halogen-free fire retardant is the mixture of coated inorganic hypophosphites and melamine salt.

3. the low smell halogen-free flameproof PLA/PC material according to claim 2 for 3D printing, which is characterized in that described The mass percent of coated inorganic hypophosphites and melamine salt is respectively 50-80% and 20-50%, the coated inorganic Phosphate is melamine cyanurate coated inorganic hypo-aluminum orthophosphate or melamine cyanurate coated inorganic calcium hypophosphite.

4. the low smell halogen-free flameproof PLA/PC material according to claim 2 for 3D printing, which is characterized in that described Melamine salt is melamine cyanurate (MCA), melamine pyrophosphate (MPP), orthophosphoric acid melamine (MMP) or just Any one or more of di(2-ethylhexyl)phosphate melamine (DMPY).

5. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described The melt index MI of polylactic acid is 8g/10min (190 DEG C of .2.16Kg).

6. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described Polycarbonate is bisphenol A-type aromatic copolycarbonate and MI is 10g/10min (300 DEG C of .0.3Kg).

7. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described Compatilizer is Methyl Methacrylate-Butadiene-Styrene Copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid Ester-any one or more of glycidyl methacrylate or Ethylene-butyl acrylate.

8. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described Antioxidant is any one of antioxidant 1010, antioxidant 1076, irgasfos 168, antioxidant B215 or antioxidant B225 or several Kind.

9. the low smell halogen-free flameproof PLA/PC material according to claim 1 for 3D printing, which is characterized in that described Lubricant be any one of stearic acid, calcium stearate, magnesium stearate, ethylene bis stearamide or pentaerythritol stearate or It is several.

10. a kind of low smell halogen-free flameproof PLA/ for 3D printing as described in any one of claim 1-9 claim The preparation method of PC material, which comprises the following steps:

It first weighs polylactic acid and polycarbonate respectively by mass percentage, adds compatilizer, fire retardant, antioxidant and lubricant Stir evenly all raw materials；Draw ratio is used to be granulated for the double screw extruder melting extrusion of 40:1 again, extrusion temperature 200 DEG C~230 DEG C, revolving speed 150-350rpm；Then pellet will be squeezed out to be placed in convection oven in 80 DEG C~100 DEG C dry 4-6h, Pellet will be squeezed out under 220 DEG C~240 DEG C and 40~50Mpa with injection molding machine and is molded into standard testing batten to be used for fire-retardant survey Examination.