CN105860463A - Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof - Google Patents
Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN105860463A CN105860463A CN201610130568.4A CN201610130568A CN105860463A CN 105860463 A CN105860463 A CN 105860463A CN 201610130568 A CN201610130568 A CN 201610130568A CN 105860463 A CN105860463 A CN 105860463A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- alloy material
- polycarbonate alloy
- increase
- volume
- 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.)
- Pending
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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention mainly relates to a compatibilized polylactic acid/polycarbonate alloy material and a preparation method thereof. The novel compatibilized polylactic acid/polycarbonate alloy material takes polylactic acid and polycarbonate as main raw materials, an appropriate amount of an AX8900 type compatibilizer EMG of Arkema France; a nucleating agent is selected from an organic nucleating agent adipyl benzoyl hydrazine (BHAD). The novel compatibilized polylactic acid/polycarbonate alloy material prepared from raw materials and auxiliary materials has more excellent elongation at break and toughness and the like compared with pure polylactic acid, is expected to replace traditional non-degradable materials, is applied in mobile communication, computers and other fields, and alleviates the environmental problems brought by white pollution.
Description
Technical field
The present invention relates to a kind of increase-volume polylactic acid/Polycarbonate alloy material and preparation method thereof.
Background technology
Polylactic acid (poly-(lactide acid), PLA) is to have excellent mechanical property, biocompatibility, biological fall
Solution property and renewable synthesis macromolecular material.Under natural environment, discarded polylactic acid article, can by hydrolysis and biological metabolism
It is completely transformed into carbon dioxide and water.Hereafter carbon dioxide and water may also pass through photosynthesis of plant and generates starch, and starch is sent out
Can become the initiation material of polylactic acid synthesis, environmentally safe after ferment, it is achieved clean Carbon cycle, it is sustainable to be that one possesses
The complete natural type Biodegradable material of developing characteristics.
But polylactic acid there is also some defects: (1) main chain rigidity is big, and flexibility is the best, and impact resistance is poor, and fragility is high；(2) heat
Deformation temperature low (being 54 ° of C under 0.46MPa load)；(3) polylactic acid crystal speed is slow, and injection molding cycle is longer, is unfavorable for raw
Produce processing.The above-mentioned drawbacks limit range of application of poly-lactic acid material, therefore, particularly significant to the study on the modification of polylactic acid.
From current research it is found that need to improve toughness and the thermostability of PLA material simultaneously, it is necessary to select a kind of resistance to
Hot height and have the macromolecule of higher toughness, meanwhile, its processing temperature must be close with the processing temperature of PLLA, prevents
PLA thermal degradation.PC is a preferable selection, and its vicat softening temperature is 144 ° of C, and it is strong to have higher shock resistance
Degree.Bayer material scientific & technical corporation of Germany is proposed a PC/PLLA alloy material, but its thermostability still cannot meet automobile, electricity
The application demand of sub-product etc..
Carry out being blended by polylactic acid and Merlon and prepare polylactic acid/Polycarbonate alloy material, on the one hand due to
The excellent mobility that polylactic acid is had, can improve Merlon and be difficult to the problem of processing and forming, on the other hand can carry
The heat resistance of high polylactic acid and mechanical strength, but below existing in the alloying preparation process of polylactic acid and Merlon
Difficult point: the problems such as the two poor compatibility, polylactic acid crystal poor performance.Therefore, people the most more study.
But, the research of people mostly concentrates on to use to have and makes having of the declines such as the color and luster of goods, outward appearance and molecular weight
Machine little molecule reactive compatibilizer, such as: in terms of ester exchange agent etc. improve compatibility of polylactic acid/polycarbonate alloy etc., but
It is that the appearance of side effect often makes goods that bad change occurs in terms of color and luster, molecular weight etc., affects the use of product.
Summary of the invention
An object of the present invention is to overcome problems of the prior art, it is provided that a kind of increase-volume polylactic acid/poly-
Carbonic ester alloy material, compares pure polylactic acid, and the elongation at break of this alloy material, impact strength, heat resistance all have difference
Degree improves.
The two of the purpose of the present invention are to provide the preparation method of this alloy material.
In order to achieve the above object, the present invention adopts the following technical scheme that
A kind of increase-volume polylactic acid/Polycarbonate alloy material, it is characterised in that the composition of this alloy material and parts by weight are:
Polylactic acid 10-90 part；
Merlon 10-90 part；
Bulking agent 1-7 part；
Nucleator 0-1 part.
Above-mentioned polylactic acid is at least one in Pfansteihl and D-ALPHA-Hydroxypropionic acid, and the weight average molecular weight of this polylactic acid is
60000g/mol-600000g/mol。
Above-mentioned Merlon includes in linear polycarbonate resin, branched polycarbonate resin and Copolycarbonate
At least one, weight average molecular weight is 10000g/mol-75000g/mol.
Above-mentioned bulking agent EMG is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
Above-mentioned nucleator is organic nucleator.
Above-mentioned organic nucleator is: adipyl benzoyl hydrazine.
A kind of method preparing above-mentioned increase-volume polylactic acid/Polycarbonate alloy material, it is characterised in that this preparation method
Comprise step in detail below: being added by all raw materials and carry out melt blending, processing temperature is 190 to 220 DEG C, and rotor speed is 50
To 70 revs/min, the time of staying is 5 to 10 minutes, cooled, dry and pelletizing, prepares described increase-volume polylactic acid/poly-carbonic acid
Ester alloy material.
The technical scheme is that addition bulking agent EMG in polylactic acid/polycarbonate alloy, due to bulking agent EMG
Amphiphilic polylactic acid phase and Merlon phase, we by differential scanning calorimeter and polarizing microscope it can be seen that alloy material
Interface between middle polylactic acid phase and the step of the vitrification point of Merlon phase gradually become shallower as and be biphase tapers into.I
Find further through the polylactic acid/polycarbonate alloy using injection molding process to make: impact strength, elongation at break and resistance to
Hot all it is significantly improved.Simultaneously from scanning electron microscope (SEM) it can be seen that along with the addition of bulking agent EMG, polylactic acid
Boundary alternate with Merlon mutually gradually thickens, and biphase size also occurs corresponding change.
Accompanying drawing explanation
Fig. 1. add the DSC heating curve under the conditions of different content compatilizer.
Fig. 2. sample h(is left) and h-e7(right) polarizing microscope light field figure (10X amplification).
Fig. 3. by sample h and the scanning electron microscope diagram of h-e7 impact fracture surface.
Fig. 4. by sample h, h-e1, h-e3, h-e7 impact strength schematic diagram.
Fig. 5. by sample h, h-e1, h-e3, h-e7 elongation at break schematic diagram.
Fig. 6. by sample h, h-e1, h-e3, h-e7 Vicat softening point schematic diagram.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is further described
Raw material sources used by the embodiment of the present invention are as follows:
Merlon is the bisphenol A polycarbonate (hereinafter referred to as PC) 2405 of Beyer Co., Ltd, molecular weight be 25000～
28000g/mol。
Polylactic acid uses the PLA4032D(hereinafter referred to as PLA of NATURE WORKS company of the U.S.).
Toughener uses the AX8900 type resin EMG(hereinafter referred to as EMG of France's Acker agate).
Nucleator uses the adipyl benzoyl hydrazine BHAD(hereinafter referred to as BHAD synthesized voluntarily).
The present invention uses the HAAKE PolyLab QC type flow graph that Thermofischer company of the U.S. produces.
Main performance method of testing of the present invention is as follows:
Notch impact strength: test by ASTM D256, specimen size is 64mm*12.7mm*3.2mm, lacks
The mouth degree of depth is 2.2mm, and test equipment is ZBC 50 pendulum machine that material tests company is newly thought carefully in Shenzhen.
Elongation at break test is tested by ASTM D638, and specimen size is 168mm*13mm*3.2mm, surveys
Examination speed is 50mm/min, and test equipment is the universal tensile testing machine that company is surveyed in Shenzhen ten thousand.
Heat resistance test is tested by ASTM D648, and specimen size is 64mm*12.7mm*3.2mm, heats up
Speed is 120 DEG C/h, test equipment be Shenzhen Stock Exchange city newly think carefully material tests company limited microcomputer control thermal deformation dimension
Card softening test machine.
The pro type of scanning electron microscope (SEM) Shi Funa scientific instrument (Shanghai) Co., Ltd..
Differential scanning calorimeter (DSC) is the Q2000 type of TA company of the U.S..
Polarizing microscope (POM) is the DM2700P type of Leica company of Germany.
Injection machine is the HAAKE MINJET II injection machine that match Mo Feishier company of the U.S. produces.
See Fig. 1～Fig. 6, h in figure, h-e1, h-e2 ... h-e7 represents interpolation phase in polylactic acid/polycarbonate alloy respectively
The mass percentage content holding agent EMG is 0,1,2 ... 7 wt%.
See Fig. 1 from the DSC heating curve added under the conditions of different content compatilizer: along with the increase of EMG content,
In alloy material, polylactic acid phase gradually becomes shallower as with the step of the vitrification point of Merlon phase, and biphase vitrification point it
Between distance the most close.It can be seen that EMG alternate serves certain compatibilization two.
