CN109553943A - A kind of preparation method and product of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material - Google Patents
A kind of preparation method and product of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material Download PDFInfo
- Publication number
- CN109553943A CN109553943A CN201811516856.9A CN201811516856A CN109553943A CN 109553943 A CN109553943 A CN 109553943A CN 201811516856 A CN201811516856 A CN 201811516856A CN 109553943 A CN109553943 A CN 109553943A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- abietyl modified
- modified montmorillonite
- printing material
- montmorillonite
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention relates to the preparation methods and product of a kind of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material, belong to 3D printing technique field, this method is that Abietyl modified montmorillonite is added in polylactic acid, and Abietyl modified montmorillonite enhancing polylactic acid 3D printing material is finally made by wire drawing.The material has preferable bending strength, impact strength and tensile strength, and its preparation process is simple, and it is easy to operate, it is low for equipment requirements, and high production efficiency, and it is environmentally friendly, it is suitble to industrialized production, it is few solves existing 3D printing wire rod type, production efficiency is low, the complex and costly problem of process.
Description
Technical field
The invention belongs to 3D printing technique fields, and in particular to a kind of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material
The preparation method and product of material.
Background technique
With the raising of social progress and scientific and technological level, the development of high molecular material and its product is also being constantly progressive,
Requirement of the people to all kinds of aspect of performance of plastic products is also being continuously improved, the Depth Study that researchers carry out various plastics
There is progress very abundant, but still every demand of market today cannot be fully met.
3D printing receives extensive concern all over the world as emerging manufacturing process, it is a kind of with mathematical model text
Based on part, with adhesive materials such as powdery metal or plastics, the technology of object is constructed by layer-by-layer printing.
Its convenient and fast processing method and accurate stereochemical structure mould ability, become current one of research emphasis and hot topic.
Polylactic acid to the less pollution of environment, and has good as a kind of outstanding new bio degradable material
Biocompatibility, while it also has excellent physics and chemical property, is suitable for the various processing such as 3D printing, blow molding, thermoplastic
Method, easy to process, application is very extensive.It can be used for processing from industry to civilian various plastic products, packaged food, fast food
Lunch box, non-woven fabrics, industry and civilian cloth etc., and then it is processed into geotextile, health care fabric, rag, amenities, outdoor anti-purple
Outer wire fabric, tent cloth, ground cushion face etc., market prospects are very good.However, polylactic acid has so excellent performance
Meanwhile also having processing cost costly, cause it to remain high in the price in market, in addition, polylactic acid quality is more crisp,
Also limit its strength character.Therefore, the polylactic acid 3D printing material of Low-cost, good mechanical properties is with important meaning
Justice.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of Abietyl modified montmorillonites to enhance polylactic acid 3D printing material
The preparation method of material；The second purpose is to provide a kind of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, a kind of preparation method of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material, the method includes walking as follows
It is rapid:
(1) montmorillonite, rosin and sodium hydroxide are added to the water by mass volume ratio 10-15:1-1.5:0.12:100, are stirred
It is filtered after mixing 5-7h, after taking solid phase dry, obtains Abietyl modified montmorillonite；The unit of the mass volume ratio is g:g:g:mL；
(2) the Abietyl modified montmorillonite obtained in step (1) and polylactic acid are carried out blending extrusion by 1:9-19 in mass ratio
Abietyl modified montmorillonite enhancing polylactic acid 3D printing material is made in wire drawing.
Preferably, in step (1), the mass volume ratio is 12:1.3:0.12:100.
Preferably, in step (1), the mixing time is 6h.
Preferably, in step (1), the drying is the dry 24-36h at 50-60 DEG C.
Preferably, in step (2), the temperature when blending is 180-210 DEG C.
Preferably, in step (2), the diameter of the Abietyl modified montmorillonite enhancing polylactic acid 3D printing material is 1.70-
1.75mm。
2, polylactic acid 3D printing material is enhanced by Abietyl modified montmorillonite prepared by the method.
