CN103665802B - A kind of preparation method of the poly-lactic acid material for 3D printing - Google Patents
A kind of preparation method of the poly-lactic acid material for 3D printing Download PDFInfo
- Publication number
- CN103665802B CN103665802B CN201310620288.8A CN201310620288A CN103665802B CN 103665802 B CN103665802 B CN 103665802B CN 201310620288 A CN201310620288 A CN 201310620288A CN 103665802 B CN103665802 B CN 103665802B
- Authority
- CN
- China
- Prior art keywords
- poly
- lactic acid
- temperature
- diameter
- nano inorganic
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
Abstract
A kind of preparation method of the poly-lactic acid material for 3D printing, specifically use inorganic nano material toughening modifying, the method first utilizes ultrasonication technology that nano inorganic toughner coupling agent is carried out organic modification of surface, again by through the nano inorganic toughner of modification and poly(lactic acid), softening agent, dispersion agent grinds, dispersion, mixing, eventually pass extruding pelletization, drawing process technology, the obtained toughening modified polylactic acid material being applicable to 3D printing technique, overcome existing 3D and print the poor toughness of poly-lactic acid material and the defect of poor processability, simple to operate, be easy to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of 3D printed material, be specifically related to a kind of preparation method of the poly-lactic acid material for 3D printing.
Background technology
3D printing technique is also known as increasing material manufacturing technology, be actually a kind of emerging technology in rapid shaping field, it is a kind of based on digital model file, uses powdery metal or plastics etc. can jointing material, is carried out the technology of constructed object by the mode successively printed.Ultimate principle is layered manufacturing, successively increases the technology that material generates 3D solid.At present, 3D printing technique is divided into again individual 3D printing technique and industrial 3D printing technique, and individual 3D printing technique receives the high praise of each side personage and likes, prospect is very wide.
In individual 3D printing technique, conventional a kind of technical matters is melted extrusion modeling forming technique (FDM), principle utilizes thermoplastic, polymeric materials in the molten state, squeeze out from shower nozzle, solidify and form the thin layer of outline shape, then superpose from level to level and finally form product.Therefore the macromolecular material that individual 3D prints needs to have excellent processing characteristics, namely not only lower melt temperature to be had, good melt fluidity and fast cooling time, also must have very little cooling meat rate and homogeneous structure, so just can not occur when 3D printing shaping that interiors of products stress distribution is uneven different with cooling meat rate, cause the underproof problem of the product printed.
Individual 3D conventional in the market prints macromolecular material mainly poly(lactic acid), ABS resin (acrylonitrile-butadiene-styrene terpolymer), nylon etc., and have nontoxic due to poly(lactic acid), without pungent smell, higher tensile strength, modulus of compression, melt temperature is lower, excellent biocompatibility, biodegradability, cooling meat rate is little, and the plurality of advantages such as transparent easy dyeing are more subject to liking of people and pay close attention to; But the matter that poly(lactic acid) has is hard, toughness is poor, shortage is flexible and elasticity, its application on the individual 3D printing technique of very easily diastrophic drawbacks limit.
Also little as the modification technology documents and materials of individual 3D printed material for poly(lactic acid) at present.Due to the backwardness of technological method and equipment, the traditional material modified and method of many uses is carried out the poly-lactic acid material of modification and is not suitable for individual 3D printing technique.In traditional method of modifying, the material modified of filling blend does not spread out completely in poly(lactic acid) system, thus cause the interiors of products stress distribution when 3D printing shaping uneven different with cooling meat rate, processing characteristics obviously reduces, thus, can correct modification method for preparing be selected to meet and be suitable for the requirement of 3D printing technique to material to modified poly-lactic acid material be very crucial.
China Patent Publication No. CN103146164A discloses a kind of poly-lactic acid material nano material toughened for rapid shaping and preparation method thereof, the method utilizes twin screw extruder to carry out blending extrusion modification to polyacrylic acid ester microsphere and poly(lactic acid), improve the defect of poly(lactic acid) poor toughness, but polyacrylic acid ester microsphere add the heterogeneity causing poly(lactic acid) system structure, processing characteristics obviously reduces, and has had a strong impact on the printing shaping of product.
