WO2015161807A1 - High-barrier polypropylene carbonate-based composite film material and preparation method thereof - Google Patents

High-barrier polypropylene carbonate-based composite film material and preparation method thereof Download PDF

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WO2015161807A1
WO2015161807A1 PCT/CN2015/077233 CN2015077233W WO2015161807A1 WO 2015161807 A1 WO2015161807 A1 WO 2015161807A1 CN 2015077233 W CN2015077233 W CN 2015077233W WO 2015161807 A1 WO2015161807 A1 WO 2015161807A1
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polypropylene carbonate
based composite
film material
composite film
parts
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PCT/CN2015/077233
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French (fr)
Chinese (zh)
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孟跃中
杨丹
杜风光
肖敏
张晓阳
王拴紧
朱光兰
翟黎鹏
韩东梅
甘力强
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河南天冠企业集团有限公司
中山大学
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Publication of WO2015161807A1 publication Critical patent/WO2015161807A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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

Definitions

  • the invention relates to the technical field of polymer materials, and more particularly to a high-resistance polypropylene carbonate-based composite film material and a preparation method thereof.
  • the well-known materials with excellent oxygen barrier properties include aluminum foil, polyethylene-vinyl alcohol, polyvinyl alcohol, PVDC, etc., but these materials have certain deficiencies, such as: aluminum foil has weak pinhole resistance, and The aluminum foil is opaque, it is difficult to judge whether the processing is reliable or not.
  • the polyethylene-vinyl alcohol and polyvinyl alcohol have excellent barrier properties against oxygen in a dry environment, but the barrier properties of the material are greatly affected by humidity. The barrier properties are greatly impaired under high humidity conditions.
  • 102321324A discloses a method using nano-silica particles to improve the barrier properties of polyethylene-vinyl alcohol and polyvinyl alcohol by humidity, but because of the high price of polyethylene-vinyl alcohol, etc., in the field of packaging applications There are still problems that cannot be widely used. PVDC cannot be degraded, has no environmentally friendly properties, and is difficult to recycle, so people are constantly researching alternatives.
  • Polypropylene carbonate prepared by using carbon dioxide as a raw material is a kind of polymer which is non-toxic, non-polluting, non-flammable, easy to process, and has good barrier properties. With the development of synthetic catalytic technology, the synthesis cost is continuously reduced, and the modification space of the material is increased, thereby increasing the application range of the material. Polypropylene carbonate is less expensive and easier to process than materials such as the high barrier polyethylene-vinyl alcohol described above.
  • Chinese Patent No. 1,640,649 A discloses a degradable composite film prepared based on a carbon dioxide resin as a barrier material, and the high barrier degradation film mentioned in the patent has a barrier layer of nano montmorillonite or clay, SiO 2 , TiO 2 , A degradable nano-polymer obtained by a polymerization method or a hybrid method of a nano-inorganic material such as CaCO 3 , and the montmorillonite described in the patent is generally commercially modified by an alkyl quaternary ammonium salt or other organic cation.
  • the organic montmorillonite prepared in the preparation process is likely to retain part of the metal ions.
  • the object of the present invention is to provide a degradable high-resistance polypropylene carbonate-based composite film material prepared by modifying polypropylene carbonate as a substrate against the defects and defects of the existing polymer barrier materials.
  • the material maintains the original properties of the substrate material, and the barrier properties, thermal properties, and mechanical properties are improved, especially the barrier property is improved, and the oxygen barrier property can be compared with the oxygen barrier property of the polyethylene-vinyl alcohol. Beautiful.
  • Another object of the present invention is to provide a process for preparing the above high-resistance polypropylene carbonate-based composite film material.
  • a high barrier polypropylene carbonate based composite film material comprising the following raw materials by weight:
  • Plasticizer 5 to 20 parts.
  • the polyvinyl alcohol is used in an amount of from 1.5 to 4 times the weight of the layered silicate.
  • the polyvinyl alcohol is used in an amount of from 3 to 4 times the weight of the layered silicate.
  • the high-barrier polypropylene carbonate-based composite film material has an oxygen transmission coefficient of 25 to 460 cm 3 ⁇ um/(m 2 ⁇ 24h ⁇ atm) and a water vapor transmission coefficient of 56 to 266 g ⁇ um/ (m 2 ⁇ 24h).
  • the polypropylene carbonate is a completely degradable product obtained by copolymerization of carbon dioxide and propylene oxide, and has a number average molecular weight of 50,000 to 250,000 Da, preferably a number average molecular weight of 50,000 to 110,000 Da.
  • the polyvinyl alcohol has a degree of polymerization of 500 to 2400 and a degree of alcoholysis of 88 to 99%.
  • the layered silicate is one or more of talc, mica, kaolinite, chlorite, halloysite, montmorillonite, saponite and vermiculite.
  • the plasticizer is a solid plasticizer or a liquid plasticizer.
  • the solid plasticizer includes one or more of a polyester polyurethane, a polyether polyurethane, a polyethylene-vinyl alcohol, and a polyethylene glycol.
  • the liquid plasticizer includes one or more of a citrate plasticizer, an epoxy plasticizer, and a polyol plasticizer.
  • the citrate plasticizer includes one or more of tributyl citrate, trioctyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate.
  • the epoxy plasticizer includes one or more of epoxidized soybean oil, methyl acetyl linolenic acid, butyl epoxide phthalate, and octyl epoxide oleate.
  • the polyol plasticizer includes one or more of glycerin, ethylene glycol, propylene glycol, and butylene glycol.
  • the high barrier polypropylene carbonate based composite film material can be widely used in the field of packaging.
  • a method for preparing the above high-resistance polypropylene carbonate-based composite film material comprises the following process steps:
  • the polyvinyl silicate nanointercalation composite material is obtained by intercalating the layered silicate with polyvinyl alcohol by aqueous solution intercalation method:
  • the solid plasticizer is dried in a vacuum oven at 80 ° C for 24 h before use, and the plasticizer is mixed with the polyvinyl alcohol nano-intercalation composite prepared in the step (1) at room temperature, and melt-blended to obtain plasticization.
  • Polyvinyl alcohol nano-intercalation composite material broken into granular form;
  • the granular plasticized polyvinyl alcohol nano-intercalation composite material prepared in the step (2) and the proportioned polypropylene carbonate are dried in a vacuum oven at 80 ° C for 24 hours, mixed and stirred at room temperature, and melt-blended to obtain a product.
  • the high-barrier polypropylene carbonate-based composite material obtained by the step (3) is tableted by a flat vulcanizing machine at 170 ° C and 10 MPa to obtain a high barrier polycarbonate.
  • the organic layered silicate is prepared by aqueous solution intercalation method, and the polyvinyl alcohol which is water-soluble, non-toxic and has certain barrier properties is used as the intercalation modifier, and the modified organosilicate is not only non-existent.
  • the problem of inorganic metal residue, and the preparation method is simple, economical and environmentally friendly;
  • the obtained high-barrier polypropylene carbonate-based composite film material can have the oxygen barrier performance comparable to that of polyethylene-vinyl alcohol, and the production process is simpler and the manufacturing cost is lower, which can effectively replace the poly-polymer.
  • Expensive high-barrier materials such as ethylene-vinyl alcohol have good economic benefits and broad application prospects.
  • the high-barrier polypropylene carbonate-based composite film material prepared by the invention has an oxygen transmission coefficient of 25-460 cm 3 ⁇ um/(m 2 ⁇ 24h ⁇ atm) and a water vapor transmission coefficient of 56-266 g ⁇ Um/(m 2 ⁇ 24h); its oxygen transmission coefficient is as low as 25cm 3 ⁇ um/(m 2 ⁇ 24h ⁇ atm), and the water vapor transmission coefficient is as low as 56g ⁇ um/(m 2 ⁇ 24h). It can completely replace high-barrier materials such as polyethylene-vinyl alcohol and is used in the production of various packaging products that require high barrier.
