CN105670254A - Preparation method of polylactic acid composite material used for hot-melt 3D printing - Google Patents
Preparation method of polylactic acid composite material used for hot-melt 3D printing Download PDFInfo
- Publication number
- CN105670254A CN105670254A CN201610101923.5A CN201610101923A CN105670254A CN 105670254 A CN105670254 A CN 105670254A CN 201610101923 A CN201610101923 A CN 201610101923A CN 105670254 A CN105670254 A CN 105670254A
- Authority
- CN
- China
- Prior art keywords
- preparation
- adopted
- lactic acid
- mixture
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2205/03—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
Abstract
The invention discloses a preparation method of a polylactic acid composite material used for hot-melt 3D printing. The preparation method comprises the following steps: adding set raw materials into a high-speed mixer according to a proportion, wherein the mass percent of all the raw materials is as follows: 55-75% of polylactic acid, 10-30% of halogen-free environmentally-friendly composite flame retardant, 1-5% of ethylene-vinyl acetate copolymer, 1-5% of compatilizer, 0.3-0.6% of antioxygen, 1-5% of flexibilizer, 0.5-2% of lubricating agent, 0.1-2% of nucleating agent, 0.5-2% of plasticizer and 0.1-0.3% of ant-dripping agent. The mixed mixture is added into a screw extruder to be subjected to melt mixing; then, the product subjected to the melt mixing is cooled through a sink to be stretched into a strand of which the diameter is Phi 1.75mm+/-0.2mm to obtain the polylactic acid composite material. The composite material prepared with the method has the advantages of good liquidity and low molding shrinkage and is suitable for quick hot-melt 3D printing forming.
Description
Technical field
The present invention relates to technical field of polymer composite materials, particularly relate to the preparation method of a kind of lactic acid composite material printed for hot-melting type 3D.
Background technology
In recent years, rapid shaping obtains significant progress, and wherein three-dimensional (3D) printing technique is increasingly mature and industrialization, applies gradually in fields such as biotechnology, aerospace, building, designs. 3D print have several, be the most also least cost be plastic hot melt deposition printing shaping, it may also be useful to plastic strip, heat at die cavity and shower nozzle place, fast plastics be melt into liquid, then print 3D goods layer by layer. More plastics variety is used to have ABS, nylon, poly(lactic acid) etc.
Poly(lactic acid), by the plastics of lactic acid polymerizes, fully biodegradable, is green ecological biological plastics completely, does not consume fossil energy, obtain application in fields such as medicine, medical treatment, organizational projects. But the flame retardant resistance of poly(lactic acid) own is not good, its oxygen index only has about 18%, for inflammable material, therefore some Application Areas needs it fire-retardant, the fire-retardant of poly(lactic acid) mostly is Halogen flame-retardant system, but the restriction (such as RoHS instruction etc.) being subject to multiple environmental regulation at present, is therefore badly in need of development environment friendly halogen-free fireproof poly(lactic acid), to expand the range of application of poly(lactic acid). The property of poly(lactic acid) own is crisp simultaneously, become more crisp after adding fire retardant, even cannot use, in addition, 3D printing shaping is rapid shaping, needing material to have high mobility, and the decline of flame-proof polylactic acid general mobility is relatively big, the preparation therefore taking into account the environmental protection flame retardant lactic acid composite material of high tenacity, high flowing is current industry difficult point urgently to be resolved hurrily.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of lactic acid composite material printed for hot-melting type 3D, the matrix material flowing property prepared by the method is excellent, and molding shrinkage is low, is suitable for hot-melting type 3D printing speed shaping.
For a preparation method for the lactic acid composite material that hot-melting type 3D prints, described method comprises:
The starting material of setting are joined in high-speed mixer in proportion;Wherein, each raw-material mass percent is: the poly(lactic acid) of 55～75%, the halogen-free environmental composite flame-retardant agent of 10～30%, 1～5% ethylene-vinyl acetate copolymer, 1～5% compatilizer, 0.3～0.6% oxidation inhibitor, 1～5% toughner, 0.5～2% lubricant, the nucleator of 0.1～2%, the softening agent of 0.5～2% and 0.1～0.3% anti-dripping agent, above-mentioned each raw-material mass percent sum is 100%;
Mixed mixture, after described high-speed mixer high speed mixes 1 minute, is joined in screw extrusion press and carries out melting mixing by above-mentioned starting material; Wherein, the screw slenderness ratio of described screw extrusion press is 32～40, and screw combinations is moderate shear rate combinations mode, and temperature is between 140～190 DEG C;
Again the product after melting mixing is cooled through tank, pull into the silk bar of diameter of phi 1.75mm ± 0.2mm, obtain described lactic acid composite material.
