CN102464873B - Bidirectional stretching polylactic acid / montmorillonoid, and preparation method and application thereof - Google Patents
Bidirectional stretching polylactic acid / montmorillonoid, and preparation method and application thereof Download PDFInfo
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- CN102464873B CN102464873B CN201010533049.5A CN201010533049A CN102464873B CN 102464873 B CN102464873 B CN 102464873B CN 201010533049 A CN201010533049 A CN 201010533049A CN 102464873 B CN102464873 B CN 102464873B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention provides a bidirectional stretching polylactic acid / montmorillonoid, and a preparation method and application thereof. The invention composite membrane of the invention comprises a mixture of 100 weight parts of polylactic acid and 1-10 weight parts of montmorillonoid, is prepared by a bidirectional stretching method and has a thickness of 10-100 mum. The composite membrane of the invention has low preparation cost, excellent barrier property and good biodegradability, and can be applied to the filed of package having high demand on oxygen permeability.
Description
Technical field
The present invention relates to a kind of poly (lactic acid) composition, more specifically, the present invention relates to a kind of biodegradable polylactic acid membrane and its preparation method and application.
Background technology
Along with the raising of industrialization degree, the consumption of plastics film is increasing, and taking oil and gas as raw-material polyethylene, polypropylene is the main raw material of plastics film, and these materials are discarded in nature and can not degrade, and can produce serious " white pollution ".And along with the worsening shortages of petroleum resources, oil price rises steadily, the raw-material cost of this class also rises steadily.
In order to solve this series of problems, a kind of poly(lactic acid) (polylactic acid, PLA) plant plastics that utilizes biotechnology to manufacture arises at the historic moment.Poly(lactic acid) be the lactic acid that makes through fermentation taking corn or potato starch as basic raw material, make through the ring-opening polymerization of polycondensation or its lactide dimer, at the biodegradable generation carbonic acid gas of occurring in nature and water, environmentally friendly.Thereby be widely used in the fields such as wrapping material, plastic sheeting for farm use, bio-medical material.But in food product pack field, because poly(lactic acid) is higher to the transmitance of oxygen, be only applicable to the food that packaging is less demanding to barrier, shelf-life is relatively short.
Adding polynite to carry out modification to poly(lactic acid) is an effective means that improves poly(lactic acid) barrier property.The montmorillonite layer being dispersed in poly(lactic acid) matrix has increased the path that gas spreads, and poly(lactic acid) gas barrier property is improved.According to Chang (Polym Sci Part B:Polym Phys, 2003,41 (1): 94-103.) and Tellen (Polymer, 2005,46 (25): 11715-11727.) people's the research such as, adopt the method for pressed film method and solution film forming, the poly-lactic acid/montmorillonite composite membrane of preparation polynite content 1～6wt%, the purer poly(lactic acid) of the transmission rates of oxygen in matrix material reduces by 15～30%, under the polynite addition of 10wt%, transmission rates can reduce by 50% left and right.The present invention has used the method for two-way stretch film forming, be more suitable for large-scale industrial production, and barriering effect is better.
Summary of the invention
The defect existing for prior art, the invention provides a kind of biaxially stretched polylactic acid/montmorillonite Composite film and its preparation method and application.Two-way stretch composite membrane of the present invention, preparation cost is cheap, has excellent barrier property, and its biodegradable is good, can be applied to oxygen-permeable is required to higher packaging field.
Biaxially stretched polylactic acid/Nano composite material of montmorillonite the film (BOPLA film) that provides a kind of barrier property good is provided one of object of the present invention.
Described composite membrane includes following component: poly(lactic acid), polynite, in poly(lactic acid) by 100 weight parts, polynite 1～10 weight part, preferably 3～5 weight parts.Composite membrane is standby by two-way stretch legal system, and thickness is 10～100 μ m.
Wherein, be selected from oneself disclosed polylactic resin in prior art as the poly(lactic acid) of composite membrane main body of the present invention.
Polynite described in two-way stretch composite membrane of the present invention is selected from least one in inorganic polynite of the prior art and organic modification montmonrillonite.
Described organic modification montmonrillonite is that inorganic polynite obtains after organic intercalation agent is processed modification.Can select various organic modification montmonrillonite of the prior art.Preferred described organic intercalation agent is selected from least one class in following two classes: the quaternary ammonium salt that the first kind is C6～C24, the preferably quaternary ammonium salt of C6～C18; More preferred examples of compounds comprises at least one in following material: Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, double hexadecyl ammonium salt, two octadecyl ammonium salt, Dodecyl trimethyl ammonium chloride, dodecylbenzyl alkyl dimethyl ammonium chloride, ammonium lauryl sulfate; Wherein, preferred Cetyltrimethylammonium bromide.Equations of The Second Kind is selected from one end of not being connected with polynite after intercalation special intercalator with polar group, and described polar group comprises amino, hydroxyl, carboxyl; More specifically examples of compounds comprises: hexanolactam, hexanediamine, decamethylene diamine etc.
