CN110157189A - A kind of 3D printing composite material and preparation method - Google Patents
A kind of 3D printing composite material and preparation method Download PDFInfo
- Publication number
- CN110157189A CN110157189A CN201910433619.4A CN201910433619A CN110157189A CN 110157189 A CN110157189 A CN 110157189A CN 201910433619 A CN201910433619 A CN 201910433619A CN 110157189 A CN110157189 A CN 110157189A
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- weight
- composite material
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- polyetherimide
- printing composite
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a kind of 3D printing composite materials, comprising: 100 parts by weight of polyphenylene sulfone resins and/or polyetherimide；23~28 parts by weight of polycarbonate；0.5~2 parts by weight of organo-clay.Compared with prior art, the present invention, simultaneously added with the modified clay of machine, improves the physical mechanical property of composite material, and reduce the extent of the destruction of fiber using polyphenylene sulfone resins, polyetherimide and polycarbonate as resin raw material.
Description
Technical field
The invention belongs to 3D printing technique field more particularly to a kind of 3D printing composite material and preparation methods.
Background technique
Additive technology (3D printing) is a kind of radical technological innovation, is a branch of Techno-Industrial, is production
The method of product and extensive stock carries out 3D printing, the increase of the Lai Shixian equipment number of plies by using computer equipment.Actively
Additive technology is promoted, the variation of matter can occur for many production fields, and can simplify organizational process.According to newest research
Analysis shows the following additive technology will be a kind of common process flow, but in order to which section's technical ability reaches this level, need
Overcome the problems, such as many and takes corresponding decision.The problem of this technology first is that required spy with existing polymer material
Property is not inconsistent, and researcher has conducted extensive research the polymer composites of 3D printing.
The U.S. Patent Publication of Patent No. US5476748A a kind of photosensitive composition, the composition include: that weight is
40~80% liquid epoxies, the cation light initiator that weight is 0.1~10%, the liquid rouge that weight is 5~40%
Ring race diacrylate or liquid aromatic diacrylate, poly- (methyl) acrylate of liquid that weight is 0~15%, weight
Ju Mi ﹑ polyester that free radical photo-initiation and weight for 0.1~10% are 5~40% or with the poly- ammonia of О Н-end group
Ester, but the photosensitive composition can not be applied to 3D printing.
The United States Patent (USP) of Patent No. US6869559B2 discloses preparation with polyphenylsulfone polymer (PPSF) and poly- carbonic acid
The method of polymer material based on ester (PC), the mixture of PPSF/PC show good Nai Hua ﹑ thermal stability
And it is not accumulated in the nozzle of three-dimensional moulding device.
The russian patent of Patent No. RU 2398732 discloses a kind of method for producing polymer nanocomposites,
Based on it is by polymer and with the modified nano silicate of organic compound, the nanocomposite being prepared, which has, to be changed
Into strength characteristics, for manufacturing the product in electricity gas Gong Cheng ﹑ mechanical engineering.This method includes mixed melting polymer-polysulfones
Or polyamide and filler-cation exchange capacity are the montmorillonite or bentonite of 60~150 milliequivalent/100 gram, concentration 1
The filler of~7% aqueous dispersion is modified in advance with organic cation, as ionic surface active agent, alkyl benzyl two
The dosage of ammonio methacrylate is the 40~150% of the cation exchange capacity of filler.The polymer nano material of this method preparation
Elasticity modulus with higher, but the polymer nano material can not be applied to 3D printing.
And the physical mechanical property of above-mentioned polymer composites is still to be improved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of 3D printing with compared with high-mechanical property
Use composite material and preparation method.
The present invention provides a kind of 3D printing composite materials, comprising:
100 parts by weight of polyphenylene sulfone resins and/or polyetherimide；
23~28 parts by weight of polycarbonate；
0.5~2 parts by weight of organo-clay.
Preferably, the polyphenylene sulfone resins and the mass ratio of polyetherimide are (40~60): (60~40).
Preferably, the organo-clay is the modified montmorillonite of organic guanidine salt；The modified illiteracy of organic guanidine salt is de-
Stone is prepared according to the following steps: organic guanidine salt being mixed in water with montmorillonite, obtains the modified montmorillonite of guanidine salt.