  • reagents, devices, and methods employed in the present invention are conventionally commercially available reagents, equipment, and methods of routine use.
  • the characteristics of the gas barrier film of the present invention were evaluated using the following evaluation methods.
  • the oxygen transmission rate was tested by coulometer method (isostatic method) using the oxygen permeability meter of China Guangzhou Standard Packaging Equipment Co., Ltd.
  • each set of samples was averaged 4 times as the value of the oxygen transmission rate of each example.
  • the value of the oxygen transmission rate is closely related to the thickness of the film. Therefore, the oxygen permeability coefficient is usually used to measure the barrier property of the gas barrier film.
  • the oxygen transmission coefficient here is obtained by multiplying the oxygen transmission rate by the film thickness. Value.
  • the water vapor transmission rate was measured by the infrared sensor method under the conditions of temperature 23 ° C and humidity 85% RH using a moisture permeability meter (Model: Model 3/61) of MOCON, USA. Further, for each of the examples, each group of samples was averaged three times for the value of the water vapor transmission rate in each of the examples. Similarly, the value of the water vapor transmission rate is also closely related to the thickness of the film. Therefore, the water vapor transmission rate coefficient is usually used to measure the barrier property of the gas barrier film. The water vapor transmission rate coefficient here refers to the water vapor transmission rate. The rate is multiplied by the value obtained for the film thickness.
  • the preparation of a high-resistance polypropylene carbonate-based composite film material is calculated according to the mass fraction: 5 parts of polyvinyl alcohol having a degree of polymerization of 500, a degree of alcoholysis of 88%, and 0.5 part of talc powder and 33 parts of deionized
  • the water is added to the reaction vessel, heated in a water bath, heated to 80 ° C, stirred and ultrasonically shaken, heated at a constant temperature for 6 h, suctioned and filtered with acetone, washed three times with absolute ethanol, and dried in a vacuum oven at 80 ° C to obtain a polyvinyl alcohol nano-insertion.
  • Layer composite material which is crushed; then, 5 parts of polyethylene-vinyl alcohol particles are dried in a vacuum oven at 80 ° C for 24 hours, and the polyethylene-vinyl alcohol and the crushed polyvinyl alcohol nano-intercalation composite material are mixed and stirred at room temperature.
  • the difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite powder, and the deionized water is 150.
  • the constant heating time was 8 h, the plasticizer was 10 parts of polyester polyurethane particles, and the polypropylene carbonate was 90 parts, and the number average molecular weight was 100,000 Da.
  • the difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 1500, the degree of alcoholysis is 95%, the layered silicate is 5 parts of chlorite powder, and the deionized water is 400. Parts, constant heating time is 10h, plasticizer is 20 parts of polyether The polyurethane, polypropylene carbonate was 80 parts, and its number average molecular weight was 150,000 Da.
  • the difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2000, the degree of alcoholysis is 99%, and the layered silicate is a mixture of 3 parts of mica and 2 parts of halloysite.
  • the deionized water is 750 parts, the constant heating time is 10 hours, the plasticizer is 10 parts of polyethylene glycol, the polypropylene carbonate is 75 parts, and the number average molecular weight is 200,000 Da.
  • the difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 a mixture of vermiculite, deionized water is 900 parts, constant heating time is 8h, plasticizer is a mixture of 10 parts of polyester polyurethane and 5 parts of polyether polyurethane, and polypropylene carbonate is 60 parts.
  • the average molecular weight is 250,000 Da.
  • the difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700.
  • the plasticizer is a mixture of 10 parts of polyethylene-vinyl alcohol and 10 parts of polyethylene glycol, 70 parts of polypropylene carbonate, and a number average molecular weight of 200,000 Da.
  • the preparation of a high-resistance polypropylene carbonate-based composite material is calculated according to the mass fraction: 10 parts of polyvinyl alcohol having a degree of polymerization of 800, a degree of alcoholysis of 90%, and 50 parts of smectite layered silicic acid
  • the salt and 150 parts of deionized water were added to the reaction vessel, heated in a water bath, heated to 80 ° C, stirred and ultrasonically shaken, heated at a constant temperature for 8 h, acetone was separated and suction filtered, washed three times with absolute ethanol, and dried in a vacuum oven at 80 ° C.
  • Polyvinyl alcohol nano-intercalation composite which is crushed; then the crushed polyvinyl alcohol nano-intercalation composite material is mixed with 10 parts of acetyl citric acid trioctyl ester liquid plasticizer at room temperature and stirred uniformly at 80 ° C ordinary oven After plasticizing for 8h, a plasticized polyvinyl alcohol nano-intercalation composite material was obtained; 90 parts of polypropylene carbonate having a number average molecular weight of 80000Da were dried in a vacuum oven at 80 ° C for 24 hours, and the obtained plasticized polyvinyl alcohol nano-intercalation layer was obtained at room temperature.
  • the composite material is mixed with the dried polypropylene carbonate, melt blended to obtain a high-resistance polypropylene carbonate-based composite material, and the polyacrylic acid is obtained by tableting at 170 ° C and 10 MPa. Ester-based high barrier Composite film material.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite, and the deionized water is 150.
  • the constant heating time is 6 h
  • the plasticizer is 10 parts of methyl acetyl linolenate
  • the plasticization time is 9 h
  • the polypropylene carbonate is 95 parts
  • the number average molecular weight is 50,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 1500, and the degree of alcoholysis is 95%.
  • the layered silicate is 5 parts of chlorite, 400 parts of deionized water, the heating time is 10h, the plasticizer is 20 parts of ethylene glycol, the plasticizing time is 10h, and the polypropylene carbonate is 80 parts. Its number average molecular weight is 150,000 Da.
  • the difference between this example and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2000, the degree of alcoholysis is 99%, and the layered silicate is a mixture of 3 parts of mica and 2 parts of halloysite.
  • the deionized water is 750 parts, the constant heating time is 9h, and the plasticizer is a mixture of 5 parts of tributyl citrate and 5 parts of acetyl tributyl citrate.
  • the plasticizing time is 9h, and the polypropylene carbonate is 75.
  • the fraction has a number average molecular weight of 200,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 a mixture of vermiculite, 900 parts of deionized water, heated at a constant temperature of 8 h, plasticizer is a mixture of 10 parts of methyl acetyl linolenate and 5 parts of butyl phthalate, polypropylene carbonate It was 60 parts and its number average molecular weight was 250,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700.
  • the constant heating time was 7 h
  • the plasticizer was a mixture of 10 parts of glycerin and 10 parts of butanediol, and the polypropylene carbonate was 70 parts, and the number average molecular weight was 200,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700.
  • the constant heating time was 7 h
  • the plasticizer was 10 parts of trioctyl citrate
  • the plasticization time was 9 h
  • the polypropylene carbonate was 70 parts
  • the number average molecular weight was 200,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 A mixture of vermiculite, 900 parts of deionized water, heated at a constant temperature of 8 h, plasticizer is a mixture of 10 parts of epoxidized soybean oil and 5 parts of octyl epoxidized soybean oleate, plasticization time is 10 h, polycarbonate The propyl ester was 60 parts and its number average molecular weight was 250,000 Da.
  • the difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite, and the deionized water is 150.
  • the constant heating time was 6 h
  • the plasticizer was 10 parts of propylene glycol
  • the plasticizing time was 9 h
  • the polypropylene carbonate was 95 parts
  • the number average molecular weight was 50,000 Da.
