技术领域Technical Field
本发明属于塑料技术领域，具体是指一种可降解复合聚乙烯塑料及其制备方法。The invention belongs to the technical field of plastics, and specifically relates to a degradable composite polyethylene plastic and a preparation method thereof.
背景技术Background technique
塑料因具有高强度、低密度和耐腐蚀等优点而成为人们生活中不可或缺的物品，由于塑料制品难以降解，使用后会产生大量的固体废弃物，导致其在环境中不断积累，引起了一系列土壤、水体污染问题。Plastic has become an indispensable item in people's lives due to its advantages such as high strength, low density and corrosion resistance. However, since plastic products are difficult to degrade, a large amount of solid waste will be generated after use, which leads to its continuous accumulation in the environment, causing a series of soil and water pollution problems.
生物降解塑料是指在如土壤、沙土等自然条件下，或堆肥化、厌氧消化、水性培养液等特定条件下，可以在微生物如细菌、真菌、藻类或酶的作用下被分解，并最终完全降解变成二氧化碳、甲烷、水及其所含元素的矿化无机盐以及新的生物质的一类可降解塑料，天然高分子型可生物降解塑料生产工艺较为简单，但制得的产品往往耐水性差、热塑性差、脆硬、力学性能水平较低，综合性能往往与传统塑料有较大的差距，需进一步提高产品性能。Biodegradable plastics refer to a type of degradable plastic that can be decomposed by microorganisms such as bacteria, fungi, algae or enzymes under natural conditions such as soil and sand, or under specific conditions such as composting, anaerobic digestion, and aqueous culture medium, and ultimately completely degraded into carbon dioxide, methane, water, mineralized inorganic salts of the elements it contains, and new biomass. The production process of natural polymer biodegradable plastics is relatively simple, but the products produced often have poor water resistance, poor thermoplasticity, are brittle, and have low mechanical properties. The overall performance is often far behind that of traditional plastics, and product performance needs to be further improved.
发明内容Summary of the invention
针对上述情况，为克服现有技术的缺陷，本发明提供了一种可降解复合聚乙烯塑料及其制备方法，为了解决聚乙烯塑料降解性差的问题，本发明提出多巴胺改性微晶纤维素、聚醚醚酮/羟基磷灰石复合材料和壳聚糖/纳米二氧化硅气凝胶加入聚乙烯中，提高聚乙烯塑料的可降解性和力学性能。In view of the above situation, in order to overcome the defects of the prior art, the present invention provides a degradable composite polyethylene plastic and a preparation method thereof. In order to solve the problem of poor degradability of polyethylene plastic, the present invention proposes adding dopamine-modified microcrystalline cellulose, polyetheretherketone/hydroxyapatite composite materials and chitosan/nano-silica aerogel into polyethylene to improve the degradability and mechanical properties of polyethylene plastic.
为了实现上述目的，本发明采取的技术方案如下：本发明提出了一种可降解复合聚乙烯塑料及其制备方法，所述可降解复合聚乙烯塑料包括如下重量份的组分：低密度聚乙烯80-100份、淀粉8-12份、多巴胺改性微晶纤维素5-8份、聚醚醚酮/羟基磷灰石复合材料10-15份、壳聚糖/纳米二氧化硅气凝胶15-20份、聚乙烯蜡2-3份、甘油3-5份。In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention is as follows: The present invention proposes a degradable composite polyethylene plastic and a preparation method thereof, wherein the degradable composite polyethylene plastic comprises the following components in parts by weight: 80-100 parts of low-density polyethylene, 8-12 parts of starch, 5-8 parts of dopamine-modified microcrystalline cellulose, 10-15 parts of polyetheretherketone/hydroxyapatite composite material, 15-20 parts of chitosan/nano-silica aerogel, 2-3 parts of polyethylene wax, and 3-5 parts of glycerol.
进一步地，所述多巴胺改性微晶纤维素的制备方法如下：Furthermore, the preparation method of the dopamine-modified microcrystalline cellulose is as follows:
取微晶纤维素置于烧杯中，加入100mL去离子水，使用盐酸缓冲液调节pH值至8.5，加入多巴胺，30℃下搅拌3-4h，结束后离心取沉淀，干燥箱中60℃干燥10h，得到多巴胺改性微晶纤维素。Place microcrystalline cellulose in a beaker, add 100 mL of deionized water, adjust the pH value to 8.5 with hydrochloric acid buffer, add dopamine, stir at 30°C for 3-4 hours, centrifuge to obtain the precipitate, and dry it in a drying oven at 60°C for 10 hours to obtain dopamine-modified microcrystalline cellulose.