Preferably, the guanidine salt is selected from two allyl guanidine acetate, diallyl guanidine trifluoroacetate, methacrylate
One of guanidine and acrylate guanidine are a variety of.
Preferably, the quality of organic guanidine salt is the 2%~10% of montmorillonite quality.
Preferably, the melt flow rate of the polyphenylene sulfone resins is preferably 10~30g/10min；The glass of the polyetherimide
Glass transition temperature is 200 DEG C~230 DEG C.
Preferably, the polyphenylene sulfone resins are Radel R-5100；The polyetherimide is ULTEM PEI 1000.
The present invention also provides a kind of preparation methods of 3D printing composite material, comprising:
By the polyphenylene sulfone resins of 100 parts by weight and/or polyetherimide, the polycarbonate of 23~28 parts by weight and 0.5~
The organo-clay Hybrid Heating of 2 parts by weight, obtains 3D printing composite material.
Preferably, the temperature of the Hybrid Heating is 140 DEG C~160 DEG C.
The present invention provides a kind of 3D printing composite materials, comprising: 100 weight of polyphenylene sulfone resins and/or polyetherimide
Measure part；23~28 parts by weight of polycarbonate；0.5~2 parts by weight of organo-clay.Compared with prior art, the present invention is with poly-
Benzene sulphone resin, polyetherimide and polycarbonate improve composite wood simultaneously added with the modified clay of machine as resin raw material
The physical mechanical property of material, and reduce the extent of the destruction of fiber.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
The present invention provides a kind of 3D printing composite materials, comprising:
100 parts by weight of polyphenylene sulfone resins and/or polyetherimide；
23~28 parts by weight of polycarbonate；
0.5~2 parts by weight of organo-clay.
The present invention is not particularly limited the source of all raw materials, is commercially available.
The present invention is basic material with polyphenylene sulfone resins (PPSU) and/or polyetherimide (PEI), more preferably with polyphenyl
Sulphone resin and the mixture of polyetherimide are as basic material；The polyphenylene sulfone resins and the mass ratio of polyetherimide are excellent
Be selected as (40~60:(60~40), more preferably (45~55): (55~45) are further preferably 50:50；The polyphenylene sulfone resins
Melt flow rate be preferably 10~30g/10min, more preferably 12~25g/10min is further preferably 14~20g/10min；At this
In invention, the polyphenylene sulfone resins are most preferably Radel R-5100；The glass transition temperature of the polyetherimide is preferred
It is 200 DEG C~230 DEG C, more preferably 210 DEG C~225 DEG C, be further preferably 215 DEG C~220 DEG C, most preferably 217 DEG C；At this
In invention, the polyetherimide is most preferably ULTEM PEI 1000.
The content of the polycarbonate is preferably 25~28 parts by weight, more preferably 26~27 parts by weight；The poly- carbonic acid
Ester is preferably the particle of brand Carbomix, is prepared according to technical specification 2226-002-13619882-2006；In the present invention
In some embodiments provided, the polycarbonate content is preferably 23 parts by weight；In some embodiments provided by the invention
In, the content of the polycarbonate is preferably 27 parts by weight；In some embodiments provided by the invention, the polycarbonate
Content be preferably 28 parts by weight；In some embodiments provided by the invention, the content of the polycarbonate is preferably 26
Parts by weight；In other embodiments provided by the invention, the content of the polycarbonate is preferably 25 parts by weight.
According to the present invention, the content of the organo-clay is preferably 1~2 parts by weight, more preferably 1.5~2 weight
Part；In some embodiments provided by the invention, the content of the organo-clay is preferably 0.5 parts by weight；In the present invention
In some embodiments provided, the content of the organo-clay is preferably 1 parts by weight；In some realities provided by the invention
It applies in example, the content of the organo-clay is preferably 1.5 parts by weight；In other embodiments provided by the invention, institute
The content for stating organo-clay is preferably 2 parts by weight；The organo-clay is preferably organically-modified montmorillonite, more
The modified montmorillonite of preferably organic guanidine salt.
