CN109401254A - A kind of halogen-free flame-proof polylactic acid material and preparation method thereof for 3D printing - Google Patents
A kind of halogen-free flame-proof polylactic acid material and preparation method thereof for 3D printing Download PDFInfo
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- CN109401254A CN109401254A CN201811457038.6A CN201811457038A CN109401254A CN 109401254 A CN109401254 A CN 109401254A CN 201811457038 A CN201811457038 A CN 201811457038A CN 109401254 A CN109401254 A CN 109401254A
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- polylactic acid
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- free flame
- acid material
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention discloses a kind of halogen-free flame-proof polylactic acid material and preparation method thereof for 3D printing, wherein the halogen-free flame-proof polylactic acid material for 3D printing by weight percentage, including following components: polylactic acid 53~78.6%；Fire retardant 15~20%；Plasticizer 2.5~5%；Toughener 6~10%；Wherein, the fire retardant is compounded by piperazine pyrophosphate with melamine phosphate.The present invention is using the compound of piperazine pyrophosphate and melamine phosphate as fire retardant, the dosage of plasticizer and toughener is optimized simultaneously, halogen-free flame-proof polylactic acid material can be made to fully meet V0 flame-retardancy requirements, and there is the characteristic without precipitation, high oxygen index (OI), also there is good toughness simultaneously, fully meet 3D printing demand.
Description
Technical field
The present invention relates to 3D printing field of material technology, and in particular to a kind of halogen-free flame-proof polylactic acid material for 3D printing
Material and preparation method thereof.
Background technique
3D printing is called increasing material manufacturing, is a kind of rapid shaping technique, and fused glass pellet technology is 3D printing technique
One of, consumptive material is heated to melting temperature using printing head, is solidified after melt outflow, successively accumulation is beaten required for being formed
The article of print.Consumptive material for 3D printing is usually made the wire rod that diameter is 3.00mm, and this requires wire rods with good tough
Property and tensile strength, thus can to avoid printing when driving wheel tractive force effect under there is a phenomenon where fracture of wires, while in order to
The fluency and printing effect for guaranteeing printing, need to be improved the mobility of consumptive material, prevent that spray head blocking occurs in print procedure
Problem.
Polylactic acid (Polylactic acid, PLA) is that the lactic acid mainly refined using cornstarch is closed as monomer, through chemistry
At Biodegradable high molecular material, have nontoxic, nonirritant, good biocompatibility, intensity high and can biology drop
The features such as solution and absorption, the application study in 3D printing field is more and more extensive in recent years.
The flame-retardant modified mainly halogen-free flame retardants to add the blending and modifying based on fire retardant, for polylactic acid of polylactic acid
Have at present: graphite, organic phosphine, phosphate, ammonium polyphosphate and its compound, hypophosphites etc., but since physical property is (fire-retardant
Property, toughness) influence limit polylactic acid in the application in 3D printing field.
Summary of the invention
It is an object of the present invention to provide a kind of halogen-free flame-proof polylactic acid materials for 3D printing, with no analysis
Out, the advantages of high oxygen index (OI), meet V0 flame-retardancy requirements, and there is good toughness.
It is another object of the present invention to provide a kind of systems of above-mentioned halogen-free flame-proof polylactic acid material for 3D printing
Preparation Method.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of halogen-free flame-proof polylactic acid material for 3D printing is provided, by weight percentage, including following components:
Polylactic acid 53~78.6%, for example, 54%, 55%, 56%, 58%, 60%, 62%, 65%, 68%, 70%,
71%, 72%, 73.5%, 75%, 75.8% or 78% etc.；
Fire retardant 15~20%, such as 15.2%, 15.4%, 15.5%, 16%, 17%, 18%, 19% or 19.5%
Deng；
Plasticizer 2.5~5%, such as 2.7%, 2.9%, 3%, 3.2%, 3.5%, 4%, 5.2%, 4.5% or 4.8%
Deng；
Toughener 6~10%, for example, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.3%,
8.5%, 8.8%, 9%, 9.1%, 9.3%, 9.5% or 9.8% etc.；
Wherein, the fire retardant is compounded by piperazine pyrophosphate with melamine phosphate.