Described inorganic polynite and organic modification montmonrillonite can pass through commercially available obtaining; Wherein organic modification montmonrillonite can also obtain by self-control.The preferred powder size of described polynite is 170～230 orders, average lamellar spacing 1～10nm, interlamellar spacing 1.5～4nm.In the present invention, this kind of polynite add the tensile property that can improve poly(lactic acid), stable pulling multiplying power can be increased to 1.5 times.
In order to increase the consistency of each component in composite membrane, in poly-lactic acid/montmorillonite composite membrane of the present invention, also comprise compatilizer, described compatilizer can be selected at least one in polycaprolactone (PCL), polyhydroxyalkanoate (PHA), polyoxyethylene glycol (PEG), epoxy resin.Adopt the compatilizers such as polyoxyethylene glycol (PEG), can improve the barrier property of the matrix material of the inorganic polynite of same equal size and organo montmorillonite; The barrier property that adopts the not polynite with terminal polar group intercalator and the compound film of the poly(lactic acid) film compound with adopting polynite with amino end group treatment agent and poly(lactic acid) is suitable, on performance and cost, has arrived balance.In poly(lactic acid) by 100 weight parts, compatilizer 0～5 weight part, preferably 2～4 weight parts.
In addition, in the course of processing of poly-lactic acid/montmorillonite composite membrane, the needs of the concrete processing of available basis, in blend material, add processing aid conventional in polylactic resin modification technology, for example: oxidation inhibitor, softening agent, toughener, fire retardant, static inhibitor, dispersion agent, nucleator, weighting agent, pigment etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Two of object of the present invention is to provide the preparation method of this kind of biaxially stretched polylactic acid/montmorillonite Composite film, said method comprising the steps of:
Including the each component including described poly(lactic acid), polynite is mixed by described content, melt blending, then after curtain coating, carry out two-way stretch, make described biaxially stretched polylactic acid/montmorillonite Composite film.
In the course of processing of polylactic acid resin composition of the present invention, material melt blending temperature is blending temperature used in common polylactic resin processing, should in the scope of its decomposition, select not only ensureing the complete melting of matrix resin but also can not make, be generally 155 DEG C～200 DEG C.In addition, according to processing needs, can in blend material, add in right amount some auxiliary agents conventional in the polylactic resin course of processing as compatilizer, dispersion agent, surface treatment agent etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
More specifically, its step of preparation method of the present invention normally first mixes all components, then carries out melt blending, curtain coating and two-way stretch, and more specifically preparation process is as follows:
(1) by poly(lactic acid), polynite in vacuum drying oven 80 DEG C, dry 8 hours, add or do not add compatilizer, put in twin screw extruder 155～200 DEG C of processing temperatures, screw speed 50～400rpm.
(2), by prepared matrix material pellet in vacuum drying oven 80 DEG C, dry 10 hours, put into casting machine curtain coating.160～195 DEG C of curtain coating temperature, curtain coating screw speed 6～20rpm.
(3) two-way stretch is carried out in the sheet material cut-parts that curtain coating gone out on biaxial orientation stretching machine, and cross directional stretch multiplying power is 3～7 times, and longitudinal tensile strength is 3～7 times, and film thickness is 15～40 μ m.
In the preparation method of the invention described above, the mixing equipment of mixing of materials can adopt various mixing equipments used in prior art, as stirrer, kneading machine etc.The melt blending equipment using is the general blending equipment in rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.The casting apparatus using can adopt various casting apparatus general in prior art, as: casting machine etc.The stretcher using is general various stretchers, as: biaxial orientation stretching machine etc.
Three of object of the present invention is to provide the application of this kind of biaxially stretched polylactic acid/montmorillonite Composite film.
Composite membrane of the present invention is for the wrapping material field of high obstructing performance; As: food fresh-keeping film, medicine packaging film, electronic product packing film etc.
The experiment proved that, adding polynite to carry out modification to poly(lactic acid) is an effective means that improves poly(lactic acid) barrier property, thus the excellent property of BOPLA film prepared by poly-lactic acid/montmorillonite matrix material of the present invention.The montmorillonite layer being dispersed in poly(lactic acid) matrix has increased the path that gas spreads, and poly(lactic acid) gas barrier property is improved.According to method provided by the invention, add 3wt% polynite, the purer poly(lactic acid) of the rate of permeation of oxygen in matrix material reduces by 50% left and right, and when addition is increased to 10wt%, oxygen permeability can reduce nearly 70% left and right.