See Fig. 2, from the polarizing microscope light field figure of sample h and h-e7: add after bulking agent EMG, polylactic acid and
Interface between Merlon is biphase tapers into, and this is owing to decreasing after EMG increase-volume caused by two alternate interfacial tensions.
See Fig. 3, from sample h and the scanning electron microscope diagram of h-e7 impact fracture surface: polylactic acid phase and poly-carbonic acid
The boundary that ester is alternate gradually thickens, and biphase size also occurs corresponding change.
Seeing Fig. 4, by sample h, h-e1, h-e3, h-e7 impact strength schematic diagram understands: along with the increase of EMG content, poly-
The impact strength of lactic acid/polycarbonate blending alloy gradually promotes, and then improves the ability of alloy material collapse resistance.
Seeing Fig. 5, by sample h, h-e1, h-e3, h-e7 elongation at break schematic diagram understands: along with the increase of EMG content,
The elongation at break of polylactic acid/polycarbonate blending alloy gradually promotes.
Seeing Fig. 6, by sample h, h-e1, h-e3, h-e7 Vicat softening point schematic diagram understands: along with the increase of EMG content,
The thermostability of polylactic acid/Polycarbonate alloy material presents slightly downward trend, but the addition of EMG is for improving material in general
Material heat resistance does not has remarkable effect.
Technical scheme is by adding bulking agent EMG in polylactic acid/polycarbonate alloy, due to bulking agent
EMG amphiphilic polylactic acid phase and Merlon phase, thus promote the biphase compatibility so that two-phase interface diminishes and refines
Phase region, is that alloy material has and compares the more preferable mechanical property of pure polylactic acid and heat resistance.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description should not be considered as limitative to the invention.After those skilled in the art have read foregoing, for the present invention
Multiple amendment and substitute all will be apparent from.Therefore, protection scope of the present invention should be limited by appended claim
Fixed.
Claims (6)
1. increase-volume polylactic acid/Polycarbonate alloy material, it is characterised in that composition and the weight percent of this alloy material contain
Amount is:
Polylactic acid 10-90%；
Merlon 10-90%；
Bulking agent 1-7%；
Organic nucleator 0-1%；
The weight/mass percentage composition sum of the most each component is 100%.
Increase-volume polylactic acid/Polycarbonate alloy material the most according to claim 1, it is characterised in that described polylactic acid is
At least one in Pfansteihl and D-ALPHA-Hydroxypropionic acid, the weight average molecular weight of this polylactic acid is 60000g/mol-600000g/mol.
Increase-volume polylactic acid/Polycarbonate alloy material the most according to claim 1, it is characterised in that described Merlon
Internal structure includes lienar for, branched chain type, and weight average molecular weight is 10000g/mol-75000g/mol.
Increase-volume polylactic acid/Polycarbonate alloy material the most according to claim 1, it is characterised in that described bulking agent
EMG is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
Increase-volume polylactic acid/Polycarbonate alloy material the most according to claim 1, it is characterised in that described organic becomes
Core agent is: adipyl benzoyl hydrazine.
6. the side prepared according to the increase-volume polylactic acid/Polycarbonate alloy material according to any one of claim 1～7
Method, it is characterised in that this preparation method comprises step in detail below: being added by all raw materials and carry out melt blending, processing temperature is
190 to 220 DEG C, rotor speed is 50 to 70 revs/min, and the time of staying is 5 to 10 minutes, cooled, dry and pelletizing, prepares
Described increase-volume polylactic acid/Polycarbonate alloy material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610130568.4A CN105860463A (en) | 2016-03-08 | 2016-03-08 | Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610130568.4A CN105860463A (en) | 2016-03-08 | 2016-03-08 | Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105860463A true CN105860463A (en) | 2016-08-17 |
Family
ID=56624639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610130568.4A Pending CN105860463A (en) | 2016-03-08 | 2016-03-08 | Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105860463A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395686A (en) * | 2018-04-23 | 2018-08-14 | 合肥羿振电力设备有限公司 | A kind of environment-friendly degradable type protective shell of mobile phone and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010583A (en) * | 2010-10-15 | 2011-04-13 | 浙江大学 | High-molecular weight long-chain branched crystalline polylactic acid material and preparation method thereof |
| CN102911400A (en) * | 2012-10-29 | 2013-02-06 | 上海大学 | Polylactic acid nucleating agent, preparation method as well as method for controlling morphology of polylactic acid nucleating agent |
