CN111621128A - Preparation method of graphene oxide grafted polycaprolactone, toughening agent and 3D printing consumable - Google Patents
Preparation method of graphene oxide grafted polycaprolactone, toughening agent and 3D printing consumable Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 40
- 239000012745 toughening agent Substances 0.000 title claims abstract description 38
- 238000010146 3D printing Methods 0.000 title claims abstract description 35
- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 34
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 44
- 239000004626 polylactic acid Substances 0.000 claims abstract description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000004698 Polyethylene Substances 0.000 claims abstract 3
- -1 polyethylene Polymers 0.000 claims abstract 2
- 229920000573 polyethylene Polymers 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 238000005491 wire drawing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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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
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- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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Abstract
The invention discloses a preparation method of graphene oxide grafted polycaprolactone and a toughening agent, wherein caprolactone-CL and graphene oxide are added in nitrogen, toluene is used as a solvent, stannous octoate is used as a catalyst, the mixture is fully reacted at 80-140 ℃, and after the reaction is finished, the mixture is cooled, concentrated, precipitated by diethyl ether and dried to obtain the graphene oxide grafted polycaprolactone; and then mixing with polyethylene for granulation, and the obtained material can be used as a toughening agent of the polylactic acid 3D printing wire rod and can improve the mechanical property of the wire rod when being used for the polylactic acid 3D printing wire rod.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of graphene oxide grafted polycaprolactone, and further relates to a polylactic acid 3D printing wire flexibilizer containing the graphene oxide grafted polycaprolactone.
Background
With the continuous development of society, environment-friendly materials are more and more popular. In the high polymer material, polylactic acid has the characteristics of environmental protection, no toxicity, no harm, biodegradability, good biocompatibility and the like, and is widely used in various fields of medicines, food packaging, fast food lunch boxes and the like.
3D printing is a technique for building objects by layer-by-layer printing using bondable materials such as powdered metals or plastics based on digital model files. 3D printing technology has applications in a variety of fields, such as aerospace, medical, jewelry, industrial design, automotive manufacturing, construction, education, and others.
The FDM 3D printing can not be separated from the polylactic acid material, the 3D printing wire made of the pure polylactic acid raw material is brittle, and the wire is easy to break in the printing process to influence the printing; secondly, the mechanical properties of the printed product are not good, and better requirements cannot be met. The modified polylactic acid raw material does not have the problems, but the modified polylactic acid on the market is expensive, so that the cost is greatly improved. Therefore, the toughness of the PLA wire rod is improved by adding the toughening agent, in general, the addition amount of the toughening agent is 2-8%, so that the toughness of the PLA wire rod is close to or even reaches the toughness of the modified PLA, and the cost can be well reduced by adding the toughening agent. Therefore, it is urgently needed to synthesize a toughening agent for polylactic acid 3D printing wires.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing graphene oxide-grafted polycaprolactone; the second purpose of the invention is to provide the graphene oxide grafted polycaprolactone prepared by the method; the third purpose of the invention is to provide a toughening agent containing the graphene oxide grafted polycaprolactone; the fourth purpose of the invention is to provide a preparation method of the toughening agent; the fifth purpose of the invention is to provide a polylactic acid 3D printing consumable prepared by utilizing the toughening agent.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the preparation method of the graphene oxide grafted polycaprolactone comprises the steps of filling nitrogen, adding caprolactone-CL, graphene oxide, toluene as a solvent and stannous octoate as a catalyst, fully reacting at 80-140 ℃, cooling after the reaction is finished, concentrating, precipitating with diethyl ether, and drying to obtain the graphene oxide grafted polycaprolactone.
In the invention, the mass ratio of caprolactone-CL to graphene oxide is 13: 2.
2. the graphene oxide grafted polycaprolactone prepared by the method.
3. The toughening agent contains the graphene oxide grafted polycaprolactone.
4. The preparation method of the toughening agent comprises the steps of mixing the graphene oxide grafted polycaprolactone with the PE and then granulating to prepare the toughening agent.