The modified montmorillonite of organic guanidine salt is preferably prepared in accordance with the following methods: by organic guanidine salt and montmorillonite in water
Middle mixing obtains urea-modified montmorillonite；The cation exchange capacity of the montmorillonite be preferably 80~150 milliequivalents/
100 grams, more preferably 90~120 milliequivalent/100 gram are further preferably 90~100 milliequivalent/100 gram, most preferably 95
Milliequivalent/100 gram；The quality of organic guanidine salt is preferably the 2%~10% of montmorillonite quality, more preferably 4%~
8%, it is further preferably 4%~6%, most preferably 5%；Organic guanidine salt be preferably two allyl guanidine acetate (Formulas I, X H),
Diallyl guanidine trifluoroacetate (Formula II, X F), methacrylate guanidine (formula III, R CH3) and acrylate guanidine (formula
IV, R H) one of or it is a variety of.
In the present invention, it is preferred to which first montmorillonite and water are mixed, then add organic guanidine salt and continue to stir；Institute
The time for stating mixing is preferably 10~40min, more preferably 20~40min, is further preferably 30min；It is described to continue to stir
Time be preferably 1~4h, more preferably 2~3h；Above-mentioned steps preferably carry out at room temperature；Continue to stir
After the completion, it is preferably repeated several times and is decanted with water, after drying at room temperature, obtain the modified montmorillonite of organic guanidine salt；The drying at room temperature
Time be preferably 20~30h, more preferably 22~28h is further preferably 24~26h.
The present invention is modified simultaneously added with machine using polyphenylene sulfone resins, polyetherimide and polycarbonate as resin raw material
Clay, improves the physical mechanical property of composite material, and reduces the extent of the destruction of fiber.
The present invention also provides a kind of preparation methods of above-mentioned 3D printing composite material, comprising: by 100 parts by weight
The organo-clay of polyphenylene sulfone resins and/or polyetherimide, the polycarbonate of 23~28 parts by weight and 0.5~2 parts by weight
Hybrid Heating obtains 3D printing composite material.
Wherein, the polyphenylene sulfone resins, polyetherimide, polycarbonate and organo-clay are with shown on, herein
It repeats no more.
By polyphenylene sulfone resins and/or polyetherimide, polycarbonate and organo-clay Hybrid Heating, obtains 3D and beat
Print uses composite material；The temperature of the Hybrid Heating is preferably 140 DEG C~160 DEG C, more preferably 146 DEG C~160 DEG C；It is described
Hybrid Heating preferably carries out in an extruder；The temperature of four heating regions of the extruder is preferably followed successively by 146 DEG C, 149
DEG C, 155 DEG C with 160 DEG C.
In order to further illustrate the present invention, with reference to embodiments to a kind of 3D printing composite wood provided by the invention
Material and preparation method thereof is described in detail.
Reagent used in following embodiment is commercially available；PPSU used is Radel R5100 in embodiment；PEI is
ULTEM PEI 1000；Polycarbonate is the particle of brand Carbomix, according to technical specification 2226-002-13619882-
2006 preparations (Russia)；Organo-clay is the modified montmorillonite of organic guanidine salt, and the quality of organic guanidine salt is montmorillonite matter
The 5% of amount；Organic guanidine salt is two allyl guanidine acetate (Formulas I, X H).
Examples 1 to 6
According to the amount of PPSU ﹑ PEI as defined in formula (table 1), Ju Tan Suan Zhi ﹑ organo-clay, it is successively loaded into
In work mixer；The pulverulent mixture of acquisition is poured into extruder, and in region I~IV, i.e., 146 DEG C of temperature, 149 DEG C,
155 DEG C corresponding at 160 DEG C to be processed, and obtains particle i.e. 3D printing composite material.
The polymer filament that diameter is 1.75 millimeters is made with the particle of acquisition, so as to subsequent use, is surveyed to obtain 3D printing
The sample of examination.3D printer RobozeOne+400 need to be used by obtaining sample.
In the research of composite material, following standard has been used:
1. Soviet Union national standard 9550-81 entirely；Plastics；The method for determining the elasticity modulus under La Shen ﹑ Ya Suo ﹑ bending；
2. Soviet Union national standard 4648-2014 (ISO 178:2010) entirely；Plastics；Static bending test method (revision)；
3. Soviet Union national standard 11262-80 (С Т С Э В 1199-78) entirely；Plastics；(N 1 becomes stretching test method
Change).
Test result is as shown in table 2.