The beneficial effects of the present invention are: the present invention provides a kind of Abietyl modified montmorillonites to enhance polylactic acid 3D printing material
The preparation method and product of material make finally to prepare by adding Abietyl modified montmorillonite in polylactic acid and controlling its additive amount
3D printed material have preferable bending strength, impact strength and tensile strength, simultaneously as cheap montmorillonite and pine
Fragrant addition, the dosage of polylactic acid is reduced under the premise of not influencing usability, reduces the overall cost of raw material.Due to
Montmorillonite has suction-operated to anionic surfactant, and rosin can generate anionic surface activity after alkali process
Agent-rosin acid, and can be attracted in the porous structure of montmorillonite and on surface, to make the stronger illiteracy of script surface polarity
De- soil material Surface Creation has the modified layer of anionic surfactant, substantially reduces the surface energy of montmorillonite, makes montmorillonite
Lipophilicity is changed by hydrophily, and then improves the interface compatibility between montmorillonite and lipophilic polylactic acid, meanwhile, pine
The addition of fragrant acid can also be such that the interlamellar spacing of montmorillonite increases, and so that the segment of lipophilic polylactic acid chain segment is can enter interlayer, into one
Step increases the compatibility between montmorillonite and polylactic acid, and the Abietyl modified montmorillonite finally prepared is made to enhance polylactic acid 3D printing
Material has preferable bending strength, impact strength and toughness.The preparation process is simple, easy to operate, low for equipment requirements, and raw
It produces high-efficient and environmentally friendly, is suitble to industrialized production, solves that existing 3D printing wire rod type is few, and production efficiency is low, mistake
The complex and costly problem of journey.
Specific embodiment
Below by a preferred embodiment of the present invention will be described in detail.
Embodiment 1
Prepare Abietyl modified montmorillonite enhancing polylactic acid 3D printing material
(1) montmorillonite, rosin and sodium hydroxide are added in deionized water by mass volume ratio 10:1:0.12:100, are stirred
It is filtered after mixing 5h, solid phase is taken after dry 36h, to obtain Abietyl modified montmorillonite at 50 DEG C；The unit of mass volume ratio is g:g:
g:mL；
(2) the Abietyl modified montmorillonite and polylactic acid that obtain in step (1) are total to by 1:19 in mass ratio at 180 DEG C
It is mixed, wire drawing is squeezed out by wire drawing machine, the Abietyl modified montmorillonite that diameter is 1.70mm, which is made, enhances polylactic acid 3D printing material.
Embodiment 2
Prepare Abietyl modified montmorillonite enhancing polylactic acid 3D printing material
(1) montmorillonite, rosin and sodium hydroxide are added in deionized water by mass volume ratio 12:1.3:0.12:100,
It is filtered after stirring 6h, solid phase is taken after dry 30h, to obtain Abietyl modified montmorillonite at 55 DEG C；The unit of mass volume ratio is g:
g:g:mL；
(2) 1:11.5 in mass ratio carries out the Abietyl modified montmorillonite and polylactic acid that obtain in step (1) at 200 DEG C
It is blended, wire drawing is squeezed out by wire drawing machine, the Abietyl modified montmorillonite that diameter is 1.70mm, which is made, enhances polylactic acid 3D printing material.
Embodiment 3
Prepare Abietyl modified montmorillonite enhancing polylactic acid 3D printing material
(1) montmorillonite, rosin and sodium hydroxide are added in deionized water by mass volume ratio 15:1.5:0.12:100,
It is filtered after stirring 7h, solid phase is taken after drying for 24 hours, to obtain Abietyl modified montmorillonite at 60 DEG C；The unit of mass volume ratio is g:
g:g:mL；
(2) the Abietyl modified montmorillonite and polylactic acid that obtain in step (1) are total to by 1:9 in mass ratio at 210 DEG C
It is mixed, wire drawing is squeezed out by wire drawing machine, the Abietyl modified montmorillonite that diameter is 1.70mm, which is made, enhances polylactic acid 3D printing material.
Comparative example 1
Pure particles of polylactic acid is carried out to wire drawing on wire drawing machine and obtains the material for the 3D printing that diameter is 1.70mm.
Comparative example 2
The difference from embodiment 1 is that the mass ratio 1:4 of Abietyl modified montmorillonite and polylactic acid.
Comparative example 3
The difference from embodiment 1 is that the mass ratio 1:29 of Abietyl modified montmorillonite and polylactic acid.