Preferably, 10-40 parts of graphene oxide grafted polycaprolactone and 60-90 parts of PE are taken according to parts by weight and are mixed and then added into a double-screw extruder, wherein the temperature of a charging barrel of the double-screw extruder from a charging port to each area of a machine head is as follows: and the first zone is 175-180 ℃, the second zone is 185-190 ℃ and the third zone is 180-185 ℃, and the toughening agent is obtained by drawing, dragging and cooling the mixture and then cutting the mixture in a granulator.
5. The polylactic acid 3D printing consumable prepared by using the toughening agent is prepared by the following method: taking 92-98 parts of PLA and 2-8 parts of a toughening agent according to parts by weight; extruding and wire-drawing by using a single screw extruder, wherein the temperature of a first temperature zone is 175-185 ℃, the temperature of a second temperature zone is 185-195 ℃, the temperature of a third temperature zone is 180-190 ℃, and the temperature of a water tank is 45-55 ℃; the extrusion speed is 720 rmp-920 rpm, the traction speed is 400 rmp-520 rpm, and the winding speed is 8 rmp-14 rpm.
The invention has the beneficial effects that: the invention discloses a synthetic method of graphene oxide grafted polycaprolactone and the synthesized graphene oxide grafted polycaprolactone, which can be mixed with PE and then granulated to prepare a toughening agent of a polylactic acid 3D printing wire, so that the toughness of the polylactic acid wire is improved, the cost can be well reduced, and the method can be widely applied to the industrial preparation of the polylactic acid 3D printing wire.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
fig. 1 is a synthesis method of graphene oxide grafted polycaprolactone.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1 Synthesis method of graphene oxide-grafted polycaprolactone
The preparation method of the graphene oxide grafted polycaprolactone (GO-g-PCL) comprises the following specific steps: charging nitrogen into a two-neck bottle with a magneton, adding caprolactone-CL (13g, 120.80mmol), graphene oxide (2g), stannous octoate Sn (Oct)2(0.311g, 0.72mmol) and toluene (60mL) are put in an oil bath kettle at 100 ℃ for reflux stirring reaction for 6h and cooled to room temperature, the mixture is precipitated by diethyl ether after concentration, and the graphene oxide grafted polycaprolactone (GO-g-PCL) is obtained after vacuum filtration and vacuum drying for 24 h. The synthetic route is shown in fig. 1, namely polycaprolactone is grafted on the surface of graphene oxide.
Mixing GO-g-PCL with PE, and granulating to obtain the toughening agent, which comprises the following steps:
taking 10 parts of GO-g-PCL and 90 parts of PE in parts by weight, mixing and adding the mixture into a double-screw extruder, wherein the temperature of a charging barrel of the double-screw extruder from a charging port to each area of a machine head is as follows: the first zone is 175 ℃, the second zone is 185 ℃ and the third zone is 180 ℃, and the mixture is extruded, drawn and cooled, and then drawn and introduced into a granulator for granulation to obtain the GO-g-PCL/PE toughening agent.
Preparing a 3D printing consumable by using the obtained GO-g-PCL/PE toughening agent and polylactic acid; comprises the following materials in parts by weight: 95 parts of PLA, 5 parts of GO-g-PCL/PE toughening agent; and (3) uniformly mixing, adding the mixture into a single-screw extruder, extruding, drawing, molding, cooling and rolling to obtain the polylactic acid 3D printing consumable.
Wherein the first temperature zone temperature of the single screw extruder is 185 ℃, the second temperature zone temperature is 195 ℃, the third temperature zone temperature is 190 ℃, and the water tank temperature is 55 ℃; the extrusion speed was 925rpm, the haul-off speed was 530rpm, and the take-up speed was 13.5 rpm.
The prepared polylactic acid 3D printing consumable has the wire diameter of 1.75 +/-0.05 mm/2.85 +/-0.05 mm.
Embodiment 3, toughening agent based on graphene oxide grafted polycaprolactone and 3D printing consumable
Mixing GO-g-PCL with PE, and granulating to obtain the toughening agent, which comprises the following steps: taking 40 parts of GO-g-PCL and 60 parts of PE in parts by weight, mixing and adding the mixture into a double-screw extruder, wherein the temperature of a charging barrel of the double-screw extruder from a charging port to each area of a machine head is as follows: extruding, drawing and cooling at 180 ℃ in the first zone, 190 ℃ in the second zone and 189 ℃, and drawing and cutting into granules in a granulator to obtain a GO-g-PCL/PE toughening agent;
the polylactic acid 3D printing consumable comprises the following substances in parts by weight: 95 parts of PLA and 5 parts of GO-g-PCL/PE toughening agent.
The method comprises the following steps:
and (3) taking 92 parts of dried PLA and 8 parts of GO-g-PCL/PE toughening agent, uniformly mixing, adding into a single-screw extruder, extruding, drawing, molding, cooling and rolling to obtain the polylactic acid 3D printing consumable.
Wherein the first temperature zone temperature of the single-screw extruder is 175 ℃, the second temperature zone temperature is 185 ℃, the third temperature zone temperature is 180 ℃, and the water tank temperature is 45 ℃; extrusion speed 720rpm, drawing speed 400rpm, and take-up speed 8 rpm.
The polylactic acid 3D printing consumable has the wire diameter of 1.75 +/-0.05 mm/2.85 +/-0.05 mm.
In the invention, 10-40 parts of GO-g-PCL and 60-90 parts of PE can be used. Polylactic acid 3D printing wire, PLA 92-98 parts, GO-g-PCL/PE toughening agent 2-8 parts; the 3D printing supplies with equivalent performance can be obtained at the extrusion speed of 720 rmp-925 rpm, the traction speed of 400 rmp-530 rpm and the winding speed of 8 rmp-14 rpm.
Comparative example 1
The polylactic acid 3D printing consumable comprises the following substances in parts by weight: 100 parts of PLA.
The method comprises the following specific steps: and adding 100 parts of dried PLA into a single-screw extruder for extrusion, wire drawing and forming, and cooling and rolling to obtain the polylactic acid 3D printing consumable.
Wherein the temperature of a first temperature zone of the single-screw extruder is 186 ℃, the temperature of a second temperature zone is 195 ℃, the temperature of a third temperature zone is 189 ℃, and the temperature of a water tank is 55 ℃; the extrusion speed was 925rpm, the drawing speed was 530rpm, and the take-up speed was 13.5 rpm.
The obtained polylactic acid 3D printing consumable has the wire diameter of 1.75 +/-0.05 mm/2.85 +/-0.05 mm.
Comparative example 2
The polylactic acid 3D printing consumable comprises the following substances in parts by weight: 95 parts of PLA and 5 parts of Graphene Oxide (GO).
The method comprises the following specific steps: and (3) taking 95 parts of dried PLA and 5 parts of Graphene Oxide (GO), uniformly mixing, adding into a single-screw extruder, extruding, drawing and molding, cooling and rolling to obtain the polylactic acid 3D printing consumable.
Wherein the temperature of a first temperature zone of the single-screw extruder is 186 ℃, the temperature of a second temperature zone is 195 ℃, the temperature of a third temperature zone is 189 ℃, and the temperature of a water tank is 55 ℃; the extrusion speed was 925rpm, the drawing speed was 530rpm, and the take-up speed was 13.5 rpm.
The polylactic acid 3D printing consumable has the wire diameter of 1.75 +/-0.05 mm/2.85 +/-0.05 mm.
Comparative example 3
The polylactic acid 3D printing consumable comprises the following substances in parts by weight: 95 parts of PLA and 5 parts of PCL.
The method comprises the following specific steps: and (3) taking 95 parts of dried PLA and 5 parts of PCL, uniformly mixing, adding into a single-screw extruder, extruding, drawing, molding, cooling and rolling to obtain the polylactic acid 3D printing consumable.