Biaxially oriented film complete processing is that first macromolecule melt makes sheet material or thick film by long and narrow head, then in special drawing machine, under the speed of certain temperature and setting, simultaneously or the stretching carried out on vertical both direction (longitudinally, laterally) of substep, and the film of making through suitable cooling or thermal treatment or special processing (as corona, coating etc.).This film, due to the orientation effect of molecular chain, is being better than non-oriented film aspect the transparency and mechanical property.It is degradation property and the tensility that biaxial stretching film BOPLA prepared by starting material not only can have good barrier to have had that the present invention adopts poly-lactic acid/montmorillonite.The method of two-way stretch film forming of the present invention is more suitable for large-scale industrial production, and the barriering effect of product is better.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.But the present invention is not limited in following embodiment.
Testing method: according to ASTM E 96, adopt MOCON oxygen flow instrument to carry out oxygen-permeable test to film: oxygen purity is 99.9%, and carrier gas is N
2/ H
2mixed gas (H
2content 1.0%), 23 DEG C of probe temperatures, relative humidity is 0.
Raw material:
Poly(lactic acid) (PLA): Hai Zheng biomaterial limited-liability company, REVODE201, MFR (190 DEG C/2.16Kg) 10～30g/10min;
Inorganic polynite: fill level, Zhejiang Feng Hong clay Chemical Co., Ltd.;
Organic modification montmonrillonite A:DK1, Cetyltrimethylammonium bromide is intercalator modification, Zhejiang Feng Hong clay Chemical Co., Ltd.;
Organic modification montmonrillonite B:DK5, hexanolactam is intercalator modification, containing the polar group of amino end group, Zhejiang Feng Hong clay Chemical Co., Ltd.;
Polyoxyethylene glycol (PEG): molecular weight 6000, Japanese import packing.
Embodiment 1
By 100 parts of poly(lactic acid), add 3 parts of inorganic polynites, in vacuum drying oven, dry after 8 hours, put into high-speed stirring and stir 2 minutes together with 1.5 parts of polyoxyethylene glycol (PEG).Put into forcing machine granulation, from barrel to head, each section of Temperature Setting is 180-190-190-190-190-195 DEG C, and screw speed is 350rpm.After granulation, pellet is put into 80 DEG C of vacuum drying ovens and be dried 10 hours.Adopt casting machine curtain coating, the temperature of each section of casting machine barrel from hopper to head is followed successively by 175-170-170-180-180 DEG C, and screw speed is 8.5rpm.The sheet material that curtain coating is obtained, is cut into the square piece of 9.3 × 9.3cm, the preparation BOPLA film that stretches in biaxial orientation stretching machine, and 75 DEG C of stretching furnace furnace temperature, first carry out longitudinal stretching, stretching ratio 3.5.Then carry out cross directional stretch, stretching ratio 4.Its oxygen-permeable test result is in table 1.
Embodiment 2
Other conditions are with embodiment 1, but replace inorganic polynite with 3 parts of organic modification montmonrillonite A.Its oxygen-permeable test result is in table 1.
Embodiment 3
Other conditions are with embodiment 1, but replace inorganic polynite with 3 parts of organic modification montmonrillonite B, do not add compatilizer.Its oxygen-permeable test result is in table 1.
Embodiment 4
Other conditions are with embodiment 3, but organic modification montmonrillonite B content is reduced to 1 part.Its oxygen-permeable test result is in table 1.
Embodiment 5
Other conditions are with embodiment 3, but organic modification montmonrillonite B content is increased to 5 parts.Its oxygen-permeable test result is in table 1.
Embodiment 6
Other conditions are with embodiment 3, but organic modification montmonrillonite B content is increased to 10 parts.Its oxygen-permeable test result is in table 1.
Embodiment 7
Other conditions are with embodiment 1, but compatilizer addition is brought up to 3 parts.Its oxygen-permeable test result is in table 1.
Embodiment 8
Other conditions are with embodiment 6, but horizontal and vertical stretching ratio is all brought up to 7 times.Investigate the tensility energy of this PLA film.
Comparative example 1
Pure PLA pellet is put into 80 DEG C of vacuum drying ovens and be dried 10 hours.Adopt casting machine curtain coating, the temperature of each section of casting machine barrel from hopper to head is followed successively by 175-170-170-180-180 DEG C, and screw speed is 8.5rpm.The sheet material that curtain coating is obtained, is cut into the square piece of 9.3 × 9.3cm, the preparation BOPLA that stretches in biaxial orientation stretching machine, and 75 DEG C of stretching furnace furnace temperature, first carry out longitudinal stretching, stretching ratio 3.5.Then carry out cross directional stretch, stretching ratio 4.Its oxygen-permeable test result is in table 1.