  • the oxygen permeability coefficient and the water vapor transmission rate coefficient of the high-barrier polypropylene carbonate-based composite material prepared by the respective groups were determined as shown in the following table.
  • the unit of oxygen transmission coefficient is: cm 3 ⁇ um / (m 2 ⁇ 24h ⁇ atm); the unit of water vapor transmission coefficient is: g ⁇ um / (m 2 ⁇ 24h)):
  • the high-barrier polypropylene carbonate-based composite film material prepared by the present invention has an oxygen permeability coefficient between 25 and 460 cm 3 ⁇ um / (m 2 ⁇ 24 h ⁇ atm), and the water vapor is transmitted through.
  • the rate coefficient is between 56 and 266 g ⁇ um/(m 2 ⁇ 24 h); it can completely replace the high barrier material such as polyethylene-vinyl alcohol, and is used for the production of various packaging products requiring high barrier;
  • Propylene ester is the main raw material for production, which greatly reduces the production cost of the enterprise and is easier to process.

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Abstract

Disclosed are a high-barrier polypropylene carbonate-based composite film material and a preparation method thereof. The film material comprises the following raw materials in parts by weight: 60-95 parts of polypropylene carbonate, 5-20 parts of polyvinyl alcohol, 0.5-10 parts of layered silicate and 5-20 parts of a plasticizer. The degradable high-barrier polypropylene carbonate-based composite film material prepared by modification using polypropylene carbonate as a base material has an oxygen permeability coefficient as low as 25cm3_um.(m2_24h_atm) and a water vapour permeability coefficient as low as 56g/(m2_24h). The material has improved barrier properties, thermal properties and mechanical properties, especially improved the barrier properties while the original characteristics of the base material are maintained and can replace completely high-barrier materials such as polyethylene-vinyl alcohol and is used for the production of various packaging products which require high-barrier.

Description

一种高阻隔聚碳酸亚丙酯基复合薄膜材料及其制备方法High-resistance polypropylene carbonate-based composite film material and preparation method thereof 技术领域Technical field
本发明涉及高分子材料技术领域，更具体地，涉及一种高阻隔聚碳酸亚丙酯基复合薄膜材料及其制备方法。The invention relates to the technical field of polymer materials, and more particularly to a high-resistance polypropylene carbonate-based composite film material and a preparation method thereof.
背景技术Background technique
目前，我们所熟知的具有优异氧气阻隔性能的材料有铝箔、聚乙烯-乙烯醇、聚乙烯醇、PVDC等，但是这些材料都存在一定的不足，如：铝箔的抗针孔能力弱，且由于铝箔不透明，很难判断加工成型是否达到可靠的热封等；聚乙烯-乙烯醇、聚乙烯醇在干燥环境下对氧气的阻隔性非常优异，但是该材料阻隔性能受湿度的影响很大，在高湿度条件下阻隔性能大大受损。中国专利102321324A公开了一种采用纳米二氧化硅粒子的方法，来改善聚乙烯-乙烯醇、聚乙烯醇阻隔性能受湿度的影响，但由于聚乙烯-乙烯醇等的价格昂贵，在包装应用领域仍然存在不能广泛使用的问题。PVDC不能降解，不具有环保特性，且回收困难，所以人们同时也在不断研究其替代品。At present, the well-known materials with excellent oxygen barrier properties include aluminum foil, polyethylene-vinyl alcohol, polyvinyl alcohol, PVDC, etc., but these materials have certain deficiencies, such as: aluminum foil has weak pinhole resistance, and The aluminum foil is opaque, it is difficult to judge whether the processing is reliable or not. The polyethylene-vinyl alcohol and polyvinyl alcohol have excellent barrier properties against oxygen in a dry environment, but the barrier properties of the material are greatly affected by humidity. The barrier properties are greatly impaired under high humidity conditions. Chinese Patent No. 102321324A discloses a method using nano-silica particles to improve the barrier properties of polyethylene-vinyl alcohol and polyvinyl alcohol by humidity, but because of the high price of polyethylene-vinyl alcohol, etc., in the field of packaging applications There are still problems that cannot be widely used. PVDC cannot be degraded, has no environmentally friendly properties, and is difficult to recycle, so people are constantly researching alternatives.
以二氧化碳为原料制备的聚碳酸亚丙酯，是一类无毒、无污染、不易燃、易加工，且具有良好的阻隔性能的聚合物。随着合成催化技术的发展，使其合成成本不断降低，材料的改性空间得以增加，从而加大了该材料的适用范围。同上述的高阻隔的聚乙烯-乙烯醇等材料相比，聚碳酸亚丙酯价格低廉，更容易加工。Polypropylene carbonate prepared by using carbon dioxide as a raw material is a kind of polymer which is non-toxic, non-polluting, non-flammable, easy to process, and has good barrier properties. With the development of synthetic catalytic technology, the synthesis cost is continuously reduced, and the modification space of the material is increased, thereby increasing the application range of the material. Polypropylene carbonate is less expensive and easier to process than materials such as the high barrier polyethylene-vinyl alcohol described above.
中国专利1640649A公开了一种基于用二氧化碳树脂作为阻隔材料制备的可降解复合膜，该专利中提到的高阻隔降解膜，其阻隔层是经纳米蒙脱土或粘土、SiO2、TiO2、CaCO3等纳米无机材料用聚合法或是混联法改性得到的可降解纳米聚合物，专利中所述的蒙脱土一般是市售的经过烷基季铵盐或是其他有机阳离子改性制备的有机蒙脱土，此制备过程制得的有机蒙脱土很可能会残留部分金属离子。Chinese Patent No. 1,640,649 A discloses a degradable composite film prepared based on a carbon dioxide resin as a barrier material, and the high barrier degradation film mentioned in the patent has a barrier layer of nano montmorillonite or clay, SiO 2 , TiO 2 , A degradable nano-polymer obtained by a polymerization method or a hybrid method of a nano-inorganic material such as CaCO 3 , and the montmorillonite described in the patent is generally commercially modified by an alkyl quaternary ammonium salt or other organic cation. In the prepared organic montmorillonite, the organic montmorillonite prepared in the preparation process is likely to retain part of the metal ions.
发明内容Summary of the invention
本发明的目的是针对现有高分子阻隔材料的不足和缺陷而提供一种以聚碳酸亚丙酯为基材，通过改性制备得到的可降解的高阻隔聚碳酸亚丙酯基复合薄膜材料，该材料在保持了基材原料原有特性的同时，阻隔性能、热学性能、力学性能均得以提高，尤其是阻隔性能的改善，其阻氧性能可以和聚乙烯-乙烯醇的阻氧性能相媲美。The object of the present invention is to provide a degradable high-resistance polypropylene carbonate-based composite film material prepared by modifying polypropylene carbonate as a substrate against the defects and defects of the existing polymer barrier materials. The material maintains the original properties of the substrate material, and the barrier properties, thermal properties, and mechanical properties are improved, especially the barrier property is improved, and the oxygen barrier property can be compared with the oxygen barrier property of the polyethylene-vinyl alcohol. Beautiful.
本发明的另一目的是提供一种上述高阻隔聚碳酸亚丙酯基复合薄膜材料的制备方法。Another object of the present invention is to provide a process for preparing the above high-resistance polypropylene carbonate-based composite film material.
一种高阻隔聚碳酸亚丙酯基复合薄膜材料，其包括以下重量份配比的原料： A high barrier polypropylene carbonate based composite film material comprising the following raw materials by weight:
聚碳酸亚丙酯 60～95份，Polypropylene carbonate 60 to 95 parts,
聚乙烯醇 5～20份，5 to 20 parts of polyvinyl alcohol,
层状硅酸盐 0.5～10份，Layered silicate 0.5 to 10 parts,
增塑剂 5～20份。Plasticizer 5 to 20 parts.
优选地，所述聚乙烯醇的用量为层状硅酸盐使用重量的1.5～4倍。Preferably, the polyvinyl alcohol is used in an amount of from 1.5 to 4 times the weight of the layered silicate.
作为进一步地优化方案，所述聚乙烯醇的用量为层状硅酸盐使用重量的3～4倍。As a further optimization, the polyvinyl alcohol is used in an amount of from 3 to 4 times the weight of the layered silicate.
所述高阻隔聚碳酸亚丙酯基复合薄膜材料，其氧气透过率系数为25～460cm3·um/(m2·24h·atm)，水蒸气透过率系数为56～266g·um/(m2·24h)。The high-barrier polypropylene carbonate-based composite film material has an oxygen transmission coefficient of 25 to 460 cm 3 ·um/(m 2 ·24h·atm) and a water vapor transmission coefficient of 56 to 266 g·um/ (m 2 · 24h).
所述聚碳酸亚丙酯为二氧化碳和环氧丙烷共聚得到的完全可降解产物，其数均分子量为50000～250000Da，优选数均分子量为50000～110000Da。The polypropylene carbonate is a completely degradable product obtained by copolymerization of carbon dioxide and propylene oxide, and has a number average molecular weight of 50,000 to 250,000 Da, preferably a number average molecular weight of 50,000 to 110,000 Da.
所述聚乙烯醇的聚合度为500～2400，醇解度为88-99％。The polyvinyl alcohol has a degree of polymerization of 500 to 2400 and a degree of alcoholysis of 88 to 99%.
所述层状硅酸盐为滑石、云母、高岭石、绿泥石、埃洛石、蒙脱石、皂石和蛭石中的一种或多种。The layered silicate is one or more of talc, mica, kaolinite, chlorite, halloysite, montmorillonite, saponite and vermiculite.
所述增塑剂为固体增塑剂或液体增塑剂。The plasticizer is a solid plasticizer or a liquid plasticizer.
所述固体增塑剂包括：聚酯型聚氨酯、聚醚型聚氨酯、聚乙烯-乙烯醇和聚乙二醇中的一种或多种。The solid plasticizer includes one or more of a polyester polyurethane, a polyether polyurethane, a polyethylene-vinyl alcohol, and a polyethylene glycol.
所述液体增塑剂包括：柠檬酸酯类增塑剂、环氧类增塑剂和多元醇增塑剂中的一种或多种。The liquid plasticizer includes one or more of a citrate plasticizer, an epoxy plasticizer, and a polyol plasticizer.
所述柠檬酸酯类增塑剂包括：柠檬酸三丁酯、柠檬酸三辛酯、乙酰柠檬酸三丁酯、乙酰柠檬酸三辛酯中的一种或多种。The citrate plasticizer includes one or more of tributyl citrate, trioctyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate.
所述环氧类增塑剂包括：环氧大豆油、环氧乙酰亚麻油酸甲酯、环氧糠油酸丁酯、环氧大豆油酸辛酯中的一种或多种。The epoxy plasticizer includes one or more of epoxidized soybean oil, methyl acetyl linolenic acid, butyl epoxide phthalate, and octyl epoxide oleate.
所述多元醇增塑剂包括：甘油、乙二醇、丙二醇、丁二醇中的一种或多种。The polyol plasticizer includes one or more of glycerin, ethylene glycol, propylene glycol, and butylene glycol.
所述高阻隔聚碳酸亚丙酯基复合薄膜材料可广泛应用于包装领域。The high barrier polypropylene carbonate based composite film material can be widely used in the field of packaging.
一种上述高阻隔聚碳酸亚丙酯基复合薄膜材料的制备方法，包含以下工艺步骤：A method for preparing the above high-resistance polypropylene carbonate-based composite film material comprises the following process steps:
(1)采用水溶液插层法使用聚乙烯醇对层状硅酸盐进行插层处理，制得聚乙烯醇纳米插层复合材料：(1) The polyvinyl silicate nanointercalation composite material is obtained by intercalating the layered silicate with polyvinyl alcohol by aqueous solution intercalation method:
按所述配比将聚乙烯醇和层状硅酸盐加入到反应容器中，并加入重量为聚乙烯醇和层状硅酸盐总重量6～30倍的去离子水，水浴加热，升温到80℃，搅拌并超声震荡，恒温加热6～10h，丙酮沉析抽滤，用无水乙醇洗涤三次，80℃真空烘箱烘干得到聚乙烯醇纳米插层复合材料， 破碎待用；Adding polyvinyl alcohol and layered silicate to the reaction vessel according to the ratio, adding deionized water with a weight of 6 to 30 times of the total weight of polyvinyl alcohol and layered silicate, heating in a water bath, and heating to 80 ° C Stirring and ultrasonic vibration, heating at a constant temperature for 6-10 h, acetone precipitation and suction filtration, washing three times with absolute ethanol, drying in a vacuum oven at 80 ° C to obtain a polyvinyl alcohol nano-intercalation composite. Broken for use;
(2)使用增塑剂对聚乙烯醇纳米插层复合材料进行增塑：(2) Plasticizing the polyvinyl alcohol nano-intercalation composite using a plasticizer:
固体类增塑剂使用前在80℃真空烘箱干燥24h，室温下取所述配比的增塑剂与步骤(1)制备的聚乙烯醇纳米插层复合材料混合搅拌，熔融共混得到增塑聚乙烯醇纳米插层复合材料，破碎成粒状；The solid plasticizer is dried in a vacuum oven at 80 ° C for 24 h before use, and the plasticizer is mixed with the polyvinyl alcohol nano-intercalation composite prepared in the step (1) at room temperature, and melt-blended to obtain plasticization. Polyvinyl alcohol nano-intercalation composite material, broken into granular form;
(3)制备复合材料的：(3) Preparation of composite materials:
将步骤(2)制备的粒状增塑聚乙烯醇纳米插层复合材料和所述配比的聚碳酸亚丙酯在80℃真空烘箱干燥24h，室温下混合搅拌均匀，并熔融共混，制得高阻隔聚碳酸亚丙酯基复合材料；The granular plasticized polyvinyl alcohol nano-intercalation composite material prepared in the step (2) and the proportioned polypropylene carbonate are dried in a vacuum oven at 80 ° C for 24 hours, mixed and stirred at room temperature, and melt-blended to obtain a product. High barrier polypropylene carbonate based composite;
(4)压片制膜：通过平板硫化机，在170℃，10MPa条件下将步骤(3)制得的高阻隔聚碳酸亚丙酯基复合材料压片制膜，即可得到高阻隔聚碳酸亚丙酯基复合薄膜材料。(4) Film-forming film: The high-barrier polypropylene carbonate-based composite material obtained by the step (3) is tableted by a flat vulcanizing machine at 170 ° C and 10 MPa to obtain a high barrier polycarbonate. A propylene ester based composite film material.
