CN104830040A - Polycarbonate composition for 3D printing technology and preparation method thereof - Google Patents
Polycarbonate composition for 3D printing technology and preparation method thereof Download PDFInfo
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- CN104830040A CN104830040A CN201510213152.4A CN201510213152A CN104830040A CN 104830040 A CN104830040 A CN 104830040A CN 201510213152 A CN201510213152 A CN 201510213152A CN 104830040 A CN104830040 A CN 104830040A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
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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
- 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 invention relates to a polycarbonate composition for 3D printing technology and a preparation method thereof. The composition is composed of the following components according to a certain ratio: polycarbonate resin, SAN-GMA, nano silicon dioxide, a flexibilizer, an antioxidant, and a lubricant. The diameter of the screw rod of an extruder used in alloy preparation is 58 mm, and the length/diameter ratio is 60. The preparation method comprises the following steps: adding PC resin, SAN-GMA resin, nano silicon dioxide, a flexibilizer, an antioxidant, and a lubricant into a mixing and stirring machine, mixing, transferring the mixture to a double-screw-rod extruder, blending, melting, extruding, and granulating to obtain the polycarbonate composition for 3D printing. Compared with the prior art, during the preparation process, the PC/ABS melting range is shortened, furthermore, nano silicon dioxide is added to enhance the heat transferring performance of the polycarbonate composition, and the warping problem during the 3D printing process is solved.
Description
Technical field
The present invention relates to polymeric material field, especially relate to a kind of polycarbonate compositions for 3D printing technique and preparation method thereof.
Background technology
3D printing technique is rapid shaping technique, is the high-new manufacturing technology of one based on bing area method, utilizes the data of three-dimensional CAD, by rapidform machine, material stacking is from level to level become the method for physical prototypes.3D prints because it makes fast, can the advantage such as online 3-D effect completely, is applied in the fields such as medical science, aviation, building gradually.
The technology that 3D prints includes the techniques such as SLA, FDM, SLS and LOM.Wherein FDM utilizes thermoplastic, polymeric materials in the molten state, squeezes out from shower nozzle, solidifies the thin layer forming outline shape, then superposition forms the finished product from level to level.Be applied to FDM technique starting material normally ABS, nylon.
Conventional PC/ABS due to its melting range wide, there is the defects such as warpage when melting superpose, limit its application in 3D printing.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of polycarbonate compositions for 3D printing technique is provided.
Object of the present invention can be achieved through the following technical solutions:
For a polycarbonate compositions for 3D printing technique, it comprises the component of following weight part:
Described polycarbonate is ester-interchange method aromatic copolycarbonate.
Preferably, the weight-average molecular weight of described polycarbonate is 25000 ~ 40000.
Preferably, the molecular weight of described SAN-GMA is 130000 ~ 150000, and wherein GMA content is 1 ~ 5wt%.
Preferably, described nano silicon particle diameter is 50 ~ 200nm.
Preferably, described toughner comprises at least one in methyl methacrylate/butadiene/styrene copolymers, methyl methacrylate/acrylic acid base polymer, acrylic acid or the like toughner, vinylformic acid-silicone rubber kinds toughner, ethylene-methyl acrylate, Ethylene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer or ethylene-vinyl acetate copolymer-functionalization maleic anhydride.
Preferably, described oxidation inhibitor comprises one or more in commercially available oxidation inhibitor 245, antioxidant 1076, irgasfos 168.
Preferably, described lubricant comprises one or more in silicone powder, pentaerythritol ester, ethylene bis stearic amide.
As described in the present invention for a preparation method for the polycarbonate compositions of 3D printing technique, it comprises the steps:
PC resin, SAN-GMA resin, nano silicon, toughner, oxidation inhibitor and lubricant are added after mixing in mixing and blending machine, by the blended granulation of twin screw extruder, screw extrusion press rotating speed is 600 ~ 900rpm, pressure is 2 ~ 3MPa, through melt extruding, granulation, obtains the polycarbonate compositions for 3D printing technique.
Preferably, described extruder screw diameter is 58mm, and length-to-diameter ratio is 60.
Compared with prior art, the beneficial effect that the present invention has is: this kind of polycarbonate compositions provided by the present invention, PC/ABS melting range is shortened by the reaction of PC and SAN-GMA, by adding nano silicon, improve the heat transfer property of material, solve the problem of warpage in 3D print procedure.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The PC-1100 of the PC Korea S lake stone selected in following examples and comparative example, the SAN-GAM SAG-005 of Shanghai Zhi Sheng company, the commercially available nano silicon of nano silicon, particle diameter is 100nm, the toughner EXL2691A of the Dow Chemical Company, oxidation inhibitor is Irganox 1076 and the Irganox168 of Ciba company, and its weight ratio is 1:1; Lubricant is commercially available tetramethylolmethane stearic acid.
Comparative example 1
Polycarbonate compositions that a kind of 3D prints and preparation method thereof, the method comprises the following steps:
(1) each component is taken by weight: PC:70, SAN-GMA:20, nano silicon: 5, toughner EXL-2691A:5, antioxidant 1010: 0.1, irgasfos 168: 0.1, lubricant PETS 0.3.
(2) fed from spout by starting material, melt extrude at 200 ~ 280 DEG C, screw extrusion press rotating speed is 500rpm, and pressure is 2MPa, and through melt extruding, namely granulation obtains product.
(3) extruder screw diameter is 58mm, and length-to-diameter ratio is 40.
Comparative example 2
Polycarbonate compositions that a kind of 3D prints and preparation method thereof, the method comprises the following steps:
((1) takes each component by weight: PC:80, SAN-GMA:10, toughner EXL-2691A:10, antioxidant 1010 0.1, irgasfos 168 0.1, lubricant PETS 0.3.
(2) fed from spout by starting material, melt extrude at 200 ~ 280 DEG C, screw extrusion press rotating speed is 500rpm, and pressure is 2MPa, and through melt extruding, namely granulation obtains product.。
(3) extruder screw diameter is 58mm, and length-to-diameter ratio is 40.
Embodiment 1
(1) each component is taken by weight: PC:70, SAN-GMA:20, nano silicon: 5, toughner EXL-2691A:5, antioxidant 1010 0.1, irgasfos 168 0.1, lubricant PETS 0.3.
(2) fed from spout by starting material, melt extrude at 200 ~ 280 DEG C, screw extrusion press rotating speed is 500rpm, and pressure is 2MPa, and through melt extruding, namely granulation obtains product.
(3) extruder screw diameter is 58mm, and length-to-diameter ratio is 60.
Embodiment 2
(1) each component is taken by weight: PC:80, SAN-GMA:10, nano silicon: 2, toughner EXL-2691A:8, antioxidant 1010 0.1, irgasfos 168 0.1, lubricant PETS 0.3.
(2) fed from spout by starting material, melt extrude at 200 ~ 280 DEG C, screw extrusion press rotating speed is 500rpm, and pressure is 2MPa, and through melt extruding, namely granulation obtains product.
(3) extruder screw diameter is 58mm, and length-to-diameter ratio is 60.
Embodiment 3
(1) each component is taken by weight: PC:75, SAN-GMA:15, nano silicon: 2, toughner EXL-2691A:8, antioxidant 1010 0.1, irgasfos 168 0.1, lubricant PETS 0.3.
(2) fed from spout by starting material, melt extrude at 200 ~ 280 DEG C, screw extrusion press rotating speed is 500rpm, and pressure is 2MPa, and through melt extruding, namely granulation obtains product.
(3) extruder screw diameter is 58mm, and length-to-diameter ratio is 60.
Embodiment 4
Test result and the 3D print result of each comparative example and embodiment are as shown in table 1.Notched Izod impact strength is tested according to ASTM D256 standard, and breach type is category-A, and batten thickness is 1/8 ";
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Notched Izod impact strength (J/m) | 450 | 900 | 700 | 820 | 670 |
| 3D sample warpage degree | ★★★ | ★★★★ | Nothing | ★ | ★ |
★ more multilist presentation surface warpage is more serious
As shown in Table 1, use the forcing machine of large length-to-diameter ratio, PC/ABS melting range is shortened by the reaction of PC and SAN-GMA, by adding nano silicon, improve the heat transfer property of material, solve the problem of warpage in 3D print procedure, embodiment 3 shows excellent impact property and 3D printing effect.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. for a polycarbonate compositions for 3D printing technique, it is characterized in that, comprise the component of following weight part:
Described polycarbonate resin is ester-interchange method aromatic polycarbonate resin.
2. polycarbonate compositions according to claim 1, is characterized in that, the weight-average molecular weight of described polycarbonate is 25000 ~ 40000.
3. polycarbonate compositions according to claim 1, is characterized in that, the molecular weight of described SAN-GMA is 130000 ~ 150000, and wherein GMA content is 1 ~ 5wt%.
4. polycarbonate compositions according to claim 1, is characterized in that, described nano silicon particle diameter is 50 ~ 200nm.