China Patent Publication No. CN103087489A discloses a kind of modified polylactic acid material and preparation method thereof, the method polyether polyamide elastomer and polynite are as properties-correcting agent, modified device is done with twin screw extruder, enhance tensile strength and the toughness of poly(lactic acid), but directly by polyether polyamide elastomer in the method, polynite and the blended instrument blending extrusion of poly(lactic acid) twin screw, equipment is single, the blended time is short, cause the polyether polyamide elastomer of filling blend and polynite not to spread out completely in poly(lactic acid) system and form homogeneous structure, during printing shaping, interiors of products stress dispersion is uneven different with cooling meat rate, poor processability, thus the toughening modified polylactic acid material that prepared by this preparation method is not suitable for 3D printing technique.
China Patent Publication No. CN102134381A discloses a kind of modified polylactic acid material and preparation method thereof, in the method, toughness reinforcing heat-resistant elastomer properties-correcting agent and polylactic acid blend are extruded modification, namely the defect of the poor toughness of poly(lactic acid) is improved, also improve the heat resisting temperature of poly(lactic acid), but be also the method for modifying adopting direct blending extrusion in the method, reduce the processing characteristics of poly(lactic acid), be not also suitable for 3D printing technique.
Above-mentioned is all adopt co-blending elastic body to improve toughness, and owing to have employed elastomerics, preparation method is single backwardness also, and modified poly(lactic acid) processing characteristics obviously reduces, and is not suitable for 3D and prints.Poly-lactic acid material is wanted to be widely used in individual 3D printing technique, the material modified selection of polydactyl acid and preparation method are very important, and can be affects modified polylactic acid material meet and be suitable for the important factor of 3D printing technique to the requirement of material.
Summary of the invention
There is equipment for current poly-lactic acid material modification method for preparing single, the defect that technological method falls behind, the present invention proposes a kind of preparation method of the poly-lactic acid material for 3D printing.For achieving the above object, the present invention first utilizes ultrasonication technology that nano inorganic toughner coupling agent is carried out organic modification of surface, again the nano inorganic toughner through modification carried out with poly(lactic acid), softening agent, dispersion agent grinding, disperse, mix, eventually pass extruding pelletization, drawing process, the obtained toughening modified polylactic acid material being applicable to 3D and printing.
The concrete preparation method of a kind of poly(lactic acid) for 3D printing of the present invention is as follows:
1) coupling agent of the nano inorganic toughner of 10-25 weight part, 0.5-2 weight part, appropriate solvent are added people in reactor, under the stirring velocity of the temperature of 60 DEG C, 100-300r/min, with ultrasonication reaction 1-3h discharging, dry, grind the nano inorganic toughner obtaining organic modification of surface process;
2) poly(lactic acid) of the nano inorganic toughner of the organic modification of surface process obtained in step 1) and 60-85 weight part, the softening agent of 1-3 weight part, the dispersion agent of 1-5 weight part joined in planetary ball mill, carry out grinding under the speed of 300-450r/min, disperse, combination treatment 1-2h discharging obtains mixture;
3) by step 2) the mixture twin screw extruder mixing extruding pelletization that obtains, the time that material stops in an extruder is 5-8 minute.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 52:1, and extruder temperature is set as successively: 120-125 DEG C, 125-135 DEG C, 135-145 DEG C, 130-140 DEG C, 135-140 DEG C, die head temperature 145-155 DEG C;
4) by step 3) in institute granulation drying baker extrude with single screw extrusion machine after dry 2-3 hour at the temperature of 50 DEG C and be processed into the filament that diameter is 1.75mm, 3mm, diameter error is within 5%.Single screw extrusion machine screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 125-135 DEG C, 130-140 DEG C, 135-145 DEG C, 140-150 DEG C, 145-155 DEG C, die head temperature 145-155 DEG C.
