CN104387732A - Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof - Google Patents
Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof Download PDFInfo
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- CN104387732A CN104387732A CN201410647194.4A CN201410647194A CN104387732A CN 104387732 A CN104387732 A CN 104387732A CN 201410647194 A CN201410647194 A CN 201410647194A CN 104387732 A CN104387732 A CN 104387732A
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Abstract
The invention provides a transparent, tear-resistant and biodegradable polylactic acid thin film and a preparation method thereof, belonging to the field of high molecular material and solving the technical problem of high brittleness, poor tear resistance and poor flexibility of the polylactic acid thin film in the prior art. The transparent, tear-resistant and biodegradable polylactic acid thin film comprises a mixture of polylactic acid, a toughening agent, a plasticizer, a lubricant and a plastic lubricant. The preparation method comprises the following steps: mechanically mixing polylactic acid, the toughening agent, the plasticizer, the lubricant and the plastic lubricant to obtain a premix at first; feeding the premix from the feeding opening of a twin-screw extruder; metering the plasticizer and adding the metered plasticizer from the liquid feeding opening of the twin-screw extruder; and pelleting by melt extrusion to finally obtain the transparent, tear-resistant and biodegradable polylactic acid thin film. The elongation at break and tearing strength of the polylactic acid thin film provided by the invention are improved obviously, the transparency of polylactic acid is retained, the brittleness defect of the polylactic acid thin film is solved, the rheological behavior of the material is improved obviously, the tensile strength is 43.2MPa at most, the elongation at break is 48%, and the right angle tear strength is 127KN/m.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of transparent anti tear poly(lactic acid) Biodegradable film and preparation method thereof.
Background technology
Different from traditional petroleum-based plastics, poly(lactic acid) to be fermented by plant amylum and the lactic acid polymerizes obtained forms, and this is a kind of renewable resources, and has biodegradation character, has very important significance to protection of the environment.Under the situation that petroleum-based energy day is becoming tight, development research polylactic resin seems particularly important.The performance of poly(lactic acid) itself is similar to general-purpose plastics polypropylene, as high in modulus, tensile strength is large and processability good.But the fragility of poly(lactic acid) is serious, and resistance to impact shock is less than 5KJ/m
2, the serious widespread use limiting it.
Poly(lactic acid) also has good processing characteristics and the transparency, can be applicable to traditional to extrude, injection moulding, the working method such as blowing.
Therefore, the shortcoming serious for the fragility of poly(lactic acid) is carrying out study on the modification both at home and abroad energetically, the toughness adopting the method for polycomponent blending and modifying to improve poly(lactic acid) is current technical way, but poly(lactic acid) is generally difficult to the transparency keeping polylactic resin after blending toughening, how to obtain existing high tenacity, the polylactic resin again with the transparency is the requirement preparing the goods such as degradable film for package and beverage bottle.
The research of poly(lactic acid)/softening agent or toughner blending and modifying is more, by poly(lactic acid) and small molecules or simple plasticizer blended, reach the object even toughness reinforcing to polylactic acid plasticize, keep the transparency of poly(lactic acid) simultaneously.Citric acid ester type (citrate plasticization and modification poly(lactic acid). (polymer material science and engineering, (2008), 24 (1): 151-154.) research (the Polymer Bulletin that), Plasticizer Epoxidized Soybean Oil is blended, (2009), 62 (1): 91-98.) all polylactic acid plasticize modification is studied, achieves obvious plasticization effect.Zhang Huiliang, Dong Lisong etc. are Chinese invention patent and paper (the Polymer Engineeringand Science of 201010281681.5 at application number, (2013,53:112-118)) have studied poly-hexanodioic acid 1,2-propylene glycol ester is to the modification work of poly(lactic acid), poly-hexanodioic acid 1,2-PD ester can improve resistance to impact shock and the tension fracture elongation rate of poly(lactic acid).Wang Xuemei, Dong Lisong etc. have studied modification work (the Journal of Applied Polymer Science of poly-butyl carbonate and polylactic acid blend, (2013,127:471-477)), poly-butyl carbonate can improve resistance to impact shock and the tension fracture elongation rate of poly(lactic acid), and above research work is not all studied polylactic acid film preparation and modification work.
Poly(lactic acid) and the component such as vanay, lubricant is blended prepares polylactic resin, for the preparation of anti tear, high transparency polylactic acid film (CN1304471C).
Application number be 200910066621.9 Chinese invention patent have studied a kind of transparent biodegradable poly lactic acid nano composite material and preparation method thereof.This nanocomposite constituents comprises poly(lactic acid), nano silicon, softening agent, oxidation inhibitor and lubricant; The complete biology of this nano composite material falls, and compared with pure poly(lactic acid), thermostability significantly improves, and has the good transparency and tensile strength and elongation at break.Can widespread use in product for agriculture, food product pack and articles for daily use etc.