| CN103160133A (en) * | 2013-03-28 | 2013-06-19 | 南京工业大学 | Fully-degradable biomass composite material and preparation method thereof |
| CN105647144A (en) * | 2014-11-28 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Production method of high-toughness PLA composite material |
-
2016
- 2016-03-08 CN CN201610130568.4A patent/CN105860463A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010583A (en) * | 2010-10-15 | 2011-04-13 | 浙江大学 | High-molecular weight long-chain branched crystalline polylactic acid material and preparation method thereof |
| CN102911400A (en) * | 2012-10-29 | 2013-02-06 | 上海大学 | Polylactic acid nucleating agent, preparation method as well as method for controlling morphology of polylactic acid nucleating agent |
| CN103160133A (en) * | 2013-03-28 | 2013-06-19 | 南京工业大学 | Fully-degradable biomass composite material and preparation method thereof |
| CN105647144A (en) * | 2014-11-28 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Production method of high-toughness PLA composite material |
Non-Patent Citations (2)
| Title |
|---|
| 单铮铮等: "相容剂对PC/PLA 共混体系性能的影响", 《塑料工业》 * |
| 孙振萍等: "PLA/PC复合材料的增韧改性研究", 《塑料科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395686A (en) * | 2018-04-23 | 2018-08-14 | 合肥羿振电力设备有限公司 | A kind of environment-friendly degradable type protective shell of mobile phone and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dong et al. | Influence of phthalic anhydride and bioxazoline on the mechanical and morphological properties of biodegradable poly (lactic acid)/poly [(butylene adipate)‐co‐terephthalate] blends | |
| Teamsinsungvon et al. | Preparation and characterization of poly (lactic acid)/poly (butylene adipate-co-terepthalate) blends and their composite | |
| Fakirov | Condensation polymers: Their chemical peculiarities offer great opportunities | |
| CN104910598A (en) | Super-tough high heat-resistant polylactic acid / elastomer blended material or article and preparation method thereof | |
| CN101570624B (en) | Method for preparing biomass base polylactic acid composite material | |
| Huang et al. | Phase morphology, rheological behavior, and mechanical properties of poly (lactic acid)/poly (butylene succinate)/hexamethylene diisocyanate reactive blends | |
| Ran et al. | Thermal and mechanical properties of blends of polylactide and poly (ethylene glycol‐co‐propylene glycol): Influence of annealing | |
| Zhang et al. | Modification of biobased polyamide 56 to achieve ultra-toughening | |
| Boruvka et al. | Structure-related properties of bionanocomposites based on poly (lactic acid), cellulose nanocrystals and organic impact modifier | |
| Li et al. | Evaluation of thermal resistance and mechanical properties of injected molded stereocomplex of poly (l‐lactic acid) and poly (d‐lactic acid) with various molecular weights | |
| JP5509588B2 (en) | Resin composition and molded article using the same | |
| Li et al. | Study of blends of linear poly (ether ether ketone) of high melt viscosity and hyperbranched poly (ether ether ketone) | |
| CN106674921A (en) | Polyester self-nucleating agent as well as preparation method and application thereof | |
| Ma et al. | Effect of triphenyl phosphite as a reactive compatibilizer on the properties of poly (L‐lactic acid)/poly (butylene succinate) blends | |
| CN105860463A (en) | Novel compatibilized polylactic acid/polycarbonate alloy material and preparation method thereof | |
| Valerio et al. | Improvement of impact toughness of biodegradable poly (butylene succinate) by melt blending with sustainable biobased glycerol elastomers | |
| Imai et al. | Modification of poly (lactate) via polymer blending with microbially produced poly [(R)-lactate-co-(R)-3-hydroxybutyrate] copolymers | |
| Mousavi et al. | Enhanced properties of polylactide/polyamide 11 blends by reactive compatibilization | |
| Zhang et al. | Study on the performance of diglycidyl ether of bisphenol-A/hyperbranched aromatic polyester epoxy resin (HTME) system and their toughness mechanism | |
| Fernández‐Tena et al. | High‐Impact PLA in Compatibilized PLA/PCL Blends: Optimization of Blend Composition and Type and Content of Compatibilizer | |
| Luo et al. | Relationship between the crystallization behavior of poly (ethylene glycol) and stereocomplex crystallization of poly (L‐lactic acid)/poly (D‐lactic acid) | |
| CN108641318B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method thereof | |
| Moradi et al. | Poly (lactic acid)/poly (butylene adipate-co-terephthalate) films reinforced with polyhedral oligomeric silsesquioxane nanoparticles: a morphological, mechanical, and thermal study | |
| Zhao et al. | Toughening and compatibilization of acrylonitrile–butadiene–styrene/poly (ethylene terephthalate) blends | |
| Wang et al. | Effect of the maleation of lignosulfonate on the mechanical and thermal properties of lignosulfonate/poly (ε‐caprolactone) blends |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160817 |
|
| WD01 | Invention patent application deemed withdrawn after publication |