In a kind of preparation method of the poly(lactic acid) printed for 3D, wherein said planetary ball mill utilizes abrasive material and test portion to roll at a high speed in grinding pot, material is produced to strong shear, impacts, rolls the object equipment reaching pulverizing, grinding, dispersion, emulsifying material, primarily of feed portion, discharging portion, rotating part, driving section (step-down gear, small transmission gear, motor, automatically controlled) composition.
In a kind of preparation method of the poly-lactic acid material printed for 3D, wherein said nano inorganic toughner is length-to-diameter ratio >=20:1, the sea of granularity≤10nm is embraced in mineral wool, brucite fiber, calcium carbonate crystal whisker, polygorskite fiber one or more; Described dispersion agent is one or more in triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, guar gum.
The present invention adopts ultrasonic wave and coupling agent to carry out organic modification of surface process to nano inorganic toughner, makes nano inorganic toughner in poly(lactic acid), have excellent stability and consistency; And adopt the technical matters of grinding, disperseing, mixing, extrude, nano inorganic toughner better can be spread out in poly(lactic acid) system, the poly(lactic acid) of the method modification is used not only to have high excellent toughness and tensile strength, also do not affect the processing stability of poly(lactic acid) when 3D printing shaping, can be widely used in 3D printing technique.
The feature that the present invention gives prominence to is:
1, the present invention adopts ultrasonic wave and coupling agent to carry out organic modification of surface process to nano inorganic toughner, makes nano inorganic toughner in poly(lactic acid), have excellent stability and consistency.
2, the present invention's technical matters of adopting grinding, disperseing, mix, extrude, nano inorganic toughner better can be spread out in poly(lactic acid) system and form homogeneous structure, during modified poly-lactic acid material printing shaping, interiors of products stress distribution evenly, cooling meat rate is identical, there is excellent forming stability, and toughness and tensile strength more excellent.
3, production process of the present invention is simple, easy to operate, is easy to suitability for industrialized production.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
1) titanate coupling agent of the nanometer sepiolite fibre of 10 weight parts, 0.5 weight part, appropriate deionized water are added people in reactor, under the stirring velocity of the temperature of 60 DEG C, 300r/min, with ultrasonication reaction 1h discharging, dry, grind the nano inorganic toughner obtaining organic modification of surface process;
2) poly(lactic acid) of the nano inorganic toughner of the organic modification of surface process obtained in step 1) and 85 weight parts, the fatty group dibasic acid of 3 weight parts, the triethyl hexyl phosphoric acid of 3 weight parts joined in planetary ball mill, carry out grinding under the speed of 300r/min, disperse, combination treatment 1h discharging obtains mixture;
3) by step 2) in the compound twin screw extruder mixing extruding pelletization that obtains, the time that material stops in an extruder is 5 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 52:1, and extruder temperature is set as successively: 120 DEG C, 125 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, die head temperature 155 DEG C;
4) by step 3) in institute granulation extrude with single screw extrusion machine after dry 2 hours at the temperature of 50 DEG C and be processed into the filament that diameter is 1.75mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, die head temperature 155 DEG C.
The PLA mixed and modified through single twin-screw extrusion is carried out detection with the salient features of the PLA after present method modification contrast, its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 66 | 85 | 54 |
| Elongation at break (%) | 53 | 83 | 6 |
| Melt flow index (g/min) | 4.2 | 4.9 | 5.6 |
embodiment 2
1) the organic complex compound coupling agent of the nanometer brucite fiber of 25 weight parts, 2 weight parts, appropriate deionized water are added people in reactor, under the stirring velocity of the temperature of 60 DEG C, 200r/min, with ultrasonication reaction 2h discharging, dry, grind the nano inorganic toughner obtaining organic modification of surface process;
2) poly(lactic acid) of the nano inorganic toughner of the organic modification of surface process obtained in step 1) and 60 weight parts, the benzoic ether of 3 weight parts, the sodium lauryl sulphate of 5 weight parts joined in planetary ball mill, carry out grinding under the speed of 400r/min, disperse, combination treatment 2h discharging obtains mixture;
3) by step 2) in the compound twin screw extruder mixing extruding pelletization that obtains, the time that material stops in an extruder is 6 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 120 DEG C, 125 DEG C, 135 DEG C, 140 DEG C, 140 DEG C, die head temperature 145 DEG C;
4) by step 3) in institute granulation extrude with single screw extrusion machine after dry 2.5 hours at the temperature of 50 DEG C and be processed into the filament that diameter is 1.75mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, die head temperature 145 DEG C.