Comparative example 2
By 100 parts of poly(lactic acid), add 10 parts of organo montmorillonite B, dry after 8 hours in vacuum drying oven, and by granulation in forcing machine, from barrel to head, each section of Temperature Setting is 180-190-190-190-190-195 DEG C, screw speed is 350rpm.After granulation, pellet is put into 80 DEG C of vacuum drying ovens and be dried 10 hours.Preheating 12min at 150 DEG C of temperature, adds 3MPa pressure compacting 1min, 25 DEG C of cooling 10min of pressurization.Its oxygen-permeable test result is in table 1.
Comparative example 3
Other conditions are with comparative example 1, but laterally longitudinal stretching multiplying power is all increased to 4.5 times.Investigate the tensility energy of this PLA film.
The oxygen transmission rate of table 1 BOPLA film
By the comparison of comparative example 2 and embodiment, can find out, add polynite can significantly improve the barrier of poly(lactic acid), even the same in polynite kind, in the identical situation of addition, the barrier by the prepared composite membrane of two-way stretch method is significantly better than compression molding.The barrier property that is 3wt% composite membrane for polynite content by two-way stretch legal system is better than compression molding and prepares the composite membrane that polynite content is 10wt%.
Can find out the contribution that the barrier property of composite membrane is improved: the inorganic polynite of the nonpolar polynite > of polarity organo montmorillonite > by embodiment 1～3.Comparative example 3～6 can find out, along with the increase of polynite content, the barrier of composite membrane improves gradually.
Investigating in the tensility energy process of film, according to technique described in embodiment 8, in the course of processing without rupture of membranes phenomenon; And technique described in comparative example 3, polylactic acid membrane can be pulled open, and the tensile property that can improve polylactic acid membrane that adds of polynite is described, and its stretching ratio improves 1.5 times.
Claims (5)
1. biaxially stretched polylactic acid/montmorillonite Composite film, includes following component: poly(lactic acid), polynite; In poly(lactic acid) by 100 weight parts, polynite 1～10 weight part; Described composite membrane is standby by two-way stretch legal system, and thickness is 10～100 μ m; Described polynite is organic modification montmonrillonite, is selected from the organic modification montmonrillonite DK5 of Zhejiang Feng Hong clay Chemical Co., Ltd..
2. poly-lactic acid/montmorillonite composite membrane as claimed in claim 1, is characterized in that including following component:
In poly(lactic acid) by 100 weight parts, polynite 3～5 weight parts.
3. poly-lactic acid/montmorillonite composite membrane as claimed in claim 1, is characterized in that:
Comprise compatilizer; In poly(lactic acid) by 100 weight parts, compatilizer 0～5 weight part;
Described compatilizer is selected from least one in polycaprolactone, polyhydroxyalkanoate, polyoxyethylene glycol, epoxy resin.
4. the preparation method of the biaxially stretched polylactic acid/montmorillonite Composite film as described in claim 1～3 arbitrary, is characterized in that:
Including the each component including described poly(lactic acid), polynite is mixed by described content, melt blending, then make described biaxially stretched polylactic acid/montmorillonite Composite film through two-way stretch method after curtain coating.
5. the application on the wrapping material of high obstructing performance of a kind of biaxially stretched polylactic acid/montmorillonite Composite film as described in claim 1～3 arbitrary.
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| CN105419262A (en) * | 2014-09-02 | 2016-03-23 | 允友成(宿迁)复合新材料有限公司 | Polylactic acid/montmorillonite nanometer composite material preparation method |
| CN106495175A (en) * | 2016-12-23 | 2017-03-15 | 仲恺农业工程学院 | Preparation method of organic modified montmorillonite |
| CN109929228A (en) * | 2019-04-17 | 2019-06-25 | 谷水英 | Green biodegradable plastics film and its processing technology |
| CN111086181A (en) * | 2019-12-28 | 2020-05-01 | 北京星和众工设备技术股份有限公司 | Preparation method of lithium battery diaphragm |
| CN112457639A (en) * | 2020-11-17 | 2021-03-09 | 杨勇 | Polylactic resin prepared from corn and preparation method thereof |
| CN115058032B (en) * | 2022-07-20 | 2024-01-26 | 扬州惠通生物新材料有限公司 | Preparation method of polylactic acid film opening master batch |
| CN115975355B (en) * | 2022-12-29 | 2024-05-07 | 广州市信联包装容器实业有限公司 | PET-based composite film with high barrier strength and toughness, and preparation method and application thereof |
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| CN1624033A (en) * | 2004-10-27 | 2005-06-08 | 华南理工大学 | Method of preparing modified imvite for polymer/inorganic nano composite material |
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| JP2003082212A (en) * | 2001-09-13 | 2003-03-19 | Unitika Ltd | Biodegradable resin film |
| JP2003261695A (en) * | 2002-03-11 | 2003-09-19 | Unitika Ltd | Polylactic acid based biaxially stretched film |
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