WO2022099655A1 - 一种可降解包装袋的材料及其制备方法 - Google Patents

一种可降解包装袋的材料及其制备方法 Download PDF

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WO2022099655A1
WO2022099655A1 PCT/CN2020/128832 CN2020128832W WO2022099655A1 WO 2022099655 A1 WO2022099655 A1 WO 2022099655A1 CN 2020128832 W CN2020128832 W CN 2020128832W WO 2022099655 A1 WO2022099655 A1 WO 2022099655A1
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parts
packaging bag
starch
degradable packaging
coupling agent
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PCT/CN2020/128832
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French (fr)
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金序能
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金序能
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives

Definitions

  • the invention relates to the field of material preparation, in particular to a preparation method of materials for degradable packaging bags.
  • White Pollution is an image title for the phenomenon of waste plastics polluting the environment. It refers to packaging bags, agricultural mulch films, disposable tableware, plastic Plastic products such as bottles are discarded as solid waste after being used. Due to random littering, they are difficult to degrade and cause pollution to the ecological environment and landscape.
  • plastic products As a new type of material, plastic products have the advantages of light weight, waterproof, durable, mature production technology and low cost. They are widely used all over the world and show an increasing trend year by year. The growth rate of plastic packaging materials in the world market is higher than that of other packaging materials, and the average annual growth rate of plastic packaging materials in 1990-1995 was 8.9%.
  • China is one of the top ten plastic products producing and consuming countries in the world.
  • plastic output was 5.19 million tons, and the imported plastic was nearly 6 million tons.
  • the total national plastic consumption in that year was about 11 million tons, of which 2.11 million tons were used for packaging.
  • Much of the plastic used in packaging is discarded in the environment in the form of used film, plastic bags and Styrofoam tableware. These waste plastic packaging are scattered in urban areas, scenic tourist areas, water bodies, and on both sides of roads, which not only affect the landscape and cause "visual pollution", but also cause potential harm to the ecological environment because of its difficulty in degradation.
  • Plastic garbage also stays in nature for a long time, generally up to 200-400 years, and some up to 500 years. Air pollution. Plastic, confetti, and dust fly with the wind. pollute water bodies. The plastic bottles and lunch boxes floating on the river and sea surface, the plastic bags and bread paper hanging on the branches above the water surface not only cause environmental pollution, but also harm the health of animals if they eat the white garbage by mistake. Undigested and starved to death. fire hazard. Almost all white garbage is combustible. In the process of natural stacking, methane and other combustible gases will be produced. Fire accidents that are easily caused by open flames or spontaneous combustion continue to occur, often causing heavy losses.
  • the present invention provides a material for a degradable packaging bag and a preparation method thereof, which solves the problems that plastic packaging is difficult to degrade and easily causes ecological pollution such as environmental pollution and marine pollution.
  • a material for a degradable packaging bag comprising the following components by weight: 16 parts to 26 parts of polyethylene; 30 parts to 55 parts of diatomaceous earth; 8 to 13 parts of modified starch; and 3 parts of plasticizer- -5 parts; coupling agent 0.8 part--1.5 part; inorganic filler 1 part--2 part; plant fiber 0.2 part--0.5 part, pectin 0.2 part--0.5 part, sodium alginate 0.2 part--0.5 part , 0.5 to 0.8 parts of warm wheel glue; 15-30 parts of purified water; wherein the polyethylene is linear low density polyethylene or a combination of high density polyethylene and linear low density polyethylene;
  • the preparation method of the modified starch is as follows: dissolving ordinary starch in sodium hydroxide solution, the quality of the sodium hydroxide solution is 1.5-5 times that of ordinary starch, then adding propylene oxide, and stirring the reaction at 55-65° C. After 3 to 5 hours, maleic anhydride was added, the reaction was stirred for 1 to 2 hours, washed, filtered with suction, and dried to obtain modified starch.
  • the starch is at least one of rice starch, corn starch, mung bean starch, lotus root starch and potato starch.
  • the plasticizer is one or more of fructose, sorbitol, glycerol, glycerol, low molecular weight polyvinyl alcohol and ethylene glycol mixed in any ratio;
  • the plant fiber is selected from one or more of bagasse powder, wood powder, bamboo powder, straw powder, grass fiber and microcrystalline cellulose.
  • the plant fiber is a powder with a particle size of 100-600 meshes.
  • the preferred particle sizes are 100 mesh, 200 mesh, 300 mesh and 400 mesh.
  • the inorganic filler is selected from one or more of talc, calcium carbonate, montmorillonite, and silica;
  • the coupling agent is one of aluminate coupling agent or titanate coupling agent.
  • the present invention also provides a material preparation method for the degradable packaging bag, comprising the following steps:
  • Step 1 Weigh each raw material component by weight, for subsequent use;
  • Step 2 Add all the raw materials to the high-speed mixer and mix for 10 to 15 minutes
  • Step 3 Add the modified starch into deionized water, continuously stir and heat to 70-90° C., and form a viscous and uniform transparent paste solution after stirring for 1-2 hours, and then add the remaining other components and continue to stir for 1-5 hours to obtain glue. liquid;
  • Step 4 Ultrasonic defoaming is performed on the glue obtained in step (2) by using ultrasonic defoaming equipment, the raw materials are continuously mixed and granulated under the condition of 170-190°C, blow-molded under the condition of 150-180°C, and inflated. The ratio is 1.5 to 3.0, and a film is obtained.
  • a novel degradable and environmentally friendly packaging material of the present invention has the beneficial effects of being degradable and easy to handle.
  • the manufacturing method of the present invention does not need to carry out a water washing procedure, nor does it require strong acid, strong alkali and bleaching agent, so there is no waste water.
  • the problem of emissions, without polluting water resources, will help to improve the problems of global warming caused by carbon dioxide (CO2).
  • Warm wheel glue is a hydrophilic colloid synthesized by the metabolic process of microorganisms. It exhibits a regular and stable structure in solution. It has a high viscosity at low concentration and has good compatibility with other colloids.
  • pectin, sodium alginate and warm wheel glue can greatly improve the effect and enhance the mechanical properties and thermodynamic stability of the product. After the modified starch and composite gelling agent are compounded, the system has better viscoelasticity and stability.
  • the present invention uses ultrasonic defoaming equipment to perform ultrasonic treatment on the glue, the purpose is to use ultrasonic cavitation to supersaturate the air dissolved in the glue, and the bubbles rise from the inside of the glue to the surface of the glue, thereby reducing the effect of bubbles adverse effects on the finished product.
  • the technical means used in the examples are conventional means well known to those skilled in the art, and the used reagents and products are also commercially available.
  • the source and trade name of the reagents used, as well as those necessary to list their components, are indicated when they appear for the first time.
  • a material for a degradable packaging bag comprising the following components by weight: 16 parts of polyethylene; 30 parts of diatomaceous earth; 8 parts of modified starch; 5 parts of plasticizer; 1.5 parts of coupling agent; 2 parts of inorganic filler; 0.5 part of plant fiber, 0.5 part of pectin, 0.5 part of sodium alginate, 0.8 part of warm wheel glue; 15-30 parts of purified water.
  • the specific preparation method includes the following steps:
  • Step 1 Weigh each raw material component by weight, for subsequent use;
  • Step 2 Add all the raw materials to the high-speed mixer and mix for 10 to 15 minutes
  • Step 3 Add the modified starch into deionized water, continuously stir and heat to 70-90° C., and form a viscous and uniform transparent paste solution after stirring for 1-2 hours, and then add the remaining other components and continue to stir for 1-5 hours to obtain glue. liquid;
  • Step 4 Ultrasonic defoaming is performed on the glue obtained in step (2) by using ultrasonic defoaming equipment, the raw materials are continuously mixed and granulated under the condition of 170-190°C, blow-molded under the condition of 150-180°C, and inflated. The ratio is 1.5 to 3.0, and a film is obtained.
  • a material for a degradable packaging bag comprising the following components by weight: 26 parts of polyethylene; 55 parts of diatomaceous earth; 13 parts of modified starch; 3 parts of plasticizer; 0.8 part of coupling agent; ; 0.2 part of plant fiber, 0.2 part of pectin, 0.2 part of sodium alginate, 0.5 part of warm wheel glue; 15-30 parts of purified water; wherein said polyethylene is linear low density polyethylene or high density polyethylene and thread
  • the combination of type low density polyethylene; the method is the same as that of Example 1.
  • a material for a degradable packaging bag comprising the following components by weight: 20 parts of polyethylene; 40 parts of diatomaceous earth; 10 parts of modified starch; 4 parts of plasticizer; 1.2 parts of coupling agent; --2 parts; 0.4 parts of plant fibers, 0.3 parts of pectin, 0.3 parts of sodium alginate, 0.6 parts of warm wheel glue; 15-30 parts of purified water; wherein the polyethylene is linear low density polyethylene or high density polyethylene
  • the combination of ethylene and linear low-density polyethylene; the method is the same as that of Example 1.
  • the degradable plastic packaging bag material prepared in the embodiment of the present invention has good mechanical properties, light transmittance and natural degradation rate; in addition, in the present invention, starch is used as the overall plastic packaging bag.
  • the main matrix of the material thereby ensuring a low production cost for the overall production process.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及材料制备领域，具体涉及可降解包装袋的材料的制备方法。一种可降解包装袋的材料，其特征在于，包括以下各重量组分组成，聚乙烯16份--26份；硅藻土30份--55份；改性淀粉8～30份；增塑剂3份--5份；偶联剂0.8份--1.5份；无机填料1份--2份；植物纤维0.2份--0.5份，果胶0.2份--0.5份、海藻酸钠0.2份--0.5份、温轮胶0.5份～0.8份；纯化水20份；其中所述聚乙烯为线型低密度聚乙烯或高密度聚乙烯与线型低密度聚乙烯的组合。

Description

一种可降解包装袋的材料及其制备方法 技术领域
本发明涉及材料制备领域，具体涉及可降解包装袋的材料的制备方法。
背景技术
白色污染(White Pollution)是对废塑料污染环境现象的一种形象称谓，是指用聚苯乙烯、聚丙烯、聚氯乙烯等高分子化合物制成的包装袋、农用地膜、一次性餐具、塑料瓶等塑料制品使用后被弃置成为固体废物，由于随意乱丢乱扔，难于降解处理，给生态环境和景观造成的污染。
塑料制品作为一种新型材料，具有质轻、防水、耐用、生产技术成熟、成本低的优点，在全世界被广泛应用且呈逐年增长趋势。塑料包装材料在世界市场中的增长率高于其它包装材料，1990-1995年塑料包装材料的年平均增长率为8.9％。
中国是世界上十大塑料制品生产和消费国之一。1995年，中国塑料产量为519万吨，进口塑料近600万吨，当年全国塑料消费总量约1100万吨，其中包装用塑料达211万吨。包装用塑料的大部分以废旧薄膜、塑料袋和泡沫塑料餐具的形式，被丢弃在环境中。这些废旧塑料包装物散落在市区、风景旅游区、水体、道路两侧，不仅影响景观，造成“视觉污染”，而且因其难以降解对生态环境造成潜在危害。
而白色污染的潜在危害，更值得引起人类的重视。例如，侵占土 地过多。塑料类垃圾在自然界停留的时间也很长，一般可达200—400年，有的可达500年。污染空气。塑料、纸屑和粉尘随风飞扬。污染水体。河、海水面上漂着的塑料瓶和饭盒，水面上方树枝上挂着的塑料袋、面包纸等，不仅造成环境污染,而且如果动物误食了白色垃圾会伤及健康，甚至会因其在消化道中无法消化而活活饿死。火灾隐患。白色垃圾几乎都是可燃物，在天然堆放过程中会产生甲烷等可燃气，遇明火或自燃易引起的火灾事故不断发生，时常造成重大损失等。