Fire retardant of the present invention using the compound of piperazine pyrophosphate and melamine phosphate as polylactic acid, and simultaneously
The dosage of toughener and plasticizer is adjusted, it is hereby achieved that having the advantages that without precipitation, high oxygen index (OI), and meets V0
The halogen-free flame-proof polylactic acid material that can be used for 3D printing of flame-retardancy requirements.Wherein, piperazine pyrophosphate and melamine phosphate
Compound belongs to phosphorus-nitrogen containing flame retardant, plays fire retardation simultaneously in gas phase and condensed phase, released when being thermally decomposed phosphoric acid,
The strong acid such as metaphosphoric acid and polyphosphoric acid promote substrate to be dehydrated into charcoal；A large amount of PO and PO can be also released when being thermally decomposed2Deng
Free radical captures H, HO, O the isoreactivity free radical generated in burning chain reaction；It decomposes and generates phosphorous glassy state
Substance is covered on substrate surface to completely cut off air, to prevent the release of fuel gas.The dosage of toughener and plasticizer it is excellent
Changing can make halogen-free flame-proof polylactic acid material while meeting V0 flame-retardancy requirements with the characteristic without precipitation, high oxygen index (OI), and have
There is good toughness, fully meets 3D printing demand.
As a preferred technical solution of the halogen-free flame-proof polylactic acid material for 3D printing, the polylactic acid exists
190 DEG C, the lower melt index of 2.16Kg load be 8g/10min, each auxiliary combination use of the polylactic acid and above-mentioned dosage can
To obtain the halogen-free flame-proof polylactic acid material haveing excellent performance.Specifically, polylactic acid of the invention is nature works institute, the U.S.
It produces, MI is 8g/10min (190 DEG C of .2.16Kg).
Wherein, by weight percentage, the fire retardant is by 40~70% piperazine pyrophosphates and 30~60% melamines
Phosphate compounds, and can play its fire retardation to the maximum extent.Wherein, weight hundred of the piperazine pyrophosphate in fire retardant
Point than be 40~70%, such as 41%, 42%, 43%, 45%, 48%, 50%, 52%, 55%, 56%, 58%, 60%,
62%, 65%, 67% or 69% etc.；Weight percent of the melamine phosphate in fire retardant is 30~60%, such as
31%, 32%, 34%, 35%, 37%, 38%, 39%, 40%, 42%, 45%, 48%, 50%, 52%, 55% or 58%
Deng.
Wherein, the melamine phosphate is selected from melamine pyrophosphate, orthophosphoric acid melamine, orthophosphoric acid two or three
Any one of poly cyanamid or at least two mixture.
Wherein, the plasticizer is selected from polyethylene glycol, POLYPROPYLENE GLYCOL, glyceryl triacetate, tributyl citrate, glucose
Any one of acid anhydrides, glycerol, lactic acid oligomer or at least two mixture.
Wherein, the toughener is selected from aliphatic polyester, aliphatic-aromatic copolyester, ethylene vinyl acetate, methyl
Any one of methylacrylate-butadiene-styrol copolymer or at least two mixture.
Wherein, by weight percentage, further include 0.2~1% antioxidant, for example, 0.21%, 0.23%, 0.25%,
0.28%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9% etc.；
Preferably, the antioxidant is antioxidant 1010 and/or irgasfos 168.
Wherein, by weight percentage, further include 0.2~1% lubricant, for example, 0.21%, 0.23%, 0.25%,
0.28%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9% etc.；
Preferably, the lubricant is selected from any one of stearic acid, calcium stearate, ethylene bis stearamide or at least two
The mixture of kind.
Wherein, by weight percentage, further include 0~10% filler, for example, 0.1%, 0.2%, 0.3%, 0.4%,
0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8% or
9% etc.；
Preferably, the filler is selected from fumed silica, superfine talcum powder, nano barium sulfate, montmorillonite, kaolin
Any one of or at least two mixture.