Comparative example 4
The difference from example 2 is that carrying out that wire drawing is blended with polylactic acid using unmodified montmorillonite.
Testing example 1 is distinguished to embodiment 3, the 3D printing material that comparative example 1 is prepared into comparative example 4
Bending strength, tensile strength and impact strength, test result are shown in Table 1, and as shown in Table 1, compared to original polylactic acid material, (comparison is real
Apply example 1) mechanical property of 3D printing material prepared in embodiment 1 to 3 promoted, and the 3D prepared in embodiment 2 is beaten
The mechanical property generally highest of material, bending strength 76MPa, tensile strength 67MPa are printed, impact strength is
3.7kJ/m2.The reason is that when the content of Abietyl modified montmorillonite in the 3D printing material finally prepared is lower, 3D printing
Material overall performance does not improve a lot compared to pure polylactic acid, and a small amount of Abietyl modified montmorillonite performance is not played, right
Than in embodiment 3, Abietyl modified montmorillonite content is less in prepared 3D printing material, tests its performance and shows, the 3D printing
The mechanical property of material is not obviously improved, and illustrating a small amount of modified montmorillonoid not excessively influences the performance of composite material.
On the other hand, when montmorillonite content Abietyl modified in 3D printing material is higher, then it will lead to 3D printing material internal defect point
Increase, influence performance, mechanical property is caused to begin to decline, such as 3D printing material prepared in comparative example 2, the material
The test data of correlated performance is decreased obviously relative to the test data of the 3D printing material correlated performance prepared in embodiment 2,
It demonstrates when montmorillonite content Abietyl modified in 3D printing material is higher, the mechanics of the 3D printing material finally prepared can be reduced
Performance.
In addition, if directly adding unmodified montmorillonite and polylactic acid blend (comparative example 4), due to the not phase at interface
Capacitive, montmorillonite and defect on polylactic acid contact surface are larger, and theoretically material property can be decreased obviously, and after tested, comparison is implemented
Bending strength, tensile strength and the impact strength of the 3D printing material prepared in example 4 are respectively 56MPa, 49MPa, 2.5kJ/m2,
Relative to the 3D printing material containing the Abietyl modified montmorillonite of equivalent in embodiment 2, mechanical property is significant lower, this is illustrated
Imvite modified necessity.
Bending strength, tensile strength and the impact strength test result of the 3D printing material prepared in each embodiment of table 1
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (7)
1. a kind of preparation method of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material, which is characterized in that the method packet
Include following steps:
(1) montmorillonite, rosin and sodium hydroxide are added to the water by mass volume ratio 10-15:1-1.5:0.12:100, stir 5-
It is filtered after 7h, after taking solid phase dry, obtains Abietyl modified montmorillonite；The unit of the mass volume ratio is g:g:g:mL；
(2) the Abietyl modified montmorillonite obtained in step (1) and polylactic acid are carried out blending extrusion wire drawing by 1:9-19 in mass ratio,
Abietyl modified montmorillonite enhancing polylactic acid 3D printing material is made.
2. the method according to claim 1, wherein the mass volume ratio is 12:1.3 in step (1):
0.12:100。
3. the method according to claim 1, wherein the mixing time is 6h in step (1).
4. the method according to claim 1, wherein the drying is dry at 50-60 DEG C in step (1)
24-36h。
5. the method according to claim 1, wherein in step (2), the temperature when blending is 180-210
℃。
6. the method according to claim 1, wherein the Abietyl modified montmorillonite enhancing is poly- newborn in step (2)
The diameter of sour 3D printing material is 1.70-1.75mm.