Application number be 200710023106.3 Chinese invention patent disclose a kind of polylactic acid blend and uses thereof.This blend is primarily of poly(lactic acid), nano silicon, amides composition.This blend, while the maintenance poly(lactic acid) transparency, compared with poly(lactic acid), has higher fusion-crystallization and lower cold crystallization temperature.
Application number be 200510067228.3 Chinese invention patent provide the method for producing transparent poly-lactic acid material, mediate poly(lactic acid) and there is the monomer of two or more double bonds in the molecule thereof; At the temperature of the fusing point to 200 DEG C of poly(lactic acid), molding kneaded product is to obtain moulded parts; Quench this moulded parts after molding; And quenched moulded parts is carried out crosslinking Treatment, and to prevent the molecule of poly(lactic acid) from carrying out recrystallize, obtained transparent poly-lactic acid material.
Application number be 200710023108.2 Chinese invention patent disclose a kind of poly(lactic acid) and modified cellulose blend and preparation method and heat-proof macromolecule material, blend forms primarily of 70 ~ 100 weight part poly(lactic acid) and 30 ~ 90 part by weight modified cellulose blendings.By this poly(lactic acid)/modified cellulose blend through melting, shaping after the thickness that obtains be 0.02 ~ 5mm, the resistance to heat product with certain transparency.The heat-proof macromolecule material obtained by poly(lactic acid) and modified cellulose blend has good heat resistance and certain transparency.
Application number be 200510049546.7 Chinese invention patent disclose a kind of poly(lactic acid) environmental protection complete degradable plastic and production method thereof.Poly(lactic acid) and polyvinyl alcohol, epoxy soybean wet goods auxiliary agent is through high-speed mixing, and granulation is dried and made poly(lactic acid) complete degradable plastic.Product is transparent, soft, and physical strength is high, moistureproof, anticorrosion, and barrier properties for gases is good.
Domestic and international to polylactic acid film study on the modification above, though the transparency of polylactic acid film can be kept, but all do not study and improve the method for its polylactic acid film tearing toughness, and the fragility of polylactic acid film seriously, not anti tear and kindliness difference are the subject matter affecting polylactic acid film widespread use.Keep high-clarity, having high tensile and tear strength simultaneously, can make goods not easy fracture, film article anti tear, and keep complete biodegradable characteristic, is the very important performance meeting polylactic acid film.
Summary of the invention
The present invention to solve polylactic acid film fragility in prior art seriously, the technical problem of not anti tear and kindliness difference, a kind of transparent anti tear poly(lactic acid) Biodegradable film and preparation method thereof is provided.
The invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are: poly(lactic acid) 55-89 part, toughner 5-30 part, softening agent 5-15 part, lubricant 0.1-1 part; Opening agent 0.1-1 part;
The number-average molecular weight of described poly(lactic acid) is 50000-200000g/mol;
Described toughner is poly-butyl carbonate, and its weight-average molecular weight is 50000-200000g/mol;
Described softening agent is poly-hexanodioic acid 1,2-PD ester, and its number-average molecular weight is 1000-20000g/mol;
Described lubricant is ethylene bis stearic acid amide;
Described opening agent is erucicamide.
The present invention also provides a kind of preparation method of transparent anti tear poly(lactic acid) Biodegradable film, step and condition as follows:
Each component is taken by described formula, first to poly(lactic acid), toughner, lubricant and opening agent machinery is mixed into Preblend, mechanically mixing time 3-10 minute, preferably 5 minutes, Preblend is added by twin screw extruder charging opening, softening agent is metered into by twin screw extruder liquid addition port simultaneously, through melt extruding granulation, and water-cooled, pelletizing, it is resin dedicated that oven dry obtains polydactyl acid blown film, then through inflation film manufacturing machine Blown Film, obtain transparent anti tear poly(lactic acid) Biodegradable film; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 DEG C, 2nd district: 160-180 DEG C, 3rd district: 160-190 DEG C, 4th district: 160-190 DEG C, 5th district: 160-190 DEG C, 6th district: 160-190 DEG C, 7th district: 160-190 DEG C, 8th district: 160-190 DEG C, head: 160-190 DEG C, screw speed: 100-300rpm; The design temperature of inflation film manufacturing machine is: a district: 150-155 DEG C, 2nd district: 160-170 DEG C, 3rd district: 160-170 DEG C, 4th district: 165-175 DEG C, 5th district: 170-180 DEG C, main-machine screw rotating speed: 50-300rpm, pulling speed 2-6m/min, blow-up ratio 2-6.