The present invention also provides a kind of preparation method of above-mentioned halogen-free flame-proof polylactic acid material for 3D printing, the preparation sides
Method the following steps are included:
S10, the polylactic acid is uniformly mixed with plasticizer, the first mixture is made；
S20, it will be mixed in toughener, filler, fire retardant, antioxidant and lubricant addition first mixture
It is even.The second mixture is made；
S30, second mixture is sent into melting and extruding pelletization in double screw extruder, the poly- cream of halogen-free flameproof is made
Sour material；
Polylactic acid is uniformly mixed by the present invention with plasticizer first in the preparation method of halogen-free flame-proof polylactic acid material,
The first mixture is made, then other auxiliary agents such as toughener, filler, fire retardant, antioxidant and lubricant are added first
In mixture, toughener, filler, fire retardant, antioxidant and lubricant can be well-dispersed in first in a short time and mixed
It closes in object, so as to the toughness, anti-flammability and oxygen index (OI) etc. for further increasing halogen-free flame-proof polylactic acid material.
Preferably, the draw ratio of the double screw extruder is 40:1；
Preferably, the temperature of extrusion is 180~200 DEG C, such as 182 DEG C, 185 DEG C, 188 DEG C, 190 DEG C, 192 DEG C, 195 DEG C
Or 198 DEG C etc..
Beneficial effects of the present invention: the present invention is using the compound of piperazine pyrophosphate and melamine phosphate as fire-retardant
Agent, while the dosage of plasticizer and toughener is optimized, halogen-free flame-proof polylactic acid material can be made to fully meet V0 fire-retardant
It is required that and fully meeting 3D printing demand with good toughness with the characteristic without precipitation, high oxygen index (OI), while also.
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
Weigh by weight 74.3 parts of polylactic acid, 5 parts of PEG2000,5 parts of aliphatic polyesters, 0.2 part of fumed silica,
10.5 parts of piperazine pyrophosphates, 4.5 parts of melamine pyrophosphates, 0.3 part of antioxidant 1010 and 0.2 part of lubricant；
Polylactic acid is uniformly mixed with plasticizer, then adds toughener, filler, fire retardant, antioxidant and lubrication
Agent uses draw ratio to be granulated for the double screw extruder melting extrusion of 40:1, and extrusion temperature is 180 DEG C~200 DEG C, will squeeze out grain
Material is molded into standard testing batten with injection molding machine and carries out flame retardant test.
Embodiment 2
59 parts of polylactic acid, 5 parts of POLYPROPYLENE GLYCOLs, 5 parts of MBS, 10 parts of talcum powder, 14 parts of piperazine pyrophosphates, 6 are weighed by weight
Part orthophosphoric acid melamine, 0.2 part of antioxidant 1010,0.3 part of irgasfos 168 and 0.5 part of calcium stearate；
Polylactic acid is uniformly mixed with plasticizer, then adds toughener, filler, fire retardant, antioxidant and lubrication
Agent uses draw ratio to be granulated for the double screw extruder melting extrusion of 40:1, and extrusion temperature is 180 DEG C~200 DEG C, will squeeze out grain
Material is molded into standard testing batten with injection molding machine and carries out flame retardant test.
Embodiment 3
59 parts of polylactic acid, 5 parts of glycerol, 5 parts of EVA, 2800,10 parts of nano barium sulfates, 12 parts of pyrophosphoric acids are weighed by weight
Piperazine, 8 parts of two melamines of orthophosphoric acid (DMPY), 0.2 part of antioxidant 1010,0.3 part of irgasfos 168 and 0.5 part of ethylene are double hard
Acyl amine；
Polylactic acid is uniformly mixed with plasticizer, then adds toughener, filler, fire retardant, antioxidant and lubrication
Agent uses draw ratio to be granulated for the double screw extruder melting extrusion of 40:1, and extrusion temperature is 180 DEG C~200 DEG C, will squeeze out grain
Material is molded into standard testing batten with injection molding machine and carries out flame retardant test.
Embodiment 4
64 parts of polylactic acid, 5 parts of tributyl citrate, 5 parts of MBS, 5 parts of montmorillonites, 10 parts of pyrophosphoric acid piperazines are weighed by weight
Piperazine, 10 parts of two melamines of orthophosphoric acid (DMPY), 0.2 part of antioxidant 1010,0.3 part of irgasfos 168 and 0.5 part of ethylene are double stearic
Amide；
Polylactic acid is uniformly mixed with plasticizer, then adds toughener, filler, fire retardant, antioxidant and lubrication
Agent uses draw ratio to be granulated for the double screw extruder melting extrusion of 40:1, and extrusion temperature is 180 DEG C~200 DEG C, will squeeze out grain
Material is molded into standard testing batten with injection molding machine and carries out flame retardant test.
Embodiment 5
64 parts of polylactic acid, 5 parts of tributyl citrate, 5 parts of MBS, 2 parts of fumed silicas, 3 parts of kaolinites are weighed by weight
Soil, 10 parts of piperazine pyrophosphates, 10 parts of two melamines of orthophosphoric acid (DMPY), 0.2 part of antioxidant 1010,0.3 part of irgasfos 168 and
0.5 part of ethylene bis stearamide；
Polylactic acid is uniformly mixed with plasticizer, then adds toughener, filler, fire retardant, antioxidant and lubrication
Agent uses draw ratio to be granulated for the double screw extruder melting extrusion of 40:1, and extrusion temperature is 180 DEG C~200 DEG C, will squeeze out grain
Material is molded into standard testing batten with injection molding machine and carries out flame retardant test.
Comparative example 1
This comparative example and above-described embodiment 5 are essentially identical, and difference is that fire retardant is 20 parts by weight orthophosphoric acid, two melamine
Amine (DMPY).
Comparative example 2
This comparative example and above-described embodiment 5 are essentially identical, and difference is that fire retardant is 20 parts by weight piperazine pyrophosphates.
Comparative example 3
This comparative example and above-described embodiment 5 are essentially identical, and difference is plasticizer and toughener, filler, fire retardant, resists
Oxygen agent and lubricant are added in polylactic acid together and are uniformly mixed.
Comparative example 4
This comparative example and above-described embodiment 5 are essentially identical, and difference is that fire retardant is 20 parts by weight orthophosphoric acid, two melamine
Amine (DMPY), and plasticizer is added in polylactic acid together with toughener, filler, fire retardant, antioxidant and lubricant and mixes
It is even.
Comparative example 5
This comparative example and above-described embodiment 5 are essentially identical, and difference is that fire retardant is 20 parts by weight piperazine pyrophosphates, and increases
Modeling agent, which is added in polylactic acid together with toughener, filler, fire retardant, antioxidant and lubricant, to be uniformly mixed.
Oxygen index (OI) according to the made sample of the method testing example 1~5 and comparative example 1~5 of GB2406.2-2009 resistance
Combustion property, according to the precipitation of the made sample of the method testing example 1~5 and comparative example 1~5 of UL 746C, elongation at break
It is tested with tensile strength according to ASTM, test result is shown in Table 1:
It is surveyed as it can be seen from table 1 material obtained by Examples 1 to 5 is able to satisfy V0 flame-retardancy requirements, oxygen index (OI) and precipitation property
Examination meets the flame retardant test requirement for 3D printing material, and has good toughness.
In addition, the dosage of toughener and plasticizer is all modified to 4 parts by weight on the basis of embodiment 1, measure
The elongation at break of batten is 11.6%, tensile strength 34.8MPa.This explanation use is by piperazine pyrophosphate, melamine phosphorus
When the compound of hydrochlorate is as fire retardant, the dosage of toughener and plasticizer is adjusted, halogen-free flame-proof polylactic acid material can be made
Anti-flammability and toughness are optimal.