Contrast carrying out detection through the salient features of the mixed and modified PLA of single twin-screw extrusion and the PLA after present method modification and pure PLA, its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 69 | 83 | 54 |
| Elongation at break (%) | 51 | 85 | 6 |
| Melt flow index (g/min) | 4.1 | 4.7 | 5.6 |
embodiment 3
1) the nano-calcium carbonate calcium pyroborate of 15 weight parts, the aluminated compound coupling agent of 1 weight part, appropriate deionized water are added people in reactor, under the stirring velocity of the temperature of 60 DEG C, 150r/min, with ultrasonication reaction 1h discharging, dry, grind the nano inorganic toughner obtaining organic modification of surface process;
2) poly(lactic acid) of the nano inorganic toughner of the organic modification of surface process obtained in step 1) and 70 weight parts, the citrate of 2 weight parts, the methyl amyl alcohol of 2 weight parts joined in planetary ball mill, carry out grinding under the speed of 350r/min, disperse, combination treatment 1h discharging obtains mixture;
3) by step 2) in the compound twin screw extruder mixing extruding pelletization that obtains, the time that material stops in an extruder is 8 minutes.Double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 120 DEG C, 125 DEG C, 130 DEG C, 140 DEG C, 145 DEG C, die head temperature 150 DEG C;
4) by step 3) in institute granulation extrude with single screw extrusion machine after dry 3 hours at the temperature of 50 DEG C and be processed into the filament that diameter is 3mm, single screw extrusion machine screw diameter is 75mm, length-to-diameter ratio is 20:1, extruder temperature is set as successively: 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 140 DEG C, die head temperature 150 DEG C.
Contrast carrying out detection through the salient features of the mixed and modified PLA of single twin-screw extrusion and the PLA after present method modification and pure PLA, its comparison and detection result is as follows:
| Test item | Tradition modification PLA | Present method modification PLA | Pure PLA |
| Tensile strength (MPa) | 67 | 81 | 54 |
| Elongation at break (%) | 54 | 90 | 6 |
| Melt flow index (g/min) | 4.2 | 5.0 | 5.6 |
Claims (1)
1., for a preparation method for the poly-lactic acid material of 3D printing, it is characterized in that concrete preparation method is as follows:
1) coupling agent of the nano inorganic toughner of 10-25 weight part, 0.5-2 weight part, appropriate solvent are joined in reactor, under the stirring velocity of the temperature of 60 DEG C, 100-300r/min, with ultrasonication reaction 1-3h discharging, dry, grind the nano inorganic toughner obtaining organic modification of surface process;
2) poly(lactic acid) of the nano inorganic toughner of the organic modification of surface process obtained in step 1) and 60-85 weight part, the softening agent of 1-3 weight part, the dispersion agent of 1-5 weight part joined in planetary ball mill, carry out grinding under the speed of 300-450r/min, disperse, combination treatment 1-2h discharging obtains mixture;
3) by step 2) the mixture twin screw extruder mixing extruding pelletization that obtains, the time that material stops in an extruder is 5-8 minute;
4) by step 3) in institute granulation drying baker extrude with single screw extrusion machine after dry 2-3 hour at the temperature of 50 DEG C and be processed into the filament that diameter is 1.75mm, 3mm, diameter error is within 5%;