本发明相对于现有技术具有如下的优点及效果：The present invention has the following advantages and effects over the prior art:
1.采用水溶液插层法制备有机层状硅酸盐，用水溶性好、无毒且具有一定阻隔性能的聚乙烯醇来做插层改性剂，制得的改性有机硅酸盐不但不存在无机金属残留的问题，而且制备方法更是简单、经济、环保；1. The organic layered silicate is prepared by aqueous solution intercalation method, and the polyvinyl alcohol which is water-soluble, non-toxic and has certain barrier properties is used as the intercalation modifier, and the modified organosilicate is not only non-existent. The problem of inorganic metal residue, and the preparation method is simple, economical and environmentally friendly;
2.采用以二氧化碳为原料制备得到的聚碳酸亚丙酯聚合物，成本低廉，且利用了污染大气的二氧化碳气体，降低了“温室效应”的影响；同时也分担了工业和生活包装用材料对石油基材料的依赖性压力；2. The use of carbon dioxide as raw material for the preparation of polypropylene carbonate polymer, low cost, and the use of carbon dioxide gas polluting the atmosphere, reducing the impact of the "greenhouse effect"; also sharing the industrial and living packaging materials Dependence pressure of petroleum-based materials;
3.制得的高阻隔聚碳酸亚丙酯基复合薄膜材料，其阻氧性能可以和聚乙烯-乙烯醇的阻氧性能相媲美，且生产工艺更加简单，制造成本更低，可有效代替聚乙烯-乙烯醇等价格昂贵的高阻隔材料，具备良好的经济效益和广阔的应用前景。3. The obtained high-barrier polypropylene carbonate-based composite film material can have the oxygen barrier performance comparable to that of polyethylene-vinyl alcohol, and the production process is simpler and the manufacturing cost is lower, which can effectively replace the poly-polymer. Expensive high-barrier materials such as ethylene-vinyl alcohol have good economic benefits and broad application prospects.
本课题组测得聚乙烯-乙烯醇(乙烯基含量为32mol％)的氧气透过率系数为30～500cm3·um/(m2·24h·atm)，水蒸气透过率系数为200～375g·um/(m2·24h)。本发明所制备的高阻隔聚碳酸亚丙酯基复合薄膜材料的氧气透过率系数为25～460cm3·um/(m2·24h·atm)，水蒸气透过率系数为56～266g·um/(m2·24h)；其氧气透过率系数低至25cm3·um/(m2·24h·atm)，水蒸气透过率系数低至56g·um/(m2·24h)，完全可以代替聚乙烯-乙烯醇等高阻隔材料，用于各种需要高阻隔的包装制品的生产。Our group measured the oxygen permeability coefficient of polyethylene-vinyl alcohol (vinyl content of 32mol%) to 30 ~ 500cm 3 · um / (m 2 · 24h · atm), the water vapor transmission coefficient is 200 ~ 375 g·um/(m 2 ·24h). The high-barrier polypropylene carbonate-based composite film material prepared by the invention has an oxygen transmission coefficient of 25-460 cm 3 ·um/(m 2 ·24h·atm) and a water vapor transmission coefficient of 56-266 g· Um/(m 2 ·24h); its oxygen transmission coefficient is as low as 25cm 3 ·um/(m 2 ·24h·atm), and the water vapor transmission coefficient is as low as 56g·um/(m 2 ·24h). It can completely replace high-barrier materials such as polyethylene-vinyl alcohol and is used in the production of various packaging products that require high barrier.
具体实施方式detailed description
下面结合具体实施例进一步详细说明本发明。除非特别说明，本发明采用的试剂、设备和方法为本技术领域常规市购的试剂、设备和常规使用的方法。 The invention will now be described in further detail with reference to specific embodiments. Unless otherwise stated, the reagents, devices, and methods employed in the present invention are conventionally commercially available reagents, equipment, and methods of routine use.
本发明的气体阻隔性膜的特性，使用以下的评价方法进行评价。The characteristics of the gas barrier film of the present invention were evaluated using the following evaluation methods.
(1)氧气透过率(1) Oxygen transmission rate
根据GB/T 19789-2005，在温度23℃，湿度0％RH条件下，使用中国广州标际包装设备有限公司的透氧仪，采用库仑计检测法(等压法)测试氧气透过率。另外，对于各实施例，每组样品各测试4次取平均值作为各实施例的氧气透过率的值。氧气透过率的数值大小与薄膜的厚度密切相关，因此通常使用氧气透过率系数来衡量气体阻隔膜的阻隔特性，这里的氧气透过率系数是指氧气透过率乘以薄膜厚度得到的数值。According to GB/T 19789-2005, under the condition of temperature 23 ° C and humidity 0% RH, the oxygen transmission rate was tested by coulometer method (isostatic method) using the oxygen permeability meter of China Guangzhou Standard Packaging Equipment Co., Ltd. In addition, for each of the examples, each set of samples was averaged 4 times as the value of the oxygen transmission rate of each example. The value of the oxygen transmission rate is closely related to the thickness of the film. Therefore, the oxygen permeability coefficient is usually used to measure the barrier property of the gas barrier film. The oxygen transmission coefficient here is obtained by multiplying the oxygen transmission rate by the film thickness. Value.
(2)水蒸气透过率(2) Water vapor transmission rate
根据GB/T 26253-2010，在温度23℃、湿度85％RH的条件下，使用美国MOCON公司的透湿仪(型号：Model 3/61)，采用红外传感器法测试水蒸气透过率。另外，对于各实施例，每组样品各测试3次取平均值作为各实施例中的水蒸气透过率的值。同样，水蒸气透过率的数值大小与薄膜的厚度也密切相关，因此通常使用水蒸气透过率系数来衡量气体阻隔膜的阻隔特性，这里的水蒸气透过率系数是指水蒸气透过率乘以薄膜厚度得到的数值。According to GB/T 26253-2010, the water vapor transmission rate was measured by the infrared sensor method under the conditions of temperature 23 ° C and humidity 85% RH using a moisture permeability meter (Model: Model 3/61) of MOCON, USA. Further, for each of the examples, each group of samples was averaged three times for the value of the water vapor transmission rate in each of the examples. Similarly, the value of the water vapor transmission rate is also closely related to the thickness of the film. Therefore, the water vapor transmission rate coefficient is usually used to measure the barrier property of the gas barrier film. The water vapor transmission rate coefficient here refers to the water vapor transmission rate. The rate is multiplied by the value obtained for the film thickness.
实施例一Embodiment 1
一种高阻隔聚碳酸亚丙酯基复合薄膜材料的制备，按照质量份数计算：先将5份聚合度为500、醇解度为88％的聚乙烯醇和0.5份滑石粉末与33份去离子水加入到反应容器中，水浴加热，升温到80℃，搅拌并超声震荡，恒温加热6h，丙酮沉析抽滤，用无水乙醇洗涤三次，80℃真空烘箱烘干，得到聚乙烯醇纳米插层复合材料，将其破碎；然后将5份聚乙烯-乙烯醇颗粒在80℃真空烘箱干燥24h，室温下将所述聚乙烯-乙烯醇与破碎后的聚乙烯醇纳米插层复合材料混合搅拌均匀，熔融共混制得增塑聚乙烯醇纳米插层复合材料，破碎成粒状；将所得粒状增塑聚乙烯醇纳米插层复合材料和95份数均分子量为50000Da的聚碳酸亚丙酯在80℃真空烘箱中干燥24h，并在室温下混合搅拌均匀，熔融共混制得高阻隔聚碳酸亚丙酯基复合材料，通过平板硫化机，在170℃，10MPa条件下压片制得高阻隔聚碳酸亚丙酯基复合薄膜材料。The preparation of a high-resistance polypropylene carbonate-based composite film material is calculated according to the mass fraction: 5 parts of polyvinyl alcohol having a degree of polymerization of 500, a degree of alcoholysis of 88%, and 0.5 part of talc powder and 33 parts of deionized The water is added to the reaction vessel, heated in a water bath, heated to 80 ° C, stirred and ultrasonically shaken, heated at a constant temperature for 6 h, suctioned and filtered with acetone, washed three times with absolute ethanol, and dried in a vacuum oven at 80 ° C to obtain a polyvinyl alcohol nano-insertion. Layer composite material, which is crushed; then, 5 parts of polyethylene-vinyl alcohol particles are dried in a vacuum oven at 80 ° C for 24 hours, and the polyethylene-vinyl alcohol and the crushed polyvinyl alcohol nano-intercalation composite material are mixed and stirred at room temperature. Uniform, melt blending to obtain a plasticized polyvinyl alcohol nano-intercalation composite material, which is broken into granules; the obtained granular plasticized polyvinyl alcohol nano-intercalation composite material and 95 parts of polypropylene carbonate having a number average molecular weight of 50,000 Da are Drying in a vacuum oven at 80 ° C for 24 h, mixing and stirring at room temperature, melt blending to obtain a high-resistance polypropylene carbonate-based composite material, which is obtained by tableting at 170 ° C and 10 MPa. Polypropylene carbonate based barrier composite film material.