Wherein the temperature of a first temperature zone of the single-screw extruder is 186 ℃, the temperature of a second temperature zone is 195 ℃, the temperature of a third temperature zone is 189 ℃, and the temperature of a water tank is 55 ℃; the extrusion speed was 925rpm, the drawing speed was 530rpm, and the take-up speed was 13.5 rpm.
The polylactic acid 3D printing consumable has the wire diameter of 1.75 +/-0.05 mm/2.85 +/-0.05 mm.
The mechanical properties of the 3D printed wires prepared in examples 2 and 3 and comparative example were then examined as shown in table 1.
Table 1, mechanical properties of the 3D printed wires are as follows:
| comparative example 1 | Comparative example 2 | Comparative example 3 | Example 2 | Example 3 | |
| Elongation at break | 6.00％ | 6.24％ | 6.54％ | 7.20％ | 7.74％ |
| Young's modulus | 3500MPa | 2975MPa | 3710MPa | 3920MPa | 4235MPa |
The result shows that the elongation at break of the PLA 3D printing wire is 6% without adding any additive, and the Young modulus is 3500 MPa; by simply adding 5% of graphene oxide, the elongation at break of the PLA wire is improved by 4%, and the Young modulus is reduced by 15%; by simply adding PCL, the elongation at break of the PLA wire rod is improved by 9 percent, and the Young modulus is improved by 6 percent; 5% of GO-g-PCL/PE toughening agent is added, wherein the weight ratio of GO-g-PCL to PE is 10:90, so that the elongation at break of the PLA wire rod can be improved by 20%, and the Young modulus can be improved by 12%; 5% of GO-g-PCL/PE toughening agent is added, wherein the weight ratio of GO-g-PCL to PE is 30:70, so that the elongation at break of the PLA wire rod can be improved by 29%, and the Young modulus can be improved by 21%. The addition of the GO-g-PCL/PE toughening agent has an obvious toughening effect on the PLA wire.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. The preparation method of the graphene oxide grafted polycaprolactone is characterized by comprising the following steps: and (2) introducing nitrogen, adding caprolactone-CL, graphene oxide, toluene as a solvent and stannous octoate as a catalyst, fully reacting at 80-140 ℃, cooling after the reaction is finished, concentrating, precipitating with diethyl ether, and drying to obtain the graphene oxide grafted polycaprolactone.
2. The method for preparing graphene oxide-grafted polycaprolactone according to claim 1, characterized in that: the mass ratio of caprolactone-CL to graphene oxide is 13: 2.
3. graphene oxide grafted polycaprolactone obtainable by the process according to claim 1 or 2.
4. A toughening agent comprising the graphene oxide-grafted polycaprolactone of claim 3.
5. A process for preparing the toughening agent of claim 4, wherein: mixing the graphene oxide grafted polycaprolactone with polyethylene, and granulating to prepare the toughening agent.
6. The method of claim 5, wherein: 10-40 parts of graphene oxide grafted polycaprolactone and 60-90 parts of PE are taken according to parts by weight and are added into a double-screw extruder after being mixed, wherein the temperature of a charging barrel of the double-screw extruder from a charging port to each area of a machine head is as follows: and the first zone is 175-180 ℃, the second zone is 185-190 ℃ and the third zone is 180-185 ℃, and the toughening agent is obtained by drawing, dragging and cooling the mixture and then cutting the mixture in a granulator.
