CN103724957A - Novel polylactic acid thin film material and preparation method thereof - Google Patents
Novel polylactic acid thin film material and preparation method thereof Download PDFInfo
- Publication number
- CN103724957A CN103724957A CN201310694299.0A CN201310694299A CN103724957A CN 103724957 A CN103724957 A CN 103724957A CN 201310694299 A CN201310694299 A CN 201310694299A CN 103724957 A CN103724957 A CN 103724957A
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- Prior art keywords
- polylactic acid
- film material
- acid film
- thin film
- novel
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Classifications
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
-
- 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
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention discloses a novel polylactic acid thin film material and a preparation method thereof. The novel polylactic acid thin film material consists of the following raw materials in percentage by weight: 73 to 92 percent of polylactic acid, 2 to 8 percent of layered nano-silicate, 2 to 8 percent of lignin, 3 to 10 percent of a compatilizer and 0.5 to 1.0 percent of ultrafine titanium dioxide. The novel polylactic acid thin film material and the preparation method thereof have the advantages that 1, the original mechanical performance of a polylactic acid material is improved, a prepared polylactic acid thin film has high barrier properties, and the use of a conventional antioxidant in a system is avoided to reduce the probability of pollution to food; 2, the ultrafine titanium dioxide can be used instead of a conventional organic ultraviolet stabilizer to effectively reduce appearance problems caused by the precipitation and migration of the ultraviolet stabilizer, and in addition, a common antibacterial agent can be partially or totally replaced due to the fact that the titanium dioxide has a certain antibacterial effect; 3, the prepared polylactic acid thin film has high biodegradability, so that environmental pollution is reduced; moreover, a preparation process is simple, low in cost and easy to industrialize.
Description
Technical field
The present invention relates to a kind of novel polylactic acid film material and preparation method thereof, belong to polymer modification and manufacture field.
Background technology
At present polymkeric substance barrier material mainly contains olefin plastics, polyester, polyamide-based, polyvinyl chloride, poly(lactic acid) alcohols, fluorinated plastics, liquid crystal type polymkeric substance etc.Oneself has caused the extensive concern of countries in the world " white pollution " that traditional polyolefin plastics waste causes; Meanwhile, the plastics industry take oil as raw material, because petroleum resources reduce gradually and can not regenerate, raw material is by worsening shortages.Degradable plastic is the effective way that solves plastic refuse environmental pollution and plastic raw materials shortage, and its market outlook are boundless.
Poly(lactic acid) (PLA) is a kind of green material, by tunning lactic acid such as corns, is that basic raw material makes, and has good biological degradability, and after use, the degradable generation carbonic acid gas of energy and water, free from environmental pollution.But common hard poly(lactic acid) is hard brittle material, not shock-resistant, while making film, if be difficult to satisfy the demand without orientation characteristic.Other character, can not satisfy the demand conventionally as thermostability, barrier, good solubility-resistence, flame retardant resistance etc., and the production cost of PLA is relatively high in addition, has also limited its purposes and result of use.
Nano lamellar nano silicate is because having the characteristics such as particle diameter is little, specific surface area is large, if by its good distribution in polyolefine material, will form very strong interaction interface, significantly improve mechanical property, thermal characteristics and the barrier property etc. of polymkeric substance.The general matrix material of preparing by melt-blending process need add compatilizer or carry out organic modification processing and improve its dispersive ability in material.Xylogen as one extensively exist, reproducible valuable source, have important development prospect preparing aspect degradable, reproducible polymer composite.Due to wooden good heatproof air aging performance and the flame retardant properties of have, there have been at present some researchs about the performance of polyolefine/xylogen, as Polymer Degradation and Stability, 2003 (81), 9～18 have studied 15 kinds of xylogen for polyacrylic ageing resistance; Polymer Degradation and Stability, 2012 (97), 541～546 have reported and have carried out graft modification with phosphorus oxychloride and imidazoles xylogen, have improved thermostability and the flame retardant properties of PP/ xylogen.