实施例二Embodiment 2
本实施例与实施例一的区别之处在于：聚乙烯醇为10份，其聚合度为800、醇解度为90％，层状硅酸盐为5份蒙脱石粉，去离子水为150份，恒温加热时间为8h，增塑剂为10份聚酯型聚氨酯颗粒，聚碳酸亚丙酯为90份，其数均分子量为100000Da。The difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite powder, and the deionized water is 150. The constant heating time was 8 h, the plasticizer was 10 parts of polyester polyurethane particles, and the polypropylene carbonate was 90 parts, and the number average molecular weight was 100,000 Da.
实施例三Embodiment 3
本实施例与实施例一的区别之处在于：聚乙烯醇为15份，其聚合度为1500、醇解度为95％，层状硅酸盐为5份绿泥石粉，去离子水为400份，恒温加热时间为10h，增塑剂为20份聚醚 型聚氨酯，聚碳酸亚丙酯为80份，其数均分子量为150000Da。The difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 1500, the degree of alcoholysis is 95%, the layered silicate is 5 parts of chlorite powder, and the deionized water is 400. Parts, constant heating time is 10h, plasticizer is 20 parts of polyether The polyurethane, polypropylene carbonate was 80 parts, and its number average molecular weight was 150,000 Da.
实施例四Embodiment 4
本实施例与实施例一的区别之处在于：聚乙烯醇为20份，其聚合度为2000、醇解度为99％，层状硅酸盐为3份云母和2份埃洛石的混合物，去离子水为750份，恒温加热时间为10h，增塑剂为10份聚乙二醇，聚碳酸亚丙酯为75份，其数均分子量为200000Da。The difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2000, the degree of alcoholysis is 99%, and the layered silicate is a mixture of 3 parts of mica and 2 parts of halloysite. The deionized water is 750 parts, the constant heating time is 10 hours, the plasticizer is 10 parts of polyethylene glycol, the polypropylene carbonate is 75 parts, and the number average molecular weight is 200,000 Da.
实施例五Embodiment 5
本实施例与实施例一的区别之处在于：聚乙烯醇为20份，其聚合度为2400、醇解度为95％，层状硅酸盐为5份高岭石、3份皂石和2份蛭石的混合物，去离子水为900份，恒温加热时间为8h，增塑剂为10份聚酯型聚氨酯与5份聚醚型聚氨酯的混合物，聚碳酸亚丙酯为60份，其数均分子量为250000Da。The difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 a mixture of vermiculite, deionized water is 900 parts, constant heating time is 8h, plasticizer is a mixture of 10 parts of polyester polyurethane and 5 parts of polyether polyurethane, and polypropylene carbonate is 60 parts. The average molecular weight is 250,000 Da.
实施例六Embodiment 6
本实施例与实施例一的区别之处在于：聚乙烯醇为15份，其聚合度为2000、醇解度为88％，层状硅酸盐为10份高岭石，去离子水为700份，增塑剂为10份聚乙烯-乙烯醇与10份聚乙二醇的混合物，聚碳酸亚丙酯为70份，其数均分子量为200000Da。The difference between this embodiment and the first embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700. The plasticizer is a mixture of 10 parts of polyethylene-vinyl alcohol and 10 parts of polyethylene glycol, 70 parts of polypropylene carbonate, and a number average molecular weight of 200,000 Da.
实施例七Example 7
一种高阻隔聚碳酸亚丙酯基复合材料的制备，按照质量份数计算：先将10份聚合度为800、醇解度为90％的聚乙烯醇、50份蒙脱石层状硅酸盐与150份去离子水加入到反应容器中，水浴加热，升温到80℃，搅拌并超声震荡，恒温加热8h，丙酮沉析抽滤，用无水乙醇洗涤三次，80℃真空烘箱烘干得到聚乙烯醇纳米插层复合材料，将其破碎；然后室温下将破碎后的聚乙烯醇纳米插层复合材料与10份乙酰柠檬酸三辛酯液体增塑剂混合搅拌均匀，在80℃普通烘箱增塑8h，得到增塑聚乙烯醇纳米插层复合材料；将90份数均分子量为80000Da的聚碳酸亚丙酯在80℃真空烘箱干燥24h，室温下将所得增塑聚乙烯醇纳米插层复合材料与干燥后的聚碳酸亚丙酯混合搅拌，熔融共混制得高阻隔聚碳酸亚丙酯基复合材料，通过平板硫化机，在170℃，10MPa条件下压片制得聚碳酸亚丙酯基高阻隔复合薄膜材料。The preparation of a high-resistance polypropylene carbonate-based composite material is calculated according to the mass fraction: 10 parts of polyvinyl alcohol having a degree of polymerization of 800, a degree of alcoholysis of 90%, and 50 parts of smectite layered silicic acid The salt and 150 parts of deionized water were added to the reaction vessel, heated in a water bath, heated to 80 ° C, stirred and ultrasonically shaken, heated at a constant temperature for 8 h, acetone was separated and suction filtered, washed three times with absolute ethanol, and dried in a vacuum oven at 80 ° C. Polyvinyl alcohol nano-intercalation composite, which is crushed; then the crushed polyvinyl alcohol nano-intercalation composite material is mixed with 10 parts of acetyl citric acid trioctyl ester liquid plasticizer at room temperature and stirred uniformly at 80 ° C ordinary oven After plasticizing for 8h, a plasticized polyvinyl alcohol nano-intercalation composite material was obtained; 90 parts of polypropylene carbonate having a number average molecular weight of 80000Da were dried in a vacuum oven at 80 ° C for 24 hours, and the obtained plasticized polyvinyl alcohol nano-intercalation layer was obtained at room temperature. The composite material is mixed with the dried polypropylene carbonate, melt blended to obtain a high-resistance polypropylene carbonate-based composite material, and the polyacrylic acid is obtained by tableting at 170 ° C and 10 MPa. Ester-based high barrier Composite film material.
实施例八Example eight
本实施例与实施例七的区别之处在于：聚乙烯醇为10份，其聚合度为800、醇解度为90％，层状硅酸盐为5份蒙脱石，去离子水为150份，恒温加热时间为6h，增塑剂为10份环氧乙酰亚麻油酸甲酯，增塑时间为9h，聚碳酸亚丙酯为95份，其数均分子量为50000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite, and the deionized water is 150. The constant heating time is 6 h, the plasticizer is 10 parts of methyl acetyl linolenate, the plasticization time is 9 h, the polypropylene carbonate is 95 parts, and the number average molecular weight is 50,000 Da.
实施例九Example nine
本实施例与实施例七的区别之处在于：聚乙烯醇为15份，其聚合度为1500、醇解度为95％， 层状硅酸盐为5份绿泥石，去离子水为400份，恒温加热时间为10h，增塑剂为20份乙二醇，增塑时间为10h，聚碳酸亚丙酯为80份，其数均分子量为150000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 1500, and the degree of alcoholysis is 95%. The layered silicate is 5 parts of chlorite, 400 parts of deionized water, the heating time is 10h, the plasticizer is 20 parts of ethylene glycol, the plasticizing time is 10h, and the polypropylene carbonate is 80 parts. Its number average molecular weight is 150,000 Da.