发明内容
本发明针对上述问题，提供一种可降解包装袋的材料及其制备方法，解决塑料包装难以降解，易造成环境污染和海洋污染等生态污染的问题。
为了达到上述目的，本发明是通过以下技术方案实现的：
一种可降解包装袋的材料，包括以下各重量组分组成，聚乙烯16份--26份；硅藻土30份--55份；改性淀粉8～13份；增塑剂3份--5份；偶联剂0.8份--1.5份；无机填料1份--2份；植物纤维0.2份--0.5份，果胶0.2份--0.5份、海藻酸钠0.2份--0.5份、温轮胶0.5份～0.8份；纯化水15-30份；其中所述聚乙烯为线型低密度聚乙烯或高密度聚乙烯与线型低密度聚乙烯的组合；
所述改性淀粉的制备方法为：将普通淀粉溶解于氢氧化钠溶液中，氢氧化钠溶液的质量为普通淀粉的1.5～5倍，然后加入环氧丙烷，在55～65℃下搅拌反应3～5h，接着加入马来酸酐，搅拌反应1～2h，洗涤、抽滤，干燥后得到改性淀粉。所述淀粉为米淀粉、玉米淀 粉、绿豆淀粉、藕淀粉和马铃薯淀粉中的至少一种。
所述增塑剂为果糖、山梨糖醇、甘油、甘油、低分子量聚乙烯醇和乙二醇的一种或两种以上以任意比混合而成；
所述植物纤维选自甘蔗渣粉、木粉、竹粉、秸秆粉、草纤维、微晶纤维素中的一种或多种。
所述植物纤维为粒度100～600目的粉末。优选的粒度为100目、200目、300目、400目。
所述无机填料选自滑石粉、碳酸钙、蒙脱土、白炭黑中的一种或多种；
所述的偶联剂为铝酸酯偶联剂或者钛酸酯偶联剂中的一种。
本发明还提供可降解包装袋的材料制备方法，包括以下步骤：
步骤1.按重量份称取各原料组分，备用；
步骤2.取各原料一同加入高速混合机中，混合10至15分钟
步骤3将改性淀粉加入到去离子水中，不断搅拌并加热到70～90℃，搅拌1～2h后形成粘稠均匀的透明糊溶液，再加入剩余其他组分继续搅拌1～5h，得到胶液；
步骤4.利用超声波消泡设备对步骤(2)得到的胶液进行超声除泡，将原料在170～190℃条件下连续密炼造粒，在150～180℃条件下吹塑成型，吹胀比为1.5～3.0，制得薄膜。
有益效果：
1、本发明的一种新型可降解环保包装材料具有可降解、易处理的有益效果，本发明的制造方法完不须进行用水洗涤程序，也不需 要强酸、强碱与漂白剂，因此没有废水排放的问题，不污染水资源，有助改善因二氧化碳(CO2)所造成的全球暖化等问题。
2、温轮胶是微生物代谢过程合成的亲水胶体，在溶液中呈现规则、稳定的结构，低浓度下即具有较高黏度，与其他胶体兼容性好。果胶、海藻酸钠、温轮胶配合使用，效果大大提高，增强了产品的机械性能和热力学稳定性。改性淀粉与复合凝胶剂进行复配后，体系具有更好的黏弹性、稳定性。
3、本发明使用超声波消泡设备对胶液进行超声处理，目的是利用超声波空化作用，使溶解在胶液中的空气过饱和，气泡从胶液内部上升至胶液表面，从而减少气泡对成品造成不良影响。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例，仅用于说明本发明而不用于限制本发明的范围，在阅读本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
若未特别指明，实施例中所采用的技术手段为本领域技术人员所熟知的常规手段，所采用的试剂和产品也均为可商业获得的。所用试剂的来源、商品名以及有必要列出其组成成分者，均在首次出现时标明。
实施例一
一种可降解包装袋的材料，包括以下各重量组分组成，聚乙烯16份；硅藻土30份；改性淀粉8；增塑剂5份；偶联剂1.5份；无 机填料2份；植物纤维0.5份，果胶0.5份、海藻酸钠0.5份、温轮胶0.8份；纯化水15-30份。
具体制备方法包括以下步骤：
包括以下步骤：
步骤1.按重量份称取各原料组分，备用；
步骤2.取各原料一同加入高速混合机中，混合10至15分钟
步骤3将改性淀粉加入到去离子水中，不断搅拌并加热到70～90℃，搅拌1～2h后形成粘稠均匀的透明糊溶液，再加入剩余其他组分继续搅拌1～5h，得到胶液；
步骤4.利用超声波消泡设备对步骤(2)得到的胶液进行超声除泡，将原料在170～190℃条件下连续密炼造粒，在150～180℃条件下吹塑成型，吹胀比为1.5～3.0，制得薄膜。
实施例二