7. enhancing polylactic acid 3D printing material by Abietyl modified montmorillonite prepared by method described in any one of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811516856.9A CN109553943B (en) | 2018-12-12 | 2018-12-12 | Preparation method and product of rosin modified montmorillonite reinforced polylactic acid 3D printing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811516856.9A CN109553943B (en) | 2018-12-12 | 2018-12-12 | Preparation method and product of rosin modified montmorillonite reinforced polylactic acid 3D printing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109553943A true CN109553943A (en) | 2019-04-02 |
| CN109553943B CN109553943B (en) | 2020-12-29 |
Family
ID=65869737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811516856.9A Active CN109553943B (en) | 2018-12-12 | 2018-12-12 | Preparation method and product of rosin modified montmorillonite reinforced polylactic acid 3D printing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109553943B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999465A (en) * | 2021-10-22 | 2022-02-01 | 翁定也 | High-thermal-stability PVC (polyvinyl chloride) film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792152A (en) * | 2009-09-23 | 2010-08-04 | 江苏强林生物能源有限公司 | Abietyl quaternary ammonium salt-modified organic nano imvite, preparation method thereof and use thereof |
| CN108707320A (en) * | 2018-03-23 | 2018-10-26 | 中国科学院宁波材料技术与工程研究所 | Highly conductive organic modification montmonrillonite/poly lactic acid nano composite material and its preparation method and application |
-
2018
- 2018-12-12 CN CN201811516856.9A patent/CN109553943B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792152A (en) * | 2009-09-23 | 2010-08-04 | 江苏强林生物能源有限公司 | Abietyl quaternary ammonium salt-modified organic nano imvite, preparation method thereof and use thereof |
| CN108707320A (en) * | 2018-03-23 | 2018-10-26 | 中国科学院宁波材料技术与工程研究所 | Highly conductive organic modification montmonrillonite/poly lactic acid nano composite material and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999465A (en) * | 2021-10-22 | 2022-02-01 | 翁定也 | High-thermal-stability PVC (polyvinyl chloride) film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109553943B (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107618243B (en) | A kind of polymer modification graphene/Kynoar high-dielectric composite material and preparation method thereof | |
| CN106057279B (en) | A kind of new polymers/Graphene compliant conductive composite membrane and preparation method thereof | |
| CN102675804B (en) | Thermoplastic konjac glucomannan/graphene oxide compound material and preparation method thereof | |
| CN107541033A (en) | A kind of high gas-obstructing character nano composite material and preparation method thereof | |
| CN103146157B (en) | Composite modified foam material of a kind of full biomass and preparation method thereof | |
| CN102580549A (en) | Method for preparing carbon nano tube modified bipolar membrane with anion groups | |
| CN107033562A (en) | Root of kudzu vine nano-cellulose fiber polylactic acid plastic film and preparation method thereof | |
| CN107474343B (en) | Method for preparing sea squirt nano microcrystalline cellulose/rubber nano composite material by one-pot method | |
| CN109608841A (en) | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material | |
| CN105384960B (en) | A kind of Kynoar/nano-cellulose super hydrophobic material and preparation method thereof | |
| CN113801339A (en) | Modified lignin and preparation method thereof | |
| CN106971865A (en) | A kind of Polymerization of Polyaniline/carbon Nanotube with high specific capacitance/bafta composite and flexible electrode and its preparation and application | |
| CN109553943A (en) | A kind of preparation method and product of Abietyl modified montmorillonite enhancing polylactic acid 3D printing material | |
| CN102516575B (en) | Method for preparing bipolar membrane modified by heavy metal ion loaded carbon nao tube | |
| CN105968777A (en) | Antistatic composite nano material film and preparation method thereof | |
| CN109593331A (en) | A kind of preparation method and product of graphene oxide tannic acid compound enhancing polylactic acid 3D printing material | |
| CN106366678A (en) | High-performance wood-plastic composite material | |
| CN103289258B (en) | A kind of high-dielectric composite material, Preparation Method And The Use | |
| CN108822511A (en) | A kind of preparation method of the full biomass 3D printing nano combined wire rod of PLA | |
| CN106273988A (en) | A kind of preparation method of the in-situ modified bamboo fiber composite material of calcium carbonate | |
| CN110903606B (en) | Plant oil-based composite material and preparation method thereof | |
| CN110240732B (en) | Rapid preparation method of super-hydrophobic conductive sponge based on tungsten disulfide and hydrophobic silver nanoparticles | |
| CN107760050A (en) | A kind of bio-based wheat stalk PP composite material and preparation method thereof | |
| CN106349727A (en) | Novel wood-plastic composite | |
| JP2023025708A (en) | Type ii unmodified cellulose microfiber, type ii unmodified cellulose microfiber compact, and method for manufacturing type ii unmodified cellulose microfiber and compact of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |