CN106751608A - A kind of preparation method of high-ductility polylactic acid-base composite material - Google Patents
A kind of preparation method of high-ductility polylactic acid-base composite material Download PDFInfo
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- CN106751608A CN106751608A CN201611100870.1A CN201611100870A CN106751608A CN 106751608 A CN106751608 A CN 106751608A CN 201611100870 A CN201611100870 A CN 201611100870A CN 106751608 A CN106751608 A CN 106751608A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of high-ductility polylactic acid-base composite material, its step is：PLA and CNT are pressed 100:5 20 mass ratio, is obtained PLA/carbon nano tube compound material, as masterbatch after drying by double screw extruder；Extrusion temperature is 160 220 DEG C, and rotating speed is 100 250rpm.Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 1 50:15‑94:5‑35:0.1 1 mass ratio, by double screw extruder temperature be 160 220 DEG C, rotating speed be 100 250rpm under conditions of extrude, obtain final product.Polylactic acid-base composite material notch impact strength is high obtained in the method, and tensile strength preferably, belongs to high-ductility polylactic acid-base composite material.
Description
Technical field
The invention belongs to high-ductility field of polymer material preparing technology.
Background technology
PLA is a kind of aliphatic polymer, and fully, production process is pollution-free, is a kind of high intensity, height for raw material sources
Modulus, degradable environment-friendly material.The biocompatibility and biodegradability of PLA are preferable, in biomedicine field
It is widely used, for example surgical sutures, slow releasing carrier of medication etc..PLA also has preferable gas permeability and the transparency, because
This also has the application prospect of large-scale commercial in fields such as agricultural, packagings.But PLA has the fragility of height, notch shock
Strength ratio is relatively low, limits application in the industrial production, so PLA toughening modifying is the focus widely paid close attention to.
Current PLA toughening modifying mainly uses two methods of chemical copolymerization and physical blending.The former is by random, embedding
The methods such as section, grafting or crosslinking reach modified purpose, but generally process is complicated, relatively costly, therefore less apply in reality
In production.The latter is including with PLA as matrix, adding plasticizer, elastomer, toughness high polymer, inorganic filler etc., due to side
Method is simple and easy to apply, and cost is relatively low, so using relatively broad.For plasticizer, elastomer and toughness high polymer, by them
Introduce PLA, although toughness is increased, but the intensity and hardness of composite can be substantially reduced, and for montmorillonite, charcoal
For the inorganic fillers such as black, CNT, although their addition can improve the mechanical performance of composite, hot property and
Electric property etc., but filler dispersity, and between matrix compatibility influence it is larger, while to the raising journey of toughness
Degree is limited.
In recent years, it is intended that by multimedia combination come coordination plasticizing PLA, such as by nano-calcium carbonate and
Thermoplastic polyurethane is added in PLA, is prepared for polylactic acid-base composite material, as a result shows nano-calcium carbonate and thermoplastic poly
Urethane can play a part of coordination plasticizing, 7kJ/m of the notch impact strength from pure PLA2Left and right highest increases to about 41kJ/
m2, but tensile strength is reduced to about 30Mpa (Wang Zhe, nano-calcium carbonate/TPU coordination plasticizings PLA from the about 70MPa of pure PLA
Form and Study on Crystallinity Homo, plastics industry, the phase of volume 44 3,2016).
The content of the invention
It is an object of the invention to provide a kind of preparation method of high-ductility polylactic acid-base composite material, breast is gathered obtained in the method
Acidic group nano composite material impact strength is high, and tensile strength is preferable.
The technical scheme adopted by the invention for realizing the object of the invention is, a kind of preparation of high-ductility polylactic acid-base composite material
Method, its step is：
PLA and CNT are pressed 100:The mass ratio of 5-20, is obtained PLA/carbon and receives by double screw extruder
Mitron composite, as masterbatch after drying；Extrusion temperature during extrusion is 160-220 DEG C, and rotating speed is 100-250rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed into 1-50:15-94:5-35:
The mass ratio of 0.1-1, by double screw extruder temperature be 160-220 DEG C, rotating speed be 100-250rpm under conditions of extrude,
Obtain final product.
Compared with prior art, the beneficial effects of the invention are as follows：
First, reactive compatibilizer is added in second extrusion --- cumyl peroxide, dynamic can be played
Crosslinked action, promotes PLA and ethylene-vinyl acetate copolymer two-phase inside and two-phase interface that chemical crosslink reaction occurs.
On the one hand cumyl peroxide can play compatibilization so that the particle diameter of ethylene-vinyl acetate copolymer dispersed phase enters one
Step reduces, the reduction of matrix ligament thickness degree, theoretical from Wu ' s, and the reduction of matrix ligament thickness degree is conducive to improving material
Impact flexibility.On the other hand, cumyl peroxide can construct three dimensional chemical network structure in material internal, improve two alternate
Interaction so that further improve material impact strength.
2nd, CNT draw ratio is very big, and compliance and locomitivity very well, blending are extruded by mother material twice, can
To disperse on the two-phase interface of PLA and ethylene-vinyl acetate copolymer in the blend, and mutually overlap joint is built into three
Dimension physical network arrangement, increases by two alternate interaction forces, promotes stress in the transmission of material internal, so as to improve material
Impact strength.
3rd, by introducing chemical network structure and physical network arrangement simultaneously, stress is produced to exceed bleed-through road in material internal,
Promote matrix that shear yielding occurs, while coordination plasticizing is played to PLA matrix, also maintain good tensile strength.
It is demonstrated experimentally that the obtained polylactic acid-base composite material of the present invention, its impact strength improves 15 times than pure PLA
It is many, improve more than 6 times than PLA/ethylene-vinyl acetate copolymer (80/20) blend, it is that a kind of high-ductility PLA base is answered
Condensation material.
Further, the CNT that the present invention is used is a diameter of 5-200nm, and length is received for 100nm-50 μm of single wall carbon
Mitron or multi-walled carbon nano-tubes,
Further, vinyl acetate block concentration is 40-80wt% in the ethylene-vinyl acetate copolymer that the present invention is used.
Below by the present invention is described in further detail with specific embodiment.
Brief description of the drawings
Fig. 1 is the microscopic appearance photo of high-ductility polylactic acid-base composite material obtained in the embodiment of the present invention one.
Specific embodiment
Embodiment one：
PLA and CNT are pressed 100:10 mass ratio, PLA/carbon nanometer is obtained by double screw extruder
Pipe composite, as masterbatch after drying；Extrusion temperature during extrusion is 185 DEG C, and rotating speed is 150rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 20:60:20:0.4 quality
Than, by double screw extruder temperature be 190 DEG C, rotating speed be 120rpm under conditions of extrude, obtain final product.
The CNT that this example is used is multi-walled carbon nano-tubes, its a diameter of 10nm, and length is 10 μm；Ethyl vinyl acetate second
The content of vinyl acetate block is 50wt% in alkene copolymer.
Test shows that material obtained in this example, its notch impact strength can reach 54.7MPa, and tensile strength is
41.1MPa, it is high to belong to impact strength, and the preferable high-ductility polylactic acid-base composite material of tensile strength.
Fig. 1 is the microscopic appearance photo of the microscopic appearance photo of high-ductility polylactic acid-base composite material obtained in this example.In figure
Material can be clearly observed for island structure；Ethylene-vinyl acetate copolymer is dispersed phase, ethylene-vinyl acetate copolymer
Particle size and matrix ligament thickness degree are small, and CNT is dispersed in two-phase interface, can improve two-phase interface active force.
Embodiment two：
PLA and CNT are pressed 100:10 mass ratio, PLA/carbon nanometer is obtained by double screw extruder
Pipe composite, as masterbatch after drying；Extrusion temperature is 160 DEG C, and rotating speed is 100rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 1:94:5:0.1 quality
Than, by double screw extruder extrusion temperature be 160 DEG C, rotating speed be 100rpm under conditions of extrude, obtain final product.
The CNT of this example is a diameter of 200nm, and length is 50 μm of SWCN, and ethene-vinyl acetate is common
Vinyl acetate block concentration is 40wt% in polymers.
Embodiment three：
PLA and CNT are pressed 100:20 mass ratio, PLA/carbon nanometer is obtained by double screw extruder
Pipe composite, as masterbatch after drying；Extrusion temperature during extrusion is 220 DEG C, and rotating speed is 250rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 25:40:35:1 quality
Than, by double screw extruder extrusion temperature be 220 DEG C, rotating speed be 250rpm under conditions of extrude, obtain final product.
The CNT of this example is a diameter of 100nm, and length is 30 μm of SWCN, and ethene-vinyl acetate is common
Vinyl acetate block concentration is 80%wt in polymers.
Example IV：
PLA and CNT are pressed 100:5 mass ratio, PLA/CNT is obtained by double screw extruder
Composite, as masterbatch after drying；Extrusion temperature during extrusion is 200 DEG C, and rotating speed is 200rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 50:15:35:0.5 quality
Than, by double screw extruder extrusion temperature be 200 DEG C, rotating speed be 200rpm under conditions of, extrusion is obtained final product.
The CNT of this example is a diameter of 50nm, and length is 10 μm of multi-walled carbon nano-tubes, ethene-vinyl acetate copolymerization
Vinyl acetate block concentration is 60wt% in thing.
Embodiment five：
PLA and CNT are pressed 100:15 mass ratio, PLA/carbon nanometer is obtained by double screw extruder
Pipe composite, as masterbatch after drying；Extrusion temperature during extrusion is 180 DEG C, and rotating speed is 150rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed 10:75:15:0.8 quality
Than, by double screw extruder extrusion temperature be 180 DEG C, rotating speed be 150rpm under conditions of extrude, obtain final product.
The CNT of this example is a diameter of 5nm, and length is the multi-walled carbon nano-tubes of 100nm, ethene-vinyl acetate copolymerization
Vinyl acetate block concentration is 50wt% in thing.
Claims (3)
1. a kind of preparation method of high-ductility polylactic acid-base composite material, its step is：
PLA and CNT are pressed 100:The mass ratio of 5-20, PLA/CNT is obtained by double screw extruder
Composite, as masterbatch after drying；Extrusion temperature during extrusion is 160-220 DEG C, and rotating speed is 100-250rpm；
Masterbatch and PLA, ethylene-vinyl acetate copolymer, cumyl peroxide are pressed into 1-50:15-94:5-35:0.1-1
Mass ratio, by double screw extruder temperature be 160-220 DEG C, rotating speed be 100-250rpm under conditions of extrude, obtain final product.
2. the preparation method of a kind of high-ductility polylactic acid-base composite material according to claim 1, it is characterised in that：Described
CNT is a diameter of 5-200nm, and length is 100nm-50 μm of SWCN or multi-walled carbon nano-tubes.
3. the preparation method of a kind of high-ductility polylactic acid-base composite material according to claim 1, it is characterised in that：Described
Vinyl acetate block concentration is 40-80wt% in ethylene-vinyl acetate copolymer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430934A (en) * | 2023-11-28 | 2024-01-23 | 广东石油化工学院 | Composite toughening polymer material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017346A (en) * | 2014-06-07 | 2014-09-03 | 西南交通大学 | Method for preparing high-ductility polymer blend alloy by melt blending |
-
2016
- 2016-12-05 CN CN201611100870.1A patent/CN106751608A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017346A (en) * | 2014-06-07 | 2014-09-03 | 西南交通大学 | Method for preparing high-ductility polymer blend alloy by melt blending |
Non-Patent Citations (2)
| Title |
|---|
| XIONG-FEI WANG ET AL: ""Super toughened immiscible poly(L-lactide)/poly(ethylene vinyl acetate)(PLLA/EVA) blend achieved by in situ cross-linking reaction and carbon nanotubes"", 《COMPOSITES PART A: APPLIED SCIENCE AND MANUFACTURING》 * |
| 杨静晖等: ""石墨烯在PLA/EVA共混物中的界面分布及其导电行为研究"", 《2013年全国高分子学术论文报告会》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430934A (en) * | 2023-11-28 | 2024-01-23 | 广东石油化工学院 | Composite toughening polymer material and preparation method thereof |
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