The poly(lactic acid) adopted is poly-L-lactic acid, and its melt flow index is between 10～40g/10min, is 15～30g/10min further.
The halogen-free environmental composite flame-retardant agent adopted is the mixture of aluminum diethylphosphinate, melamine polyphosphate and linear phenolic resin, and its mass ratio is 1:1:0.2.
The compatilizer adopted is the mixture of polycthylene grafted maleic anhydride, styrene-acrylonitrile-glycidyl methacrylate terpolymer and ethylene butyl acrylate multipolymer;
The oxidation inhibitor adopted is the mixture of antioxidant 1010 and 168, and its mass ratio is between 1:1～1:5, it is preferable to 1:2.
The toughner adopted is polyphosphonitrile and the mixture of MBS core-shell type MBS, and its mass ratio is 1:2.
The lubricant adopted is one or more the mixture in ethylene bis stearamide, oxidized polyethlene wax and carnauba wax.
The nucleator adopted is the mixture of sebacic acid dibenzoyl hydrazine and nano silicon.
The softening agent adopted is triphenylphosphate;
The anti-dripping agent adopted is ptfe micropowder.
Described screw extrusion press is peg type single screw extrusion machine, twin screw extruder or reciprocating single screw extrusion machine;
More preferably twin screw extruder.
As seen from the above technical solution provided by the invention, the matrix material flowing property prepared by aforesaid method is excellent, and molding shrinkage is low, and flame retardant properties reaches UL-94V0 level, and impelling strength can reach 15kJ/m2Above, it is applicable to hot-melting type 3D printing speed shaping, can be used for the fire-retardant 3D of requirement and print goods.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in embodiment being described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for the those of ordinary skill of this area, under the prerequisite not paying creative work, it is also possible to obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is preparation method's schematic flow sheet that the embodiment of the present invention is provided for the lactic acid composite material that hot-melting type 3D prints;
Fig. 2 is the work structuring schematic diagram of twin screw extruder for the preparation of lactic acid composite material in example of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to protection scope of the present invention.
The embodiment of the present invention being described in further detail below in conjunction with accompanying drawing, be illustrated in figure 1 preparation method's schematic flow sheet that the embodiment of the present invention is provided for the lactic acid composite material that hot-melting type 3D prints, described method comprises:
Step 11: the starting material of setting are joined in high-speed mixer in proportion;
In this step, above-mentioned each raw-material mass percent can be: the poly(lactic acid) of 55～75%, the halogen-free environmental composite flame-retardant agent of 10～30%, 1～5% ethylene-vinyl acetate copolymer (EVA), 1～5% compatilizer, 0.3～0.6% oxidation inhibitor, 1～5% toughner, 0.5～2% lubricant, the nucleator of 0.1～2%, the softening agent of 0.5～2% and 0.1～0.3% anti-dripping agent, above-mentioned each raw-material mass percent sum is 100%.
In specific implementation, the poly(lactic acid) adopted is poly-L-lactic acid (PLLA), and its melt flow index (MI) is 10～40g/10min (190 DEG C, 2.16kg) between, if polylactic acid molecule amount is too high here, melting viscosity is big, and shower nozzle drippage is slow, affects print speed; If polylactic acid molecule amount is too low, goods mechanical property is not good, it is preferable to the poly(lactic acid) of 15～30g/10min.
The halogen-free environmental composite flame-retardant agent adopted is the mixture of aluminum diethylphosphinate, melamine polyphosphate and linear phenolic resin, and its mass ratio is 1:1:0.2. Aluminum diethylphosphinate is novel environment friendly inorganic combustion inhibitor, use composite with melamine polyphosphate, it is possible to reach flame retardant synergistic effect; Novolac, mainly as char-forming agent, increases into layer of charcoal density, thus plays fire retardation.
In the ethylene-vinyl acetate copolymer EVA adopted, VA content is 15～35%, melt flow index MI is 5～30g/10min (190 DEG C, 2.16kg). Adding the toughness that EVA can improve matrix material, can increase 3D prints the cohesiveness between each layer (weld mark strength) simultaneously.
The compatilizer adopted is the mixture of polycthylene grafted maleic anhydride (percentage of grafting is 1～4%), styrene-acrylonitrile-glycidyl methacrylate terpolymer and ethylene butyl acrylate multipolymer; Adopt, with the compatilizer of epoxide group, also there is the effect to poly(lactic acid) chain extension, thus improve the toughness of lactic acid composite material further.
The oxidation inhibitor adopted is the mixture of antioxidant 1010 and 168, and its mass ratio is at 1:1～1:5, it is preferable that 1:2, avoids the degraded in the course of processing.
The toughner adopted is polyphosphonitrile and the mixture of MBS core-shell type MBS, and its mass ratio is 1:2, and polyphosphonitrile molecular-weight average is between 40000～100000. Polyphosphonitrile rubber has fire retardation simultaneously; MBS is hud typed elastomerics, and core is crosslinked polybutadiene rubber, plays toughening effect, and shell is methyl methacrylate polymer, good with the consistency of poly(lactic acid).
The lubricant adopted is one or more the mixture in ethylene bis stearamide (EBS), oxidized polyethlene wax (OPE) and carnauba wax. Adopting hybrid lubricant that 3D can be made to print more smooth and easy, product surface is bright, attractive in appearance simultaneously.
The nucleator adopted is the mixture of sebacic acid dibenzoyl hydrazine and nano silicon. Add crystallization velocity and the crystallization property improved that nucleator can improve poly(lactic acid), thus improve printing speed efficiency and product properties. Wherein nano silicon can, as nucleator, also be both toughener, it is possible to improves intensity and the thermotolerance of lactic acid composite material.
The softening agent adopted is triphenylphosphate (TPP), can improve the mobility of poly(lactic acid) on the one hand, be suitable for rapid shaping;Can also have fire retardation on the other hand.
The anti-dripping agent adopted is ptfe micropowder, drips, thus reach UL-94V0 level during for preventing matrix material from burning.
Step 12: mixed mixture, after described high-speed mixer high speed mixes 1 minute, is joined in screw extrusion press and carries out melting mixing by above-mentioned starting material;
In this step, the screw slenderness ratio of described screw extrusion press is 32～40, and screw combinations is moderate shear rate combinations mode, and temperature is between 140～190 DEG C.
In specific implementation, described screw extrusion press is peg type single screw extrusion machine, twin screw extruder or reciprocating single screw extrusion machine; More preferably twin screw extruder.
Step 13: cooled through tank by the product after melting mixing again, pulls into the silk bar of diameter of phi 1.75mm ± 0.2mm, obtains described lactic acid composite material.
Above-mentioned obtained lactic acid composite material can for fusion sediment 3D printer.
With concrete example, above-mentioned preparation method and prepared product are described in detail below, each raw-material percent mass proportioning that following table 1 adopts for embodiment 1-3:
Table 1
Then the starting material of above-described embodiment 1-3 are joined in high-speed mixer by formula rate;
Mixture is joined melting mixing in screw extrusion press by high-speed mixing after 1 minute;
And then through tank cooling, pull into the silk bar of diameter of phi 1.75mm ± 0.2mm, obtain for the lactic acid composite material that fusion sediment 3D printer uses.
In above-mentioned preparation process, the screw extrusion press used is peg type single screw extrusion machine, twin screw extruder or reciprocating single screw extrusion machine, preferred twin screw extruder, its screw slenderness ratio is 32～40, screw combinations is moderate shear rate combinations mode, the work structuring schematic diagram of the twin screw extruder being illustrated in figure 2 in example of the present invention for the preparation of lactic acid composite material, the working temperature of this twin screw extruder is between 140～190 DEG C.
Then the lactic acid composite material prepared by above-described embodiment 1-3 is carried out performance test by following standard:
Melt flow rate (MFR) (MI): carry out according to GB/T3682-2000 standard
Tensile strength and elongation at break: carry out according to GB/T1040-2006 standard.
Flexural strength and modulus in flexure: carry out according to GB/T9341-2008 standard.
Letter fine strain of millet notch shock performance: carry out according to GB/T1043-2008 standard.
Heat-drawn wire: carry out according to GB/T1634-2004 standard; Maximum deflection normal stress 0.46MPa, heat-up rate: 2 DEG C/min.
Molding shrinkage: undertaken by GB/T15585-1995 standard.
Oxygen index: perform by GB/T2406-2009 standard.
Flame retardant resistance: perform by UL-94 standard.
The performance perameter of the lactic acid composite material prepared by final embodiment 1-3 is as shown in table 2 below:
Table 2
As can be seen from Table 2: after adding compatilizer, toughner in poly(lactic acid), the fire-retardant property of matrix material improves greatly, and impelling strength improves greatly, and molding shrinkage obviously declines, the melt flow rate (MFR) decline of matrix material is few simultaneously, still meets the requirement that melting 3D prints.
It thus is seen that matrix material flowing property prepared by the method provided according to the embodiment of the present invention is excellent, molding shrinkage is low, and flame retardant properties reaches UL-94V0 level, and impelling strength can reach 15kJ/m2Above, being applicable to hot-melting type 3D printing speed shaping, can be used for the fire-retardant 3D of requirement and print goods, its over-all properties improves greatly, and the dimensional stability of obtained goods increases, thus is conducive to improving the precision printing goods.
The above; it is only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, any it is familiar with those skilled in the art in the technical scope of present disclosure; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention. Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim book.
Claims (9)
1. the preparation method of the lactic acid composite material printed for hot-melting type 3D, it is characterised in that, described method comprises:
The starting material of setting are joined in high-speed mixer in proportion; Wherein, each raw-material mass percent is: the poly(lactic acid) of 55～75%, the halogen-free environmental composite flame-retardant agent of 10～30%, 1～5% ethylene-vinyl acetate copolymer, 1～5% compatilizer, 0.3～0.6% oxidation inhibitor, 1～5% toughner, 0.5～2% lubricant, the nucleator of 0.1～2%, the softening agent of 0.5～2% and 0.1～0.3% anti-dripping agent, above-mentioned each raw-material mass percent sum is 100%;
Mixed mixture, after described high-speed mixer high speed mixes 1 minute, is joined in screw extrusion press and carries out melting mixing by above-mentioned starting material; Wherein, the screw slenderness ratio of described screw extrusion press is 32～40, and screw combinations is moderate shear rate combinations mode, and temperature is between 140～190 DEG C;
Again the product after melting mixing is cooled through tank, pull into the silk bar of diameter of phi 1.75mm ± 0.2mm, obtain described lactic acid composite material.
2. preparation method according to claim 1, it is characterised in that,
The poly(lactic acid) adopted is poly-L-lactic acid, and its melt flow index is between 10～40g/10min, is 15～30g/10min further.
3. preparation method according to claim 1, it is characterised in that,
The halogen-free environmental composite flame-retardant agent adopted is the mixture of aluminum diethylphosphinate, melamine polyphosphate and linear phenolic resin, and its mass ratio is 1:1:0.2.
4. preparation method according to claim 1, it is characterised in that,
The compatilizer adopted is the mixture of polycthylene grafted maleic anhydride, styrene-acrylonitrile-glycidyl methacrylate terpolymer and ethylene butyl acrylate multipolymer;
The oxidation inhibitor adopted is the mixture of antioxidant 1010 and 168, and its mass ratio is between 1:1～1:5, it is preferable to 1:2.
5. preparation method according to claim 1, it is characterised in that,
The toughner adopted is polyphosphonitrile and the mixture of MBS core-shell type MBS, and its mass ratio is 1:2.
6. preparation method according to claim 1, it is characterised in that,
The lubricant adopted is one or more the mixture in ethylene bis stearamide, oxidized polyethlene wax and carnauba wax.
7. preparation method according to claim 1, it is characterised in that,
The nucleator adopted is the mixture of sebacic acid dibenzoyl hydrazine and nano silicon.
8. preparation method according to claim 1, it is characterised in that,
The softening agent adopted is triphenylphosphate;
The anti-dripping agent adopted is ptfe micropowder.
9. preparation method according to claim 1, it is characterised in that,
Described screw extrusion press is peg type single screw extrusion machine, twin screw extruder or reciprocating single screw extrusion machine;
More preferably twin screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610101923.5A CN105670254A (en) | 2016-02-24 | 2016-02-24 | Preparation method of polylactic acid composite material used for hot-melt 3D printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610101923.5A CN105670254A (en) | 2016-02-24 | 2016-02-24 | Preparation method of polylactic acid composite material used for hot-melt 3D printing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105670254A true CN105670254A (en) | 2016-06-15 |
Family
ID=56305963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610101923.5A Pending CN105670254A (en) | 2016-02-24 | 2016-02-24 | Preparation method of polylactic acid composite material used for hot-melt 3D printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670254A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167606A (en) * | 2016-07-29 | 2016-11-30 | 苏州秉创科技有限公司 | A kind of PVC base modification 3D printing consumables |
| CN106280330A (en) * | 2016-08-09 | 2017-01-04 | 东莞市晶谷新材料技术有限公司 | A kind of wood plastic composite for 3D printing and preparation method thereof |
| CN107383817A (en) * | 2017-08-23 | 2017-11-24 | 广东波斯科技股份有限公司 | A kind of Biodegradable low-cost flame-retardant 3D printing consumptive material and its preparation method and application |
| CN108467580A (en) * | 2018-03-19 | 2018-08-31 | 华东理工大学 | A kind of 3D low temperature printed material and preparation method thereof |
| CN109575539A (en) * | 2018-10-31 | 2019-04-05 | 诺思贝瑞新材料科技（苏州）有限公司 | A kind of high-ductility matt modified polylactic acid material and preparation method thereof for 3D printing |
| CN110511697A (en) * | 2019-09-09 | 2019-11-29 | 广州飞胜智能科技股份有限公司 | One kind can 3D printing modified hot melt adhesive composite material, preparation method and applications |
| CN112080113A (en) * | 2020-09-17 | 2020-12-15 | 方金丹 | High-toughness flame-retardant PLA composite material and preparation method thereof |
| CN113185818A (en) * | 2021-04-09 | 2021-07-30 | 浙江汇盎新材料科技有限公司 | Biodegradable polylactic acid high-transparency film and preparation method thereof |
| CN114981358A (en) * | 2020-01-16 | 2022-08-30 | 弗洛里昂转换包装有限公司 | Polylactic acid flame retardant blend |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304895A (en) * | 2013-06-14 | 2013-09-18 | 慈溪金岛塑化有限公司 | Efficient halogen-free intumescent flame-retardant polypropylene material |
| CN104725802A (en) * | 2015-03-27 | 2015-06-24 | 北京石油化工学院 | Preparation method of polylactic acid composite material for hot-melt 3D printing |
| CN104893334A (en) * | 2015-06-08 | 2015-09-09 | 东北林业大学 | Green environment-friendly 3D printing wire and preparation method thereof |
-
2016
- 2016-02-24 CN CN201610101923.5A patent/CN105670254A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304895A (en) * | 2013-06-14 | 2013-09-18 | 慈溪金岛塑化有限公司 | Efficient halogen-free intumescent flame-retardant polypropylene material |
| CN104725802A (en) * | 2015-03-27 | 2015-06-24 | 北京石油化工学院 | Preparation method of polylactic acid composite material for hot-melt 3D printing |
| CN104893334A (en) * | 2015-06-08 | 2015-09-09 | 东北林业大学 | Green environment-friendly 3D printing wire and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167606A (en) * | 2016-07-29 | 2016-11-30 | 苏州秉创科技有限公司 | A kind of PVC base modification 3D printing consumables |
| CN106280330A (en) * | 2016-08-09 | 2017-01-04 | 东莞市晶谷新材料技术有限公司 | A kind of wood plastic composite for 3D printing and preparation method thereof |
| CN107383817A (en) * | 2017-08-23 | 2017-11-24 | 广东波斯科技股份有限公司 | A kind of Biodegradable low-cost flame-retardant 3D printing consumptive material and its preparation method and application |
| CN108467580A (en) * | 2018-03-19 | 2018-08-31 | 华东理工大学 | A kind of 3D low temperature printed material and preparation method thereof |
| CN108467580B (en) * | 2018-03-19 | 2020-10-23 | 华东理工大学 | 3D low-temperature printing material and preparation method thereof |
| CN109575539A (en) * | 2018-10-31 | 2019-04-05 | 诺思贝瑞新材料科技（苏州）有限公司 | A kind of high-ductility matt modified polylactic acid material and preparation method thereof for 3D printing |
| CN109575539B (en) * | 2018-10-31 | 2021-01-05 | 诺思贝瑞新材料科技（苏州）有限公司 | High-toughness matte modified polylactic acid material for 3D printing and preparation method thereof |
| CN110511697A (en) * | 2019-09-09 | 2019-11-29 | 广州飞胜智能科技股份有限公司 | One kind can 3D printing modified hot melt adhesive composite material, preparation method and applications |
| CN114981358A (en) * | 2020-01-16 | 2022-08-30 | 弗洛里昂转换包装有限公司 | Polylactic acid flame retardant blend |
| CN112080113A (en) * | 2020-09-17 | 2020-12-15 | 方金丹 | High-toughness flame-retardant PLA composite material and preparation method thereof |
| CN113185818A (en) * | 2021-04-09 | 2021-07-30 | 浙江汇盎新材料科技有限公司 | Biodegradable polylactic acid high-transparency film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105670254A (en) | Preparation method of polylactic acid composite material used for hot-melt 3D printing | |
| JP5950576B2 (en) | Thermoplastic flame retardant alloy and process for its preparation | |
| CN104725802A (en) | Preparation method of polylactic acid composite material for hot-melt 3D printing | |
| US11560473B2 (en) | Dimensionally stable acrylic alloy for 3-D printing | |
| CN108239391B (en) | Light flame-retardant reinforced polyamide composition and preparation method thereof | |
| CN104918997A (en) | Polybutylene terephthalate resin composition, and molded article | |
| JPS6160746A (en) | Thermoplastic resin composition | |
| CN103183935B (en) | High-ductility PBT/PC (polybutylece terephthalate/polycarbonate) alloy and preparation method thereof | |
| CN112646310B (en) | PC/ABS composite material and preparation method and application thereof | |
| JP2019119888A (en) | Thermoplastic resin composition for blow molding, and molded article molded from the same | |
| CN110105738B (en) | Flame-retardant PC/ABS material and preparation method and application thereof | |
| CN107033575B (en) | Laser direct organization polycarbonate Alloys composition, preparation and application | |
| CN107513255A (en) | A kind of 3D printing toughness reinforcing heat-resisting PET material and preparation method thereof | |
| CN107778638A (en) | A kind of halogen-free flame-retardant ultra-high molecular weight polyvinyl material and preparation method thereof | |
| CN104497532A (en) | Halogen-free flame-retardant high-gloss high-glass fiber reinforced PC material and preparation method thereof | |
| CN105111703A (en) | Preparation method of conductive polylactic acid composite for thermal fusion 3D printing | |
| CN109575503A (en) | A kind of fretting map flame-proof ABS laser engraving material and preparation method thereof | |
| JPS60260647A (en) | Thermoplastic forming composition and manufacture | |
| CN102040809A (en) | Polyethylene terephthalate composite material and method for preparing same | |
| CN110283441B (en) | Mesoporous molecular sieve compound laser direct forming material and application thereof | |
| JP2019116570A (en) | Heat storage resin composition, manufacturing method therefor and molded body | |
| JP2006130924A (en) | Multi-layer structure | |
| CN104559023A (en) | High-strength smooth ABS/PC (acrylonitrile-butadiene-styrene/polycarbonate) alloy material for 3D printing, and preparation method and application thereof | |
| CN109796740B (en) | Stain-resistant PC/PET alloy and preparation method thereof | |
| JP4921923B2 (en) | Resin composition for extrusion molding, molded product and laminated product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160615 |
|
| RJ01 | Rejection of invention patent application after publication |