Under heat or various radiation conditions, easily there is degradation with aging in poly(lactic acid) simultaneously.Traditional method is to add a certain amount of oxidation inhibitor and photostabilizer to improve.Most photostabilizers, if various photomask agent, ultraviolet absorbers, radical scavenger etc. are all organic compound or the oligopolymer that molecular weight is lower.When these photostabilizers are under high temperature or UV-irradiation, there is the trend of separating out to product surface gradually.Simultaneously traditional antioxidant 1010,168 etc. joins in polyolefine material, and likely in use transport phenomena occurs in migration.Therefore be necessary to consider that the consumption of various auxiliary agents in thin-film material and compatibility problem cause migration precipitation problem.
Patent CN103160082A has just improved PLA mechanics mechanical property by adding polynite and EVA-g-MAH, and other performances do not relate to.Patent CN102464873A has improved the barrier property of PLA film by adding the polynite of modification, about the migration problem of auxiliary agent, all do not mention.
Summary of the invention
The object of the present invention is to provide a kind of novel polylactic acid film material and preparation method thereof, the polylactic acid film making has improved the original mechanical property of poly-lactic acid material, there is good barrier simultaneously, can better meet the requirement to wrapping material such as food, medicine.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of novel polylactic acid film material, is comprised of the raw material of following weight percent:
Further, a kind of novel polylactic acid film material, is comprised of the raw material of following weight percent:
Wherein, the weight-average molecular weight that described poly(lactic acid) is poly(lactic acid) is 5～400,000, and molecular weight distribution is 1.2～2.4, and degree of crystallinity is 10%～60%.
Described layered nano silicate is without one or more the mixture in the polynite of organic modification, kaolin, wilkinite, saponite, halloysite, potter's clay and clay.
Described xylogen is wood pulp xylogen, without any modification.
Described compatilizer is one or more the mixture in its polycaprolactone, polyhydroxyalkanoate, polyoxyethylene glycol and epoxy resin.
Described Behavior of Ultrafine Titanium Dioxide Particles, its size distribution of 80% is at 150-240nm.
The preparation method of above-mentioned novel polylactic acid film material, its step is as follows:
(1) poly(lactic acid) is placed in vacuum drying oven and is dried 8 hours, then take by weight ratio to obtain each raw material;
(2) various raw materials and additive are mixed 5～15 minutes in super mixer;
(3) mixed raw material is added in twin screw extruder, cooling granulation after melt extruding, makes lactic acid composite material, and its technique is: 160～170 ℃, a district, two 170～180 ℃, districts, three 180～190 ℃, districts, four 175～185 ℃, districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
(4) lactic acid composite material of preparation is placed in to blow molding machine blowing and obtains polylactic acid film, wherein barrel temperature is 175～185 ℃.
Advantage of the present invention is:
1, the polylactic acid film that prepared by the present invention has improved the original mechanical property of poly-lactic acid material, has good barrier simultaneously; In system, do not use traditional oxidation inhibitor, reduced the possibility of pollution to food.
2, the present invention uses superfine titanic oxide to replace traditional organic ultraviolet photostabilizer, can effectively reduce the problem of appearance that UV light stabilizing agent migration precipitation causes; Titanium dioxide also has certain antibacterial effect simultaneously, can partly or entirely substitute conventional antiseptic-germicide.
3, the polylactic acid film of preparing that the present invention proposes has good biological degradability, reduces the pollution to environment.Prepare production technique simple, cost is low simultaneously, easily industrialization.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail: in embodiment and comparative example composite-material formula, poly(lactic acid) (PLA) used is the REVODE201 that Hai Zheng biomaterial limited-liability company produces.Layered nano silicate used is selected the nanoclay of non-modified.Xylogen used is wood pulp xylogen, without any modification.Compatilizer used is polyoxyethylene glycol.Superfine titanic oxide used is the DLS-210 of E.I.Du Pont Company's size distribution of 80% of producing in 150-240 nanometer.
Poly(lactic acid) is placed on to dry 8h in vacuum drying oven, then in super mixer, is dry mixed 5～15 minutes with other raw materials, additive; The raw material mixing is added in twin screw extruder, and through melt extruding, cooling granulation obtains lactic acid composite material, and its technique is: 160～170 ℃, a district, two 170～180 ℃, districts, three 180～190 ℃, districts, four 175～185 ℃, districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.Finally the lactic acid composite material of preparation is placed in to blow molding machine blowing and obtains polylactic acid film, wherein barrel temperature is 175～185 ℃.
performance evaluation mode and implementation standard:
The comprehensive mechanical property of polylactic acid film is passed judgment on by testing its tensile strength, elongation at break and angle tear strength.Tensile strength, elongation at break are pressed the test of GB/T1040-2006 method; Angle tear strength is pressed the test of QB/T1130-1991 method.