一种可降解包装袋的材料，包括以下各重量组分组成，聚乙烯26份；硅藻土55份；改性淀粉13份；增塑剂3份；偶联剂0.8份；无极填料1份；植物纤维0.2份，果胶0.2份、海藻酸钠0.2份、温轮胶0.5份份；纯化水15-30份；其中所述聚乙烯为线型低密度聚乙烯或高密度聚乙烯与线型低密度聚乙烯的组合；方法同实施例一。
实施例三
一种可降解包装袋的材料，包括以下各重量组分组成，聚乙烯20份；硅藻土40份；改性淀粉10份；增塑剂4份；偶联剂1.2份；无极填料1份--2份；植物纤维0.4份，果胶0.3份、海藻酸钠0.3份、 温轮胶0.6份；纯化水15-30份；其中所述聚乙烯为线型低密度聚乙烯或高密度聚乙烯与线型低密度聚乙烯的组合；方法同实施例一。
对制备产物的性能测试：
对实施例一至三，制备所得的降解包装袋的材料透光率、自然降解天数，以及耐用性能分别作了测试。
表一：耐用性
  市售包装袋 实施例一 实施例二 实施例三
拉伸强度(MPa) 18.7 19.6 19.7 21.3
断裂伸长率(％) 245 248 255 265
表二：透光率
  市售包装袋 实施例一 实施例二 实施例三
透光率 95.3 96.6 96.8 96.8
表三：自然降解时间
  市售包装袋 实施例一 实施例二 实施例三
25天自然降解率 75 97.6 95. 95.8
由此可见，本发明实施例中所制得的可降解的塑料包装袋材料具有较好的力学性能、透光性和自然降解率；另外，在本发明中，保持以淀粉作为整体塑料包装袋材料的主要基体，由此保证整体制备过程具有较低的制备成本。以上显示和描述了本发明的基本原理和主要特征和本发明的优点。
以上仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来书，在不脱离本发明的原理的前提下，还可以作数若 干改进和润饰，这些改进和润饰也应当视为本发明的保护范围。

Claims (8)

  1. 一种可降解包装袋的材料，其特征在于，包括以下各重量组分组成：聚乙烯16份--26份；硅藻土30份--55份；改性淀粉8～13份；增塑剂3份--5份；偶联剂0.8份--1.5份；无机填料1份--2份；植物纤维0.2份--0.5份，果胶0.2份--0.5份、海藻酸钠0.2份--0.5份、温轮胶0.5份～0.8份；纯化水10-30份；其中，所述聚乙烯为线型低密度聚乙烯或高密度聚乙烯与线型低密度聚乙烯的组合。
  2. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述淀粉为米淀粉、玉米淀粉、绿豆淀粉、藕淀粉和马铃薯淀粉中的至少一种。
  3. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述增塑剂为果糖、山梨糖醇、甘油、甘油、低分子量聚乙烯醇和乙二醇的一种或两种以上以任意比混合而成；
  4. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述植物纤维选自甘蔗渣粉、木粉、竹粉、秸秆粉、草纤维、微晶纤维素中的一种或多种。
  5. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述植物纤维为粒度100～600目的粉末。优选的粒度为100目、200目、300目、400目。
  6. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述无机填料选自滑石粉、碳酸钙、蒙脱土、白炭黑中的一种或多种；
  7. 根据权利要求1所述的，可降解包装袋的材料，其特征在于，所述的偶联剂为铝酸酯偶联剂或者钛酸酯偶联剂中的一种。
  8. 一种制备权利要求1所述的可降解包装袋的材料的方法，其特征在于：
    包括以下步骤：
    步骤1.按重量份称取各原料组分，备用；
    步骤2.取各原料一同加入高速混合机中，混合10至15分钟
    步骤3将改性淀粉加入到去离子水中，不断搅拌并加热到70～90℃，搅拌1～2h后形成粘稠均匀的透明糊溶液，再加入剩余其他组分继续搅拌1～5h，得到胶液；
    步骤4.利用超声波消泡设备对步骤(2)得到的胶液进行超声除泡，将原料在170～190℃条件下连续密炼造粒，在150～180℃条件下吹塑成型，吹胀比为1.5～3.0，制得薄膜。
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