The invention has the beneficial effects as follows:
One provided by the invention transparent anti tear poly(lactic acid) Biodegradable film and preparation method thereof, use poly-butyl carbonate as the toughner of poly(lactic acid), and with poly-hexanodioic acid 1, 2-propylene glycol ester is softening agent, effectively can improve tension fracture elongation rate and the tearing toughness of polylactic acid film, and softening agent is nonpoisonous and tasteless, meet environmental requirement, tear strength is up to 100KN/m, solve the defect that polylactic acid film fragility is serious, and maintain the transparency of poly(lactic acid), softening agent obviously can improve the rheological behaviour of material, improve the processing characteristics of polylactic acid film, the refractive index of poly(lactic acid) is 1.454, poly-butyl carbonate is a kind of biodegradable aliphatic polycarbonate, its last degraded product is 1, 4-butyleneglycol, carbonic acid gas and two (4-hydroxybutyl) carbonic ether.Poly-hexanodioic acid 1,2-PD ester is also Biodegradable aliphatic polyester, and their refractive index is all very close with poly(lactic acid), and can keep the polylactic acid film transparency, when film thickness 0.04mm, transmittance reaches more than 86%, and mist degree is less than 9.6%.This blending modification method equipment is simple, and technique is advanced.Transparent anti tear polylactic acid film product applications is extensive, and alternative PE, PVC etc., make various environmentally-friendly transparent plastics bag, especially in food product packing film field, and wide market.The industrialization of poly(lactic acid) is conducive to the needs of the energy and material resources long term growth, promotes deep processing of farm products, reduces the dependence to oil, solves white pollution, promotes the development of Novel environment-friendlymaterial material industry, has great economy and social effect.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, transparent anti tear poly(lactic acid) Biodegradable film provided by the invention and preparation method thereof is described.Poly(lactic acid) in following examples is by Zhejiang Hisun Biomaterials Co., Ltd, and model is EVODE110; Poly-butyl carbonate is provided by Chinese Academy of Sciences's Beijing chemistry institute; In following examples, film stretching performance is that the standard of GB/T 1010.3-2006 carries out testing; Tearing toughness carries out testing according to the standard of QB/T 1130-91; Transmittance and mist degree are that WGT-S type Optical haze instrument that the close Scientific Instruments Corporation of above Nereid produces selects thickness to be the test that the thin-film material of 0.04mm carries out.
Poly-hexanodioic acid 1,2-PD ester is by unit of the present invention oneself synthesis, and the poly-hexanodioic acid 1,2-PD ester used in following examples is prepared all by the following method:
With 1,2-PD and hexanodioic acid prepared by polycondensation under catalyst action, obtains the poly-hexanodioic acid 1,2-PD ester of different number-average molecular weight by controlling temperature of reaction, reaction times and pressure.
Embodiment 1: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
Poly(lactic acid) is taken by above formula, poly-butyl carbonate, ethylene bis stearic acid amide, erucicamide, each component is carried out mechanical blending 5 minutes, mixed raw material is added in twin screw extruder, in extrusion, forcing machine side line peristaltic pump quantitatively adds above-mentioned poly-hexanodioic acid 1, 2-propylene glycol ester, the condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 DEG C, 2nd district: 160-180 DEG C, 3rd district: 160-190 DEG C, 4th district: 160-190 DEG C, 5th district: 160-190 DEG C, 6th district: 160-190 DEG C, 7th district: 160-190 DEG C, 8th district: 160-190 DEG C, head: 160-190 DEG C, screw speed: 100-300rpm, extruding pelletization obtains poly(lactic acid) blown film resin after drying.By this resin through inflation film manufacturing machine Blown Film, the design temperature of inflation film manufacturing machine is: a district: 150-155 DEG C, 2nd district: 160-170 DEG C, 3rd district: 160-170 DEG C, 4th district: 165-175 DEG C, 5th district: 170-180 DEG C, main-machine screw rotating speed: 50-300rpm, pulling speed 2-6m/min, blow-up ratio 2-6.Plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 2: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 3: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 4: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 5: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 6: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 7: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Embodiment 8: the invention provides a kind of transparent anti tear poly(lactic acid) Biodegradable film, moiety and the mass fraction proportioning of its formula are:
This step extruding pelletization and blown film operation identical with embodiment 1, plastics thickness control is at 0.04mm, and the mechanical property of testing film and transmittance, test result lists in table 1.
Table 1 polylactic acid film mechanical property and transmittance test result
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (7)
1. a transparent anti tear poly(lactic acid) Biodegradable film, is characterized in that, moiety and the mass fraction proportioning of its formula are: poly(lactic acid) 55-89 part, toughner 5-30 part, softening agent 5-15 part, lubricant 0.1-1 part; Opening agent 0.1-1 part; Described toughner is poly-butyl carbonate, and softening agent is poly-hexanodioic acid 1,2-PD ester, and lubricant is ethylene bis stearic acid amide, and opening agent is erucicamide.
2. transparent anti tear poly(lactic acid) Biodegradable film according to claim 1, is characterized in that, the number-average molecular weight of described poly(lactic acid) is 50000-200000g/mol.