5. polycarbonate compositions according to claim 1, it is characterized in that, described toughner comprises at least one in methyl methacrylate/butadiene/styrene copolymers, methyl methacrylate/acrylic acid base polymer, acrylic acid or the like toughner, vinylformic acid-silicone rubber kinds toughner, ethylene-methyl acrylate, Ethylene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer or ethylene-vinyl acetate copolymer-functionalization maleic anhydride.
6. polycarbonate compositions according to claim 1, is characterized in that, described oxidation inhibitor comprises one or more in commercially available oxidation inhibitor 245, antioxidant 1076, irgasfos 168.
7. polycarbonate compositions according to claim 1, is characterized in that, described lubricant comprises one or more in silicone powder, pentaerythritol ester, ethylene bis stearic amide.
8. a preparation method for the polycarbonate compositions of the polycarbonate compositions of a kind of 3D printing as claimed in claim 1, is characterized in that, comprise the following steps:
PC resin, SAN-GMA resin, nano silicon, toughner, oxidation inhibitor and lubricant are added after mixing in mixing and blending machine, by the blended granulation of twin screw extruder, screw extrusion press rotating speed is 600 ~ 900rpm, pressure is 2 ~ 3MPa, through melt extruding, granulation, obtains the polycarbonate compositions for 3D printing technique.
9. preparation method according to claim 8, is characterized in that, the screw diameter of described twin screw extruder is 58mm, and length-to-diameter ratio is 60.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733285A (en) * | 2016-05-05 | 2016-07-06 | 北京隆源自动成型***有限公司 | Walnut sand 3D printing material and preparation method thereof |
| CN106633766A (en) * | 2016-11-28 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-ABS material and preparation method thereof |
| CN106674953A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-ABA material and preparation method thereof |
| CN106674952A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-AES material and preparation method thereof |
| CN106674855A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-MBS material and preparation method thereof |
| WO2017123743A1 (en) * | 2016-01-15 | 2017-07-20 | Sabic Global Technologies B.V. | Improved performance monofilament manufactured articles |
| WO2018101537A1 (en) * | 2016-11-29 | 2018-06-07 | 주식회사 삼양사 | Eco-friendly polycarbonate resin composition having excellent adhesion |
| CN108976743A (en) * | 2018-06-15 | 2018-12-11 | 北京濮源新材料技术研究院(普通合伙) | The modified producing method of aromatic copolycarbonate engineering plastics |
| CN112500690A (en) * | 2020-11-13 | 2021-03-16 | 万华化学(四川)有限公司 | Polycarbonate composition suitable for 3D printing, preparation method and application thereof |
| CN113817304A (en) * | 2021-09-18 | 2021-12-21 | 金旸（厦门）新材料科技有限公司 | Composite nano silicon dioxide modified PC/ABS alloy material and preparation method thereof |
| US11339263B2 (en) | 2015-03-16 | 2022-05-24 | Shpp Global Technologies B.V. | Fibrillated polymer compositions and methods of their manufacture |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11339263B2 (en) | 2015-03-16 | 2022-05-24 | Shpp Global Technologies B.V. | Fibrillated polymer compositions and methods of their manufacture |
| WO2017123743A1 (en) * | 2016-01-15 | 2017-07-20 | Sabic Global Technologies B.V. | Improved performance monofilament manufactured articles |
| CN105733285A (en) * | 2016-05-05 | 2016-07-06 | 北京隆源自动成型***有限公司 | Walnut sand 3D printing material and preparation method thereof |
| CN106633766A (en) * | 2016-11-28 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-ABS material and preparation method thereof |
| CN106674953A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-ABA material and preparation method thereof |
| CN106674952A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-AES material and preparation method thereof |
| CN106674855A (en) * | 2016-11-28 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | 3D printing PC-MBS material and preparation method thereof |
| WO2018101537A1 (en) * | 2016-11-29 | 2018-06-07 | 주식회사 삼양사 | Eco-friendly polycarbonate resin composition having excellent adhesion |
| CN108976743A (en) * | 2018-06-15 | 2018-12-11 | 北京濮源新材料技术研究院(普通合伙) | The modified producing method of aromatic copolycarbonate engineering plastics |
| CN112500690A (en) * | 2020-11-13 | 2021-03-16 | 万华化学(四川)有限公司 | Polycarbonate composition suitable for 3D printing, preparation method and application thereof |
| CN112500690B (en) * | 2020-11-13 | 2022-11-08 | 万华化学(四川)有限公司 | Polycarbonate composition suitable for 3D printing, preparation method and application thereof |
| CN113817304A (en) * | 2021-09-18 | 2021-12-21 | 金旸（厦门）新材料科技有限公司 | Composite nano silicon dioxide modified PC/ABS alloy material and preparation method thereof |
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Application publication date: 20150812 |