Wherein said nano inorganic toughner is length-to-diameter ratio >=20:1, mineral wool is embraced in the nanometer sea of granularity≤10nm, nanometer brucite fiber, nano-calcium carbonate calcium pyroborate, one or more in nanometer palygorskite fiber; Described dispersion agent is one or more in triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, guar gum; Described double-screw extruder screw diameter is 75mm, and length-to-diameter ratio is 52:1, and extruder temperature is set as successively: 120-125 DEG C, 125-135 DEG C, 135-145 DEG C, 130-140 DEG C, 135-140 DEG C, die head temperature 145-155 DEG C; Described single screw extrusion machine screw diameter is 75mm, and length-to-diameter ratio is 20:1, and extruder temperature is set as successively: 125-135 DEG C, 130-140 DEG C, 135-145 DEG C, 140-150 DEG C, 145-155 DEG C, die head temperature 145-155 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620288.8A CN103665802B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of the poly-lactic acid material for 3D printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620288.8A CN103665802B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of the poly-lactic acid material for 3D printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103665802A CN103665802A (en) | 2014-03-26 |
| CN103665802B true CN103665802B (en) | 2015-09-02 |
Family
ID=50304622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310620288.8A Active CN103665802B (en) | 2013-11-29 | 2013-11-29 | A kind of preparation method of the poly-lactic acid material for 3D printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103665802B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106715100B (en) * | 2014-05-09 | 2019-11-15 | 苏州聚复高分子材料有限公司 | Highly crystalline polylactic acid wire rod for material extruded type increasing material manufacturing |
| CN105462193A (en) * | 2014-09-03 | 2016-04-06 | 东北林业大学 | Whisker reinforced biodegradable polyester composite material and preparation method |
| CN104177798A (en) * | 2014-09-19 | 2014-12-03 | 上海材料研究所 | Modified polylactic acid composite material suitable for 3D printing and preparation method of composite material |
| CN104312119A (en) * | 2014-11-06 | 2015-01-28 | 芜湖瀚博电子科技有限公司 | Straw 3D printing consumable and preparation method thereof |
| CN104672826A (en) * | 2015-02-10 | 2015-06-03 | 利丰新材料科技（深圳）有限公司 | 3D printed PLA consumable and preparation method thereof |
| CN104693773A (en) * | 2015-03-17 | 2015-06-10 | 华南协同创新研究院 | Polypropylene carbonate composite material for 3D printing and preparation method thereof |
| CN105419266A (en) * | 2015-12-17 | 2016-03-23 | 宁夏共享能源有限公司 | 3D (three dimensional) printing material and preparation method thereof |
| CN106893277A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of inorganics filled biodegradable 3D printing consumptive material and preparation method thereof |
| CN106905675A (en) * | 2015-12-22 | 2017-06-30 | 上海邦中新材料有限公司 | A kind of compound 3D printing material of PLA and polyphenylene sulfide |
| CN105504713B (en) * | 2015-12-29 | 2017-07-14 | 广西三集科技有限公司 | A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere |
| CN105482395A (en) * | 2016-01-05 | 2016-04-13 | 华南协同创新研究院 | Light-emitting PLA wire for 3D printing and preparation method and application thereof |
| CN106221163A (en) * | 2016-08-25 | 2016-12-14 | 中国电子科技集团公司第四十六研究所 | A kind of 3D prints by environment-friendly modified poly-lactic acid material and preparation technology thereof |
| CN106751379A (en) * | 2016-11-23 | 2017-05-31 | 中国科学院化学研究所 | Product prepared by a kind of fused glass pellet technique and preparation method thereof |
| CN107325504B (en) * | 2017-06-22 | 2019-09-20 | 清华大学 | A kind of 3 D-printing composite thermoelectric material |
| CN109337313B (en) * | 2018-09-12 | 2021-02-23 | 泉州市康馨化工科技有限公司 | Method for forming gradient composite material by using 3D printing |
| CN109291417A (en) * | 2018-09-14 | 2019-02-01 | 莱芜职业技术学院 | Novel degradable polylactic acid 3D printing material preparation method and application |
| CN110682512A (en) * | 2019-10-15 | 2020-01-14 | 武义斯汀纳睿三维科技有限公司 | Preparation method of enhanced 3D printing material |
| CN111500036A (en) * | 2020-05-15 | 2020-08-07 | 王智辉 | Heat-resistant high-strength 3D printing material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268178A (en) * | 2011-05-27 | 2011-12-07 | 东华大学 | Transparent plasticized polylactic acid nano resin slice with low mobility and preparation method thereof |