进一步地，所述微晶纤维素与多巴胺的质量比为1:0.3-0.4，离心的转速为3000-4000rpm，时间为1-2h。Furthermore, the mass ratio of microcrystalline cellulose to dopamine is 1:0.3-0.4, the centrifugal speed is 3000-4000 rpm, and the time is 1-2h.
进一步地，所述聚醚醚酮/羟基磷灰石复合材料的制备方法如下：Furthermore, the preparation method of the polyetheretherketone/hydroxyapatite composite material is as follows:
取羟基磷灰石和聚醚醚酮加入无水乙醇中，置于超声分散器中超声分散1小时，然后抽滤分离出混合物，置于烘箱中90℃干燥10h，用双螺杆挤出机混合挤出，得到聚醚醚酮/羟基磷灰石复合材料。Take hydroxyapatite and polyetheretherketone, add them to anhydrous ethanol, place them in an ultrasonic disperser for ultrasonic dispersion for 1 hour, then filter out the mixture, place it in an oven to dry at 90°C for 10 hours, and extrude it with a twin-screw extruder to obtain a polyetheretherketone/hydroxyapatite composite material.
进一步地，所述羟基磷灰石和聚醚醚酮的质量比为1-2:20，超声分散的功率为300W，挤出温度为370℃-400℃，转速为60r/min。Furthermore, the mass ratio of hydroxyapatite to polyetheretherketone is 1-2:20, the power of ultrasonic dispersion is 300W, the extrusion temperature is 370°C-400°C, and the rotation speed is 60r/min.
进一步地，所述壳聚糖/纳米二氧化硅气凝胶的制备方法包括如下步骤：Furthermore, the preparation method of the chitosan/nano-silica aerogel comprises the following steps:
S1、取壳聚糖加入50mL0.2%的乙酸溶液中，50℃下500r/min磁力搅拌30min，得到壳聚糖溶液，取纳米二氧化硅加入50mL无水乙醇中，搅拌30min，得到混合液；S1. Add chitosan to 50 mL of 0.2% acetic acid solution, stir magnetically at 50 °C and 500 r/min for 30 min to obtain a chitosan solution, add nano-silica to 50 mL of anhydrous ethanol, stir for 30 min to obtain a mixed solution;
S2、将步骤S1所得壳聚糖溶液和混合液移至烧杯中，40℃水浴500r/min磁力搅拌24h，然后置于离心机中8000r/min离心除去上清液，依次用乙醇溶液和超纯水洗涤沉淀至上清液无色后，沉淀放置于-20℃冰箱冷冻24h，冷冻干燥得到壳聚糖/纳米二氧化硅气凝胶。S2. The chitosan solution and the mixed solution obtained in step S1 were transferred to a beaker, magnetically stirred at 500 r/min in a 40°C water bath for 24 h, and then centrifuged at 8000 r/min in a centrifuge to remove the supernatant. The precipitate was washed with ethanol solution and ultrapure water in turn until the supernatant was colorless, and the precipitate was placed in a -20°C refrigerator for 24 h, and freeze-dried to obtain chitosan/nano-silica aerogel.
进一步地，在步骤S1中，所述壳聚糖和纳米二氧化硅的质量比为3:1-2。Furthermore, in step S1, the mass ratio of chitosan to nano-silicon dioxide is 3:1-2.
本发明提供了一种可降解复合聚乙烯塑料的制备方法，具体包括如下步骤：The present invention provides a method for preparing a degradable composite polyethylene plastic, which specifically comprises the following steps:
将淀粉、多巴胺改性微晶纤维素、聚醚醚酮/羟基磷灰石复合材料、壳聚糖/纳米二氧化硅气凝胶搅拌混合均匀，然后加入聚乙烯蜡、甘油继续搅拌混合，最后加入低密度聚乙烯混合均匀后置于密炼机中进行密炼，结束后冷却破碎，转入双螺杆挤出机中，混合后挤出造粒，用注射机制备定型，得到可降解复合聚乙烯塑料。Starch, dopamine-modified microcrystalline cellulose, polyetheretherketone/hydroxyapatite composite material, and chitosan/nano-silica aerogel are stirred and mixed evenly, and then polyethylene wax and glycerin are added and continued to be stirred and mixed, and finally low-density polyethylene is added and mixed evenly, and then placed in an internal mixer for internal mixing. After the mixture is mixed, it is cooled and crushed, transferred to a twin-screw extruder, extruded into granules after mixing, and shaped by an injection machine to obtain a degradable composite polyethylene plastic.