7. The polylactic acid 3D printing consumable prepared by the toughening agent of claim 4, which is prepared by the following method: taking 92-98 parts of PLA and 2-8 parts of a toughening agent according to parts by weight; extruding and wire-drawing by using a single screw extruder, wherein the temperature of a first temperature zone is 175-185 ℃, the temperature of a second temperature zone is 185-195 ℃, the temperature of a third temperature zone is 180-190 ℃, and the temperature of a water tank is 45-55 ℃; the extrusion speed is 720 rmp-920 rpm, the traction speed is 400 rmp-520 rpm, and the winding speed is 8 rmp-14 rpm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094491A (en) * | 2020-09-28 | 2020-12-18 | 江苏华信新材料股份有限公司 | Preparation method of graphene/polycarbonate composite material |
| CN113416313A (en) * | 2021-05-25 | 2021-09-21 | 暨南大学 | Biodegradable compatilizer and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| CN102816418A (en) * | 2012-09-06 | 2012-12-12 | 南京航空航天大学 | Blended foam material based on polycaprolactone (PCL) and modified polylactic acid (PLA) and preparation method thereof |
| CN103980682A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing polycaprolactone material and preparation method thereof |
| CN105367760A (en) * | 2015-11-22 | 2016-03-02 | 云南民族大学 | Preparation method of poly epsilon-caprolactone |
| CN106042374A (en) * | 2015-12-27 | 2016-10-26 | 南京新月材料科技有限公司 | Method for solving problem of fused deposition 3D printing strength |
| CN106543662A (en) * | 2015-09-18 | 2017-03-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/PCL bio-based materials |
| CN109401237A (en) * | 2018-09-28 | 2019-03-01 | 成都新柯力化工科技有限公司 | A kind of polylactic acid 3D printing silk material graphene toughened master batch and preparation method |
| CN109627717A (en) * | 2018-12-10 | 2019-04-16 | 广州飞胜高分子材料有限公司 | A kind of 3D printing composite material that shading is antibacterial, preparation method and applications |
-
2020
- 2020-06-22 CN CN202010574151.3A patent/CN111621128A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504145A (en) * | 2011-11-15 | 2012-06-20 | 苏州大学 | Preparation method for polymer grafted graphene oxide |
| CN102816418A (en) * | 2012-09-06 | 2012-12-12 | 南京航空航天大学 | Blended foam material based on polycaprolactone (PCL) and modified polylactic acid (PLA) and preparation method thereof |
| CN103980682A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing polycaprolactone material and preparation method thereof |
| CN106543662A (en) * | 2015-09-18 | 2017-03-29 | 黑龙江鑫达企业集团有限公司 | A kind of 3D printing PLA/PCL bio-based materials |
| CN105367760A (en) * | 2015-11-22 | 2016-03-02 | 云南民族大学 | Preparation method of poly epsilon-caprolactone |
| CN106042374A (en) * | 2015-12-27 | 2016-10-26 | 南京新月材料科技有限公司 | Method for solving problem of fused deposition 3D printing strength |
| CN109401237A (en) * | 2018-09-28 | 2019-03-01 | 成都新柯力化工科技有限公司 | A kind of polylactic acid 3D printing silk material graphene toughened master batch and preparation method |
| CN109627717A (en) * | 2018-12-10 | 2019-04-16 | 广州飞胜高分子材料有限公司 | A kind of 3D printing composite material that shading is antibacterial, preparation method and applications |
Non-Patent Citations (3)
| Title |
|---|
| BOTLHOKO,OJ,ET AL.: ""influence of functionalized exfoliated reduced graphene oxide nanoparticle localization on mechanical,thermal and electronic properties of nanobiocomposites"", 《EUROPEAN POLYMER JOURNAL》 * |
| GUANG-SHUO WANG ETAL.: ""Morphology，crystallization and mechanical properties of poly(ε-caprolactone)/grapheme oxide nanocomposites"", 《CHINESE JOURNAL OF POLYMER SCIENCE》 * |
| 轩朝阳等: ""聚己内酯/无机纳米复合材料的研究与应用进展"", 《塑料科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094491A (en) * | 2020-09-28 | 2020-12-18 | 江苏华信新材料股份有限公司 | Preparation method of graphene/polycarbonate composite material |
| CN112094491B (en) * | 2020-09-28 | 2023-04-14 | 江苏华信高新材料有限公司 | Preparation method of graphene/polycarbonate composite material |
| CN113416313A (en) * | 2021-05-25 | 2021-09-21 | 暨南大学 | Biodegradable compatilizer and preparation method and application thereof |
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