实施例十Example ten
本实施例与实施例七的区别之处在于：聚乙烯醇为20份，其聚合度为2000、醇解度为99％，层状硅酸盐为3份云母和2份埃洛石的混合物，去离子水为750份，恒温加热时间为9h，增塑剂为5份柠檬酸三丁酯与5份乙酰柠檬酸三丁酯的混合物，增塑时间为9h，聚碳酸亚丙酯为75份，其数均分子量为200000Da。The difference between this example and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2000, the degree of alcoholysis is 99%, and the layered silicate is a mixture of 3 parts of mica and 2 parts of halloysite. The deionized water is 750 parts, the constant heating time is 9h, and the plasticizer is a mixture of 5 parts of tributyl citrate and 5 parts of acetyl tributyl citrate. The plasticizing time is 9h, and the polypropylene carbonate is 75. The fraction has a number average molecular weight of 200,000 Da.
实施例十一Embodiment 11
本实施例与实施例七的区别之处在于：聚乙烯醇为20份，其聚合度为2400、醇解度为95％，层状硅酸盐为5份高岭石、3份皂石和2份蛭石的混合物，去离子水为900份，恒温加热时间为8h，增塑剂为10份环氧乙酰亚麻油酸甲酯与5份环氧糠油酸丁酯的混合物，聚碳酸亚丙酯为60份，其数均分子量为250000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 a mixture of vermiculite, 900 parts of deionized water, heated at a constant temperature of 8 h, plasticizer is a mixture of 10 parts of methyl acetyl linolenate and 5 parts of butyl phthalate, polypropylene carbonate It was 60 parts and its number average molecular weight was 250,000 Da.
实施例十二Example twelve
本实施例与实施例七的区别之处在于：聚乙烯醇为15份，其聚合度为2000、醇解度为88％，层状硅酸盐为10份高岭石，去离子水为700份，恒温加热时间为7h，增塑剂为10份甘油与10份丁二醇的混合物，聚碳酸亚丙酯为70份，其数均分子量为200000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700. The constant heating time was 7 h, the plasticizer was a mixture of 10 parts of glycerin and 10 parts of butanediol, and the polypropylene carbonate was 70 parts, and the number average molecular weight was 200,000 Da.
实施例十三Example thirteen
本实施例与实施例七的区别之处在于：聚乙烯醇为15份，其聚合度为2000、醇解度为88％，层状硅酸盐为10份高岭石，去离子水为700份，恒温加热时间为7h，增塑剂为10份柠檬酸三辛酯，增塑时间为9h，聚碳酸亚丙酯为70份，其数均分子量为200000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 15 parts, the degree of polymerization is 2000, the degree of alcoholysis is 88%, the layered silicate is 10 parts of kaolinite, and the deionized water is 700. The constant heating time was 7 h, the plasticizer was 10 parts of trioctyl citrate, the plasticization time was 9 h, the polypropylene carbonate was 70 parts, and the number average molecular weight was 200,000 Da.
实施例十四Embodiment 14
本实施例与实施例七的区别之处在于：聚乙烯醇为20份，其聚合度为2400、醇解度为95％，层状硅酸盐为5份高岭石、3份皂石和2份蛭石的混合物，去离子水为900份，恒温加热时间为8h，增塑剂为10份环氧大豆油与5份环氧大豆油酸辛酯的混合物，增塑时间为10h，聚碳酸亚丙酯为60份，其数均分子量为250000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 20 parts, the degree of polymerization is 2400, the degree of alcoholysis is 95%, and the layered silicate is 5 parts of kaolinite, 3 parts of saponite and 2 A mixture of vermiculite, 900 parts of deionized water, heated at a constant temperature of 8 h, plasticizer is a mixture of 10 parts of epoxidized soybean oil and 5 parts of octyl epoxidized soybean oleate, plasticization time is 10 h, polycarbonate The propyl ester was 60 parts and its number average molecular weight was 250,000 Da.
实施例十五Example fifteen
本实施例与实施例七的区别之处在于：聚乙烯醇为10份，其聚合度为800、醇解度为90％，层状硅酸盐为5份蒙脱石，去离子水为150份，恒温加热时间为6h，增塑剂为10份丙二醇，增塑时间为9h，聚碳酸亚丙酯为95份，其数均分子量为50000Da。The difference between this embodiment and the seventh embodiment is that the polyvinyl alcohol is 10 parts, the degree of polymerization is 800, the degree of alcoholysis is 90%, the layered silicate is 5 parts of montmorillonite, and the deionized water is 150. The constant heating time was 6 h, the plasticizer was 10 parts of propylene glycol, the plasticizing time was 9 h, the polypropylene carbonate was 95 parts, and the number average molecular weight was 50,000 Da.
以上各组实施例分别进行3组实验，经测定，各组实施例所制得的高阻隔聚碳酸亚丙 酯基复合材料，其氧气透过率系数和水蒸气透过率系数如下表所示(氧气透过率系数单位为：cm3·um/(m2·24h·atm)；水蒸气透过率系数单位为：g·um/(m2·24h))：Each of the above groups of experiments was carried out in three sets of experiments. The oxygen permeability coefficient and the water vapor transmission rate coefficient of the high-barrier polypropylene carbonate-based composite material prepared by the respective groups were determined as shown in the following table. (The unit of oxygen transmission coefficient is: cm 3 · um / (m 2 · 24h · atm); the unit of water vapor transmission coefficient is: g·um / (m 2 · 24h)):
Figure PCTCN2015077233-appb-000001
Figure PCTCN2015077233-appb-000001
由上述实验数据可知本发明所制备的高阻隔聚碳酸亚丙酯基复合薄膜材料的氧气透过率系数在25～460cm3·um/(m2·24h·atm)之间，水蒸气透过率系数在56～266g·um/(m2·24h)之间；完全可以代替聚乙烯-乙烯醇等高阻隔材料，用于各种需要高阻隔的包装制品的生产；以价格低廉的聚碳酸亚丙酯为主要生产原料，极大地降低了企业的生产成本，且更容易加工生产。 It can be seen from the above experimental data that the high-barrier polypropylene carbonate-based composite film material prepared by the present invention has an oxygen permeability coefficient between 25 and 460 cm 3 · um / (m 2 · 24 h · atm), and the water vapor is transmitted through. The rate coefficient is between 56 and 266 g·um/(m 2 ·24 h); it can completely replace the high barrier material such as polyethylene-vinyl alcohol, and is used for the production of various packaging products requiring high barrier; Propylene ester is the main raw material for production, which greatly reduces the production cost of the enterprise and is easier to process.

Claims (15)

  1. 一种高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：它包括以下重量份配比的原料：A high barrier polypropylene carbonate based composite film material characterized in that it comprises the following raw materials by weight ratio:
    聚碳酸亚丙酯 60～95份，Polypropylene carbonate 60 to 95 parts,
    聚乙烯醇 5～20份，5 to 20 parts of polyvinyl alcohol,
    层状硅酸盐 0.5～10份，Layered silicate 0.5 to 10 parts,
    增塑剂 5～20份。Plasticizer 5 to 20 parts.
  2. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述聚乙烯醇的用量为层状硅酸盐使用重量的1.5～4倍。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the polyvinyl alcohol is used in an amount of from 1.5 to 4 times the weight of the layered silicate.
  3. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述聚乙烯醇的用量为层状硅酸盐使用重量的3～4倍。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the polyvinyl alcohol is used in an amount of from 3 to 4 times the weight of the layered silicate.