本发明取得的有益效果如下：The beneficial effects achieved by the present invention are as follows:
微晶纤维素是天然纤维素的水解产物，具有较完整的结晶结构和大的长径比，因此拥有可降解性和优异的机械性能，多巴胺能够在碱性条件下自氧化形成聚多巴胺而包覆在微晶纤维素表面，改善微晶纤维素与基体的相容性和在基体的分散性，进而提高塑料的力学性能；聚醚醚酮有良好的化学稳定性、耐水性和热稳定性，羟基磷灰石作为天然骨材料中主要无机成分使得骨材料具有优异的机械性能，因此向聚醚醚酮中加入羟基磷灰石作为无机填料，能够提高复合材料的机械性能，加入到聚乙烯中能够提高塑料的综合性能；壳聚糖具有非常好的降解性，但本身稳定性较差，将壳聚糖和纳米二氧化硅复合制备成气凝胶加入聚乙烯中，提高塑料可降解性的同时有较好的稳定性，而且气凝胶的多孔结构，能够为微生物提供更多的吸附位置，更有利于降解；聚乙烯蜡和甘油有效地减少了各组分之间的摩擦，改善内部的柔顺度和表面光滑度，使得整体的力学性能得到提升。Microcrystalline cellulose is a hydrolysis product of natural cellulose, with a relatively complete crystalline structure and a large aspect ratio, so it has degradability and excellent mechanical properties. Dopamine can be self-oxidized under alkaline conditions to form polydopamine and coated on the surface of microcrystalline cellulose, improving the compatibility of microcrystalline cellulose with the matrix and the dispersibility in the matrix, thereby improving the mechanical properties of plastics; polyetheretherketone has good chemical stability, water resistance and thermal stability. Hydroxyapatite, as the main inorganic component in natural bone materials, makes bone materials have excellent mechanical properties. Therefore, adding hydroxyapatite to polyetheretherketone as an inorganic filler can improve the mechanical properties of the composite material, and adding it to polyethylene can improve the comprehensive performance of plastics; chitosan has very good degradability, but its own stability is poor. Chitosan and nano-silicon dioxide are composited to prepare aerogels and added to polyethylene, which improves the degradability of plastics while having good stability. In addition, the porous structure of aerogels can provide more adsorption sites for microorganisms, which is more conducive to degradation; polyethylene wax and glycerol effectively reduce the friction between the components, improve the internal flexibility and surface smoothness, and improve the overall mechanical properties.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1-3和对比例1-3拉伸性能测试结果图；FIG1 is a graph showing the tensile properties test results of Examples 1-3 and Comparative Examples 1-3 of the present invention;
图2为本发明实施例1-3和对比例1-3弯曲性能测试结果图；FIG2 is a graph showing the bending performance test results of Examples 1-3 and Comparative Examples 1-3 of the present invention;
图3为本发明实施例1-3和对比例1-3生物降解性测试结果图；FIG3 is a graph showing the biodegradability test results of Examples 1-3 and Comparative Examples 1-3 of the present invention;
图4为本发明实施例1所制备的可降解复合聚乙烯塑料的扫描电镜图。FIG. 4 is a scanning electron microscope image of the degradable composite polyethylene plastic prepared in Example 1 of the present invention.
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
除非另行定义，文中所使用的所有专业与科学用语与本领域技术人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明中。文中所述的较佳实施方法与材料仅作示范之用，但不能限制本申请的内容。Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.
下述实施例中的实验方法，如无特殊说明，均为常规方法；下述实施例中所用的试验材料，如无特殊说明，均为从商业渠道购买得到的。The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.