Barrier properties for gases test: test according to GB/T1038-2000 method; Water vapor permeability test: test according to GB/T1037-1988 method;
The transmittance of film is pressed the test of GB/T2410-2008 method.
The thermo-oxidative stability of film is passed judgment on by DSC and TGA test.The oxidation induction time (OIT) of DSC test material, probe temperature is 180 ℃; Temperature T 5% during TGA test material 5% thermal weight loss.
The formula of embodiment and comparative example and properties test result are shown in lower each table:
Table 1 embodiment 1～4 and comparative example 1～5 material prescription table (% by weight)
Table 2 embodiment 1～4 and comparative example 1～5 test result
From embodiment 1～4 and comparative example 5, can find out, adding of nanoclay and xylogen improved the original mechanical property of poly-lactic acid material, has good light transmission, barrier and thermo-oxidative ageing ability simultaneously; Embodiment 2～3 and comparative example 1～4 can find out, nanoclay and xylogen have synergy in the barrier property of material and heat oxygen aging resistance ability.
Claims (8)
1. a novel polylactic acid film material, is characterized in that: the raw material by following weight percent forms:
2. novel polylactic acid film material according to claim 1, is characterized in that: the raw material by following weight percent forms:
3. novel polylactic acid film material according to claim 1 and 2, is characterized in that: the weight-average molecular weight that described poly(lactic acid) is poly(lactic acid) is 5～400,000, and molecular weight distribution is 1.2～2.4, and degree of crystallinity is 10%～60%.
4. novel polylactic acid film material according to claim 1 and 2, is characterized in that: described layered nano silicate is without one or more the mixture in the polynite of organic modification, kaolin, wilkinite, saponite, halloysite, potter's clay and clay.
5. novel polylactic acid film material according to claim 1 and 2, is characterized in that: described xylogen is wood pulp xylogen, without any modification.
6. novel polylactic acid film material according to claim 1 and 2, is characterized in that: described compatilizer is one or more the mixture in its polycaprolactone, polyhydroxyalkanoate, polyoxyethylene glycol and epoxy resin.
7. novel polylactic acid film material according to claim 1 and 2, is characterized in that: described Behavior of Ultrafine Titanium Dioxide Particles, its size distribution of 80% is at 150-240nm.
8. a method of preparing novel polylactic acid film material described in claim 1 or 2, is characterized in that: its step is as follows:
(1) take by weight ratio to obtain each raw material, then poly(lactic acid) is placed in vacuum drying oven and is dried 8 hours;
(2) various raw materials are mixed 5～15 minutes in super mixer;
(3) mixed raw material is added in twin screw extruder, cooling granulation after melt extruding, makes lactic acid composite material, and its technique is: 160～170 ℃, a district, two 170～180 ℃, districts, three 180～190 ℃, districts, four 175～185 ℃, districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa;
(4) lactic acid composite material of preparation is placed in to blow molding machine blowing and obtains polylactic acid film, wherein barrel temperature is 175～185 ℃.