  4. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述高阻隔聚碳酸亚丙酯基复合薄膜材料，其氧气透过率系数为25～460cm3·um/(m2·24h·atm)，水蒸气透过率系数为56～266g·um/(m2·24h)。The high-barrier polypropylene carbonate-based composite film material according to claim 1, wherein the high-barrier polypropylene carbonate-based composite film material has an oxygen transmission coefficient of 25 to 460 cm 3 · um. / (m 2 · 24h·atm), the water vapor transmission rate coefficient is 56 to 266 g·um / (m 2 · 24 h).
  5. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述聚碳酸亚丙酯为二氧化碳和环氧丙烷共聚得到的完全可降解产物，其数均分子量为50000～250000Da，优选数均分子量为50000～110000Da。The high-barrier polypropylene carbonate-based composite film material according to claim 1, wherein the polypropylene carbonate is a completely degradable product obtained by copolymerizing carbon dioxide and propylene oxide, and has a number average molecular weight of 50,000. ～250000Da preferably has a number average molecular weight of 50,000 to 110,000 Da.
  6. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述聚乙烯醇的聚合度为500～2400，醇解度为88-99％。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the polyvinyl alcohol has a polymerization degree of 500 to 2400 and an alcoholysis degree of 88 to 99%.
  7. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述层状硅酸盐为滑石、云母、高岭石、绿泥石、埃洛石、蒙脱石、皂石和蛭石中的一种或多种。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the layered silicate is talc, mica, kaolinite, chlorite, halloysite, and montmorillonite. One or more of soapstone and vermiculite.
  8. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述增塑剂为固体增塑剂或液体增塑剂。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the plasticizer is a solid plasticizer or a liquid plasticizer.
  9. 如权利要求8所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述固体增塑剂包括：聚酯型聚氨酯、聚醚型聚氨酯、聚乙烯-乙烯醇和聚乙二醇中的一种或多种。The high barrier polypropylene carbonate-based composite film material according to claim 8, wherein the solid plasticizer comprises: a polyester polyurethane, a polyether polyurethane, a polyethylene-vinyl alcohol, and a polyethylene glycol. One or more of them.
  10. 如权利要求8所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述液体增塑剂包括：柠檬酸酯类增塑剂、环氧类增塑剂和多元醇增塑剂中的一种或多种。The high barrier polypropylene carbonate-based composite film material according to claim 8, wherein the liquid plasticizer comprises: a citric acid ester plasticizer, an epoxy plasticizer, and a polyol plasticizer. One or more of the agents.
  11. 如权利要求10所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述柠檬酸酯类增塑剂包括：柠檬酸三丁酯、柠檬酸三辛酯、乙酰柠檬酸三丁酯、乙酰柠檬酸三辛酯中的一种或多种。The high-barrier polypropylene carbonate-based composite film material according to claim 10, wherein the citrate plasticizer comprises: tributyl citrate, trioctyl citrate, and acetyl citrate One or more of butyl ester and acetyl trioctyl citrate.
  12. 如权利要求10所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述环氧类增塑剂包括：环氧大豆油、环氧乙酰亚麻油酸甲酯、环氧糠油酸丁酯、环氧大豆油酸辛酯中的 一种或多种。The high barrier polypropylene carbonate-based composite film material according to claim 10, wherein the epoxy plasticizer comprises: epoxy soybean oil, epoxy acetyl linolenic acid methyl ester, epoxy eucalyptus oil Of butyl acrylate and octyl epoxide One or more.
  13. 如权利要求10所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述多元醇增塑剂包括：甘油、乙二醇、丙二醇、丁二醇中的一种或多种。The high barrier polypropylene carbonate-based composite film material according to claim 10, wherein the polyol plasticizer comprises one or more of glycerin, ethylene glycol, propylene glycol and butylene glycol. .
  14. 如权利要求1所述的高阻隔聚碳酸亚丙酯基复合薄膜材料，其特征在于：所述高阻隔聚碳酸亚丙酯基复合薄膜材料可广泛应用于包装领域。The high barrier polypropylene carbonate-based composite film material according to claim 1, wherein the high barrier polypropylene carbonate-based composite film material is widely used in the field of packaging.
  15. 一种上述任意一项权利要求所述的高阻隔聚碳酸亚丙酯基复合薄膜材料的制备方法，其特征在于：包含以下工艺步骤：A method for preparing a high barrier polypropylene carbonate-based composite film material according to any of the preceding claims, comprising the following process steps:
    (1)采用水溶液插层法使用聚乙烯醇对层状硅酸盐进行插层处理，制得聚乙烯醇纳米插层复合材料：(1) The polyvinyl silicate nanointercalation composite material is obtained by intercalating the layered silicate with polyvinyl alcohol by aqueous solution intercalation method:
    按所述配比将聚乙烯醇和层状硅酸盐加入到反应容器中，并加入重量为聚乙烯醇和层状硅酸盐总重量6～30倍的去离子水，水浴加热，升温到80℃，搅拌并超声震荡，恒温加热6～10h，丙酮沉析抽滤，用无水乙醇洗涤三次，80℃真空烘箱烘干得到聚乙烯醇纳米插层复合材料，破碎待用；Adding polyvinyl alcohol and layered silicate to the reaction vessel according to the ratio, adding deionized water with a weight of 6 to 30 times of the total weight of polyvinyl alcohol and layered silicate, heating in a water bath, and heating to 80 ° C Stirring and ultrasonic vibration, heating at a constant temperature for 6-10 h, acetone precipitation and suction filtration, washing three times with absolute ethanol, drying in a vacuum oven at 80 ° C to obtain a polyvinyl alcohol nano-intercalation composite material, and crushing for use;
    (2)使用增塑剂对聚乙烯醇纳米插层复合材料进行增塑：(2) Plasticizing the polyvinyl alcohol nano-intercalation composite using a plasticizer:
    固体类增塑剂使用前在80℃真空烘箱干燥24h，室温下取所述配比的增塑剂与步骤(1)制备的聚乙烯醇纳米插层复合材料混合搅拌，熔融共混得到增塑聚乙烯醇纳米插层复合材料，破碎成粒状；The solid plasticizer is dried in a vacuum oven at 80 ° C for 24 h before use, and the plasticizer is mixed with the polyvinyl alcohol nano-intercalation composite prepared in the step (1) at room temperature, and melt-blended to obtain plasticization. Polyvinyl alcohol nano-intercalation composite material, broken into granular form;
    (3)制备复合材料的：(3) Preparation of composite materials:
    将步骤(2)制备的粒状增塑聚乙烯醇纳米插层复合材料和所述配比的聚碳酸亚丙酯在80℃真空烘箱干燥24h，室温下混合搅拌均匀，并熔融共混，制得高阻隔聚碳酸亚丙酯基复合材料；The granular plasticized polyvinyl alcohol nano-intercalation composite material prepared in the step (2) and the proportioned polypropylene carbonate are dried in a vacuum oven at 80 ° C for 24 hours, mixed and stirred at room temperature, and melt-blended to obtain a product. High barrier polypropylene carbonate based composite;
    (4)压片制膜：(4) Tablet filming:
    通过平板硫化机，在170℃，10MPa条件下将步骤(3)制得的高阻隔聚碳酸亚丙酯基复合材料压片制膜，即可得到高阻隔聚碳酸亚丙酯基复合薄膜材料。 The high-barrier polypropylene carbonate-based composite film material obtained by the high-barrier polypropylene carbonate-based composite material obtained in the step (3) is tableted by a flat vulcanizing machine at 170 ° C and 10 MPa to obtain a high-resistance polypropylene carbonate-based composite film material.
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