| CN103146164A (en) * | 2013-04-07 | 2013-06-12 | 苏州聚复高分子材料有限公司 | Nano-toughened polylactic acid material for rapid prototyping and preparation method thereof |
-
2013
- 2013-11-29 CN CN201310620288.8A patent/CN103665802B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268178A (en) * | 2011-05-27 | 2011-12-07 | 东华大学 | Transparent plasticized polylactic acid nano resin slice with low mobility and preparation method thereof |
| CN103146164A (en) * | 2013-04-07 | 2013-06-12 | 苏州聚复高分子材料有限公司 | Nano-toughened polylactic acid material for rapid prototyping and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103665802A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665802B (en) | A kind of preparation method of the poly-lactic acid material for 3D printing | |
| CN102060564B (en) | Light-weight environmental-friendly stone paper and preparation method thereof | |
| KR101318135B1 (en) | making method using thermoplastic polyurethane coating yarn | |
| CN106827707B (en) | A kind of imitation wood wood-plastic co-extrusion section bar preparation method | |
| CN101397375B (en) | PVC low foaming wood-plastic decorating material and production method thereof | |
| CN106832905A (en) | Polymer matrix micro-/ nano composite material powder and preparation method thereof | |
| CN104592730B (en) | A kind of polylactic acid/polyester alloy and preparation method thereof | |
| CN108456407A (en) | A kind of degradable package material and preparation method thereof | |
| CN107216517B (en) | Preparation method of ultrahigh molecular weight polyethylene 3D printing supplies | |
| CN105647137A (en) | 3D printing polylactic acid /leather powder composite materials and preparation method thereof | |
| CN103726126B (en) | PET is utilized to produce the method for flat filament | |
| CN106633722A (en) | Anti-tearing biodegradable material with high toughness and preparation method of anti-tearing biodegradable material | |
| CN102516666B (en) | Polypropylene-based microcellular foaming wood-plastic composite material and production method thereof | |
| CN104262915B (en) | Prepare the method for the polylactic acid based plasticising wood plastic composite of low mobility | |
| CN104672826A (en) | 3D printed PLA consumable and preparation method thereof | |
| CN109535674A (en) | Using the PPC/PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation | |
| CN102978741A (en) | Manufacturing method for high-strength netting twine | |
| CN102423952A (en) | Production method and device of waterproof rolled material | |
| CN100494236C (en) | Modified starch preparation method | |
| JP7130256B2 (en) | RESIN COMPOSITION FOR MODELING MATERIAL FOR FOTUS LAYER METHOD 3D PRINTER AND FILAMENT-FORMED PRODUCT THEREOF | |
| CN101920549A (en) | Formula and process for preparing wide chlorinated polyethylene waterproof roll material by extrusion molding method | |
| CN1453305A (en) | Prepn of polyolefine resin specially for permeating curtain coated film | |
| CN110240779A (en) | A kind of high-precision is without plug type stalk FDM 3D printing consumptive material and preparation method thereof | |
| CN105504250A (en) | Preparation method of low-cost degradable plastics | |
| CN109401227A (en) | Using the PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: OUYANG LIWEI Inventor before: Chen Qing Inventor before: Li Xingwen |
|
| COR | Change of bibliographic data | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20151231 Address after: 528467 Tanzhou, Zhongshan, Zhenlong Tong Street, No. 3, No. two, building fourth, block A, Patentee after: Zhongshan macromolecule material Co., Ltd. Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Patentee before: Chengdu Xinkeli Chemical Sci-Tech Co., Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 528400 Tanzhou, Zhongshan, Zhenlong Tong Street, No. 3, No. two, building A, block fourth, two, Patentee after: Zhongshan Jian Technology Co., Ltd. Address before: 528467 Tanzhou, Zhongshan, Zhenlong Tong Street, No. 3, No. two, building fourth, block A, Patentee before: Zhongshan macromolecule material Co., Ltd. |