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 (10)
1. a kind of halogen-free flame-proof polylactic acid material for 3D printing, which is characterized in that by weight percentage, including with the following group
Point:
Wherein, the fire retardant is compounded by piperazine pyrophosphate with melamine phosphate.
2. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that the polylactic acid
Melt index under 190 DEG C, 2.16Kg load is 8g/10min.
3. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that percentage by weight
Than meter, the fire retardant is compounded by 40~70% piperazine pyrophosphates with 30~60% melamine phosphates.
4. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that the melamine
Amine phosphate is selected from any one of melamine pyrophosphate, orthophosphoric acid melamine, two melamine of orthophosphoric acid or at least
Two kinds of mixture.
5. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that the plasticizer
In polyethylene glycol, POLYPROPYLENE GLYCOL, glyceryl triacetate, tributyl citrate, glucose anhydride, glycerol, lactic acid oligomer
It is any or at least two mixture.
6. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that the toughener
Selected from aliphatic polyester, aliphatic-aromatic copolyester, ethylene vinyl acetate, methyl methacrylate-butadiene-benzene second
Any one of alkene copolymer or at least two mixture.
7. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that percentage by weight
It further include 0.2~1% antioxidant than meter；
Preferably, the antioxidant is antioxidant 1010 and/or irgasfos 168.
8. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that percentage by weight
It further include 0.2~1% lubricant than meter；
Preferably, the lubricant is selected from any one of stearic acid, calcium stearate, ethylene bis stearamide or at least two
Mixture.
9. the halogen-free flame-proof polylactic acid material according to claim 1 for 3D printing, which is characterized in that percentage by weight
It further include 0~10% filler than meter；
Preferably, the filler is in fumed silica, superfine talcum powder, nano barium sulfate, montmorillonite, kaolin
It is any or at least two mixture.
10. the preparation method of the halogen-free flame-proof polylactic acid material according to any one of claims 1 to 9 for 3D printing,
Characterized by comprising the following steps:
S10, the polylactic acid is uniformly mixed with plasticizer, the first mixture is made；
S20, it will be mixed in the toughener, filler, fire retardant, antioxidant and lubricant addition first mixture
It is even.The second mixture is made；
S30, second mixture is sent into melting and extruding pelletization in double screw extruder, halogen-free flame-proof polylactic acid material is made
Material；
Preferably, the draw ratio of the double screw extruder is 40:1；
Preferably, the temperature of extrusion is 180~200 DEG C.
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| CN110655767A (en) * | 2019-10-24 | 2020-01-07 | 福州大学 | Toughened polylactic acid 3D printing extrusion wire and preparation method thereof |
| CN111393734A (en) * | 2020-04-23 | 2020-07-10 | 四川轻化工大学 | Halogen-free flame retardant, halogen-free flame-retardant low-density polyethylene material and preparation method thereof |
| CN112030267A (en) * | 2020-08-21 | 2020-12-04 | 安徽同光邦飞生物科技有限公司 | Preparation method of flame-retardant polylactic acid material for 3D printing |
| CN112759905A (en) * | 2019-11-01 | 2021-05-07 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
| CN115433399A (en) * | 2022-10-09 | 2022-12-06 | 廊坊北化高分子材料有限公司 | Flame-retardant waterproof thermoplastic elastomer material, preparation method thereof and waterproof roll |
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| CN110655767A (en) * | 2019-10-24 | 2020-01-07 | 福州大学 | Toughened polylactic acid 3D printing extrusion wire and preparation method thereof |
| CN112759905A (en) * | 2019-11-01 | 2021-05-07 | 南通林格橡塑制品有限公司 | Halogen-free flame-retardant polylactic acid mixture |
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| CN111393734A (en) * | 2020-04-23 | 2020-07-10 | 四川轻化工大学 | Halogen-free flame retardant, halogen-free flame-retardant low-density polyethylene material and preparation method thereof |
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Application publication date: 20190301 |