3. transparent anti tear poly(lactic acid) Biodegradable film according to claim 1, is characterized in that, the weight-average molecular weight of described poly-butyl carbonate is 50000-200000g/mol.
4. transparent anti tear poly(lactic acid) Biodegradable film according to claim 1, is characterized in that, the number-average molecular weight of described poly-hexanodioic acid 1,2-PD ester is 1000-20000g/mol.
5. the preparation method of transparent anti tear poly(lactic acid) Biodegradable film according to claim 1, is characterized in that, step and condition as follows:
Each component is taken by described formula, first to poly(lactic acid), toughner, lubricant and opening agent machinery is mixed into Preblend, Preblend is added by twin screw extruder charging opening, softening agent is metered into by twin screw extruder liquid addition port simultaneously, through melt extruding granulation, and water-cooled, pelletizing, it is resin dedicated that oven dry obtains polydactyl acid blown film, then through inflation film manufacturing machine Blown Film, obtain transparent anti tear poly(lactic acid) Biodegradable film; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 DEG C, 2nd district: 160-180 DEG C, 3rd district: 160-190 DEG C, 4th district: 160-190 DEG C, 5th district: 160-190 DEG C, 6th district: 160-190 DEG C, 7th district: 160-190 DEG C, 8th district: 160-190 DEG C, head: 160-190 DEG C, screw speed: 100-300rpm; The design temperature of inflation film manufacturing machine is: a district: 150-155 DEG C, 2nd district: 160-170 DEG C, 3rd district: 160-170 DEG C, 4th district: 165-175 DEG C, 5th district: 170-180 DEG C, main-machine screw rotating speed: 50-300rpm, pulling speed 2-6m/min, blow-up ratio 2-6.
6. the preparation method of transparent anti tear poly(lactic acid) Biodegradable film according to claim 5, is characterized in that, the time of described mechanically mixing is 3-10 minute.
7. the preparation method of transparent anti tear poly(lactic acid) Biodegradable film according to claim 6, is characterized in that, the time of described mechanically mixing is 5 minutes.
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| CN107011634A (en) * | 2016-07-26 | 2017-08-04 | 北京工商大学 | Biodegradable transparent polyester film that a kind of inorganic nano-filler is modified and preparation method thereof |
| CN107603168A (en) * | 2017-10-16 | 2018-01-19 | 中国科学院长春应用化学研究所 | A kind of PLA base film and preparation method thereof |
| CN108017887A (en) * | 2016-11-02 | 2018-05-11 | 黑龙江鑫达企业集团有限公司 | A kind of PLA-PBSA inflation films and preparation method thereof |
| CN108822514A (en) * | 2018-07-06 | 2018-11-16 | 黑龙江鑫达企业集团有限公司 | A kind of completely biological degradation polylactic acid base inflation film and preparation method thereof |
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| CN107011634A (en) * | 2016-07-26 | 2017-08-04 | 北京工商大学 | Biodegradable transparent polyester film that a kind of inorganic nano-filler is modified and preparation method thereof |
| CN108017887A (en) * | 2016-11-02 | 2018-05-11 | 黑龙江鑫达企业集团有限公司 | A kind of PLA-PBSA inflation films and preparation method thereof |
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| CN108822514A (en) * | 2018-07-06 | 2018-11-16 | 黑龙江鑫达企业集团有限公司 | A kind of completely biological degradation polylactic acid base inflation film and preparation method thereof |
| CN109206868A (en) * | 2018-08-29 | 2019-01-15 | 桐城市强峰包装有限公司 | A kind of Plastics and preparation method thereof |
| CN111205542A (en) * | 2020-02-28 | 2020-05-29 | 厦门维豪环保科技有限公司 | Low-shrinkage composite PE (polyethylene) laminating film material and preparation method thereof |
| CN111978691A (en) * | 2020-09-11 | 2020-11-24 | 中国科学院长春应用化学研究所 | Biodegradable mulching film and preparation method thereof |
| CN114685961A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
| CN114685961B (en) * | 2020-12-29 | 2024-04-05 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
| CN113088057A (en) * | 2021-05-20 | 2021-07-09 | 中国科学院长春应用化学研究所 | Reinforced and toughened polylactic acid blending material and preparation method thereof |
| CN113637297A (en) * | 2021-08-14 | 2021-11-12 | 安徽颍美科技股份有限公司 | Preparation method and production process of full-biodegradable material |
| CN113956640A (en) * | 2021-12-15 | 2022-01-21 | 中化泉州能源科技有限责任公司 | Biodegradable PLA film and preparation method thereof |
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| CN115386204A (en) * | 2022-09-20 | 2022-11-25 | 淄博龙沙高分子材料科技有限公司 | Biodegradable winding film and preparation method thereof |
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Application publication date: 20150304 |