实施例1Example 1
一种可降解复合聚乙烯塑料，包括如下重量份的组分：低密度聚乙烯80份、淀粉8份、多巴胺改性微晶纤维素5份、聚醚醚酮/羟基磷灰石复合材料10份、壳聚糖/纳米二氧化硅气凝胶15份、聚乙烯蜡2份、甘油3份。A degradable composite polyethylene plastic comprises the following components in parts by weight: 80 parts of low-density polyethylene, 8 parts of starch, 5 parts of dopamine-modified microcrystalline cellulose, 10 parts of polyetheretherketone/hydroxyapatite composite material, 15 parts of chitosan/nano-silica aerogel, 2 parts of polyethylene wax and 3 parts of glycerol.
所述多巴胺改性微晶纤维素的制备方法如下：The preparation method of the dopamine-modified microcrystalline cellulose is as follows:
取1g微晶纤维素置于烧杯中，加入100mL去离子水，使用盐酸缓冲液调节pH值至8.5，加入0.3g多巴胺，30℃下搅拌3h，结束后离心取沉淀，离心的转速为3000rpm，时间为1h，干燥箱中60℃干燥10h，得到多巴胺改性微晶纤维素。Take 1g of microcrystalline cellulose and put it in a beaker, add 100mL of deionized water, use hydrochloric acid buffer to adjust the pH value to 8.5, add 0.3g of dopamine, stir at 30°C for 3h, centrifuge to obtain the precipitate after the end, the centrifugation speed is 3000rpm, the time is 1h, and dry at 60°C in a drying oven for 10h to obtain dopamine-modified microcrystalline cellulose.
所述聚醚醚酮/羟基磷灰石复合材料的制备方法如下：The preparation method of the polyetheretherketone/hydroxyapatite composite material is as follows:
取1g羟基磷灰石和20g聚醚醚酮加入无水乙醇中，置于超声分散器中超声分散1小时，超声分散的功率为300W，然后抽滤分离出混合物，置于烘箱中90℃干燥10h，用双螺杆挤出机混合挤出，挤出温度为370℃，转速为60r/min，得到聚醚醚酮/羟基磷灰石复合材料。Take 1g of hydroxyapatite and 20g of polyetheretherketone, add them to anhydrous ethanol, place them in an ultrasonic disperser for ultrasonic dispersion for 1 hour, the ultrasonic dispersion power is 300W, then filter and separate the mixture, place it in an oven at 90°C and dry it for 10 hours, and extrude it with a twin-screw extruder at an extrusion temperature of 370°C and a rotation speed of 60r/min to obtain a polyetheretherketone/hydroxyapatite composite material.
所述壳聚糖/纳米二氧化硅气凝胶的制备方法包括如下步骤：The preparation method of the chitosan/nano-silicon dioxide aerogel comprises the following steps:
S1、取3g壳聚糖加入50mL0.2%的乙酸溶液中，50℃下500r/min磁力搅拌30min，得到壳聚糖溶液，取1g纳米二氧化硅加入50mL无水乙醇中，搅拌30min，得到混合液；S1. Take 3 g of chitosan and add it to 50 mL of 0.2% acetic acid solution, stir it with magnetic force at 500 r/min at 50°C for 30 min to obtain a chitosan solution, take 1 g of nano-silica and add it to 50 mL of anhydrous ethanol, stir it for 30 min to obtain a mixed solution;
S2、将步骤S1所得壳聚糖溶液和混合液移至烧杯中，40℃水浴500r/min磁力搅拌24h，然后置于离心机中8000r/min离心除去上清液，依次用乙醇溶液和超纯水洗涤沉淀至上清液无色后，沉淀放置于-20℃冰箱冷冻24h，冷冻干燥得到壳聚糖/纳米二氧化硅气凝胶。S2. The chitosan solution and the mixed solution obtained in step S1 were transferred to a beaker, magnetically stirred at 500 r/min in a 40°C water bath for 24 h, and then centrifuged at 8000 r/min in a centrifuge to remove the supernatant. The precipitate was washed with ethanol solution and ultrapure water in turn until the supernatant was colorless, and the precipitate was placed in a -20°C refrigerator for 24 h, and freeze-dried to obtain chitosan/nano-silica aerogel.