Priority Applications (1)
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| CN201310694299.0A CN103724957A (en) | 2013-12-17 | 2013-12-17 | Novel polylactic acid thin film material and preparation method thereof |
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| CN201310694299.0A CN103724957A (en) | 2013-12-17 | 2013-12-17 | Novel polylactic acid thin film material and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104859127A (en) * | 2015-04-27 | 2015-08-26 | 安徽松泰包装材料有限公司 | Antibacterial packaging film preparation process |
| CN105733216A (en) * | 2016-03-07 | 2016-07-06 | 贵州大学 | Polylactic acid-modified and reinforced composite material |
| CN106519619A (en) * | 2016-11-24 | 2017-03-22 | 安徽省天乐塑业有限公司 | Food packaging film and preparation method thereof |
| CN106854283A (en) * | 2016-12-22 | 2017-06-16 | 常州百佳薄膜科技有限公司 | A kind of nanometer barrier additive and preparation method thereof and Related product |
| CN107586440A (en) * | 2017-09-29 | 2018-01-16 | 安徽五源食品有限公司 | A kind of dried beef environmental protection freshness protection package and preparation method thereof |
| CN107841103A (en) * | 2016-09-20 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of Novel polylactic acid thin film and preparation method thereof |
| CN109233231A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A method of lignin/polylactic acid laminated film is prepared using Pickering lotion |
| CN109810482A (en) * | 2019-02-18 | 2019-05-28 | 巩义市欧洁源环保技术服务有限公司 | A kind of prepared slices of Chinese crude drugs inner wrapping polylactic acid membrane material and preparation method thereof |
| CN110903491A (en) * | 2019-12-12 | 2020-03-24 | 湖南绿燊环保科技有限公司 | Flame retardant, modified polylactic acid and preparation method thereof |
| CN111019172A (en) * | 2019-12-31 | 2020-04-17 | 濮阳宏业高新科技发展有限公司 | Application of laminated silica in film processing |
| CN113234306A (en) * | 2021-05-28 | 2021-08-10 | 罗嘉瑜 | Composite material for preparing food utensil and preparation method thereof |
| CN114714724A (en) * | 2022-04-28 | 2022-07-08 | 云阳金田塑业有限公司 | Hot melt adhesive transfer film and preparation method thereof |
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| CN1769341A (en) * | 2005-10-18 | 2006-05-10 | 贵州省材料技术创新基地 | Nanometer aging-resistant flame-proof profax resin composition |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104859127A (en) * | 2015-04-27 | 2015-08-26 | 安徽松泰包装材料有限公司 | Antibacterial packaging film preparation process |
| CN105733216A (en) * | 2016-03-07 | 2016-07-06 | 贵州大学 | Polylactic acid-modified and reinforced composite material |
| CN107841103A (en) * | 2016-09-20 | 2018-03-27 | 黑龙江鑫达企业集团有限公司 | A kind of Novel polylactic acid thin film and preparation method thereof |
| CN106519619A (en) * | 2016-11-24 | 2017-03-22 | 安徽省天乐塑业有限公司 | Food packaging film and preparation method thereof |
| CN106854283B (en) * | 2016-12-22 | 2019-08-06 | 常州百佳年代薄膜科技股份有限公司 | A kind of nanometer barrier additive and preparation method thereof and Related product |
| CN106854283A (en) * | 2016-12-22 | 2017-06-16 | 常州百佳薄膜科技有限公司 | A kind of nanometer barrier additive and preparation method thereof and Related product |
| CN107586440A (en) * | 2017-09-29 | 2018-01-16 | 安徽五源食品有限公司 | A kind of dried beef environmental protection freshness protection package and preparation method thereof |
| CN109233231A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A method of lignin/polylactic acid laminated film is prepared using Pickering lotion |
| CN109233231B (en) * | 2018-08-17 | 2020-12-18 | 东华大学 | Method for preparing lignin/polylactic acid composite film by using Pickering emulsion |
| CN109810482A (en) * | 2019-02-18 | 2019-05-28 | 巩义市欧洁源环保技术服务有限公司 | A kind of prepared slices of Chinese crude drugs inner wrapping polylactic acid membrane material and preparation method thereof |
| CN110903491A (en) * | 2019-12-12 | 2020-03-24 | 湖南绿燊环保科技有限公司 | Flame retardant, modified polylactic acid and preparation method thereof |
| CN111019172A (en) * | 2019-12-31 | 2020-04-17 | 濮阳宏业高新科技发展有限公司 | Application of laminated silica in film processing |
| CN113234306A (en) * | 2021-05-28 | 2021-08-10 | 罗嘉瑜 | Composite material for preparing food utensil and preparation method thereof |
| CN114714724A (en) * | 2022-04-28 | 2022-07-08 | 云阳金田塑业有限公司 | Hot melt adhesive transfer film and preparation method thereof |
| CN114714724B (en) * | 2022-04-28 | 2023-11-17 | 云阳金田塑业有限公司 | Hot melt adhesive transfer film and preparation method thereof |
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Application publication date: 20140416 |