The ingredient of 1 embodiment composite material of table
2 composite property test result of table
Claims (9)
1. a kind of 3D printing composite material characterized by comprising
100 parts by weight of polyphenylene sulfone resins and/or polyetherimide；
23~28 parts by weight of polycarbonate；
0.5~2 parts by weight of organo-clay.
2. 3D printing composite material according to claim 1, which is characterized in that the polyphenylene sulfone resins and polyetherimide
The mass ratio of amine is (40~60): (60~40).
3. 3D printing composite material according to claim 1, which is characterized in that the organo-clay is organic guanidine
The modified montmorillonite of salt；The modified montmorillonite of organic guanidine salt is prepared according to the following steps: organic guanidine salt and montmorillonite are existed
It is mixed in water, obtains the modified montmorillonite of guanidine salt.
4. 3D printing composite material according to claim 3, which is characterized in that the guanidine salt is selected from two allyl guanidine acetic acid
One of salt, diallyl guanidine trifluoroacetate, methacrylate guanidine and acrylate guanidine are a variety of.
5. 3D printing composite material according to claim 3, which is characterized in that the quality of organic guanidine salt is to cover to take off
The 2%~10% of stone quality.
6. 3D printing composite material according to claim 1, which is characterized in that the melt flow rate of the polyphenylene sulfone resins is excellent
It is selected as 10~30g/10min；The glass transition temperature of the polyetherimide is 200 DEG C~230 DEG C.
7. 3D printing composite material according to claim 1, which is characterized in that the polyphenylene sulfone resins are Radel R-
5100；The polyetherimide is ULTEM PEI 1000.
8. a kind of preparation method of 3D printing composite material characterized by comprising
By the polyphenylene sulfone resins of 100 parts by weight and/or polyetherimide, the polycarbonate of 23~28 parts by weight and 0.5~2 weight
The organo-clay Hybrid Heating of part, obtains 3D printing composite material.
9. preparation method according to claim 8, which is characterized in that the temperature of the Hybrid Heating is 140 DEG C~160
℃。
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| CN201910433619.4A CN110157189A (en) | 2019-05-23 | 2019-05-23 | A kind of 3D printing composite material and preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI745906B (en) * | 2020-03-27 | 2021-11-11 | 國立臺灣大學 | Poly(allylguanidine) and the manufacture method and the use thereof |
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| CN1784295A (en) * | 2003-05-05 | 2006-06-07 | 斯特拉塔西斯公司 | Material and method for three-dimensional modeling |
| RU2012127600A (en) * | 2012-07-03 | 2014-01-10 | Общество с ограниченной ответственностью "ПолиХимГрупп" | POLYAMIDE NANOCOMPOSITE MATERIAL |
| CN107353644A (en) * | 2017-07-27 | 2017-11-17 | 广州新诚生物科技有限公司 | A kind of 3D printing material and preparation method thereof |
| CN108291083A (en) * | 2015-10-05 | 2018-07-17 | 阿雷沃公司 | Amorphous poly(aryl ether ketone) and its blend for lamination manufacture |
| WO2018197577A1 (en) * | 2017-04-25 | 2018-11-01 | Eos Gmbh Electro Optical Systems | Method for producing a three-dimensional object |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1784295A (en) * | 2003-05-05 | 2006-06-07 | 斯特拉塔西斯公司 | Material and method for three-dimensional modeling |
| RU2012127600A (en) * | 2012-07-03 | 2014-01-10 | Общество с ограниченной ответственностью "ПолиХимГрупп" | POLYAMIDE NANOCOMPOSITE MATERIAL |
| CN108291083A (en) * | 2015-10-05 | 2018-07-17 | 阿雷沃公司 | Amorphous poly(aryl ether ketone) and its blend for lamination manufacture |
| WO2018197577A1 (en) * | 2017-04-25 | 2018-11-01 | Eos Gmbh Electro Optical Systems | Method for producing a three-dimensional object |
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| 张玉龙等: "《纳米复合材料手册》", 31 July 2005, 中国石化出版社 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI745906B (en) * | 2020-03-27 | 2021-11-11 | 國立臺灣大學 | Poly(allylguanidine) and the manufacture method and the use thereof |
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Application publication date: 20190823 |