本实施例提供了一种可降解复合聚乙烯塑料的制备方法，具体包括如下步骤：This embodiment provides a method for preparing a degradable composite polyethylene plastic, which specifically comprises the following steps:
将淀粉、多巴胺改性微晶纤维素、聚醚醚酮/羟基磷灰石复合材料、壳聚糖/纳米二氧化硅气凝胶搅拌混合均匀，然后加入聚乙烯蜡、甘油继续搅拌混合，最后加入低密度聚乙烯混合均匀后置于密炼机中进行密炼，结束后冷却破碎，转入双螺杆挤出机中，混合后挤出造粒，用注射机制备定型，得到可降解复合聚乙烯塑料。Starch, dopamine-modified microcrystalline cellulose, polyetheretherketone/hydroxyapatite composite material, and chitosan/nano-silica aerogel are stirred and mixed evenly, and then polyethylene wax and glycerin are added and continued to be stirred and mixed. Finally, low-density polyethylene is added and mixed evenly, and then placed in an internal mixer for internal mixing. After the mixing is completed, it is cooled and crushed, transferred to a twin-screw extruder, extruded into granules after mixing, and formed by an injection machine to obtain a degradable composite polyethylene plastic.
实施例2Example 2
一种可降解复合聚乙烯塑料，包括如下重量份的组分：低密度聚乙烯100份、淀粉12份、多巴胺改性微晶纤维素8份、聚醚醚酮/羟基磷灰石复合材料15份、壳聚糖/纳米二氧化硅气凝胶20份、聚乙烯蜡3份、甘油5份。A degradable composite polyethylene plastic comprises the following components in parts by weight: 100 parts of low-density polyethylene, 12 parts of starch, 8 parts of dopamine-modified microcrystalline cellulose, 15 parts of polyetheretherketone/hydroxyapatite composite material, 20 parts of chitosan/nano-silicon dioxide aerogel, 3 parts of polyethylene wax and 5 parts of glycerol.
所述多巴胺改性微晶纤维素的制备方法如下：The preparation method of the dopamine-modified microcrystalline cellulose is as follows:
取1g微晶纤维素置于烧杯中，加入100mL去离子水，使用盐酸缓冲液调节pH值至8.5，加入0.4g多巴胺，30℃下搅拌4h，结束后离心取沉淀，离心的转速为4000rpm，时间为2h，干燥箱中60℃干燥10h，得到多巴胺改性微晶纤维素。Take 1g of microcrystalline cellulose and put it in a beaker, add 100mL of deionized water, use hydrochloric acid buffer to adjust the pH value to 8.5, add 0.4g of dopamine, stir at 30°C for 4h, centrifuge to obtain the precipitate after the end, the centrifugation speed is 4000rpm, the time is 2h, and dry in a drying oven at 60°C for 10h to obtain dopamine-modified microcrystalline cellulose.
所述聚醚醚酮/羟基磷灰石复合材料的制备方法如下：The preparation method of the polyetheretherketone/hydroxyapatite composite material is as follows:
取2g羟基磷灰石和20g聚醚醚酮加入无水乙醇中，置于超声分散器中超声分散1小时，超声分散的功率为300W，然后抽滤分离出混合物，置于烘箱中90℃干燥10h，用双螺杆挤出机混合挤出，挤出温度为400℃，转速为60r/min，得到聚醚醚酮/羟基磷灰石复合材料。Take 2g of hydroxyapatite and 20g of polyetheretherketone, add them to anhydrous ethanol, place them in an ultrasonic disperser for ultrasonic dispersion for 1 hour, the ultrasonic dispersion power is 300W, then filter and separate the mixture, place it in an oven at 90°C and dry it for 10h, and extrude it with a twin-screw extruder at an extrusion temperature of 400°C and a rotation speed of 60r/min to obtain a polyetheretherketone/hydroxyapatite composite material.
所述壳聚糖/纳米二氧化硅气凝胶的制备方法包括如下步骤：The preparation method of the chitosan/nano-silicon dioxide aerogel comprises the following steps:
S1、取3g壳聚糖加入50mL0.2%的乙酸溶液中，50℃下500r/min磁力搅拌30min，得到壳聚糖溶液，取2g纳米二氧化硅加入50mL无水乙醇中，搅拌30min，得到混合液；S1. Take 3 g of chitosan and add it to 50 mL of 0.2% acetic acid solution, stir it with magnetic force at 500 r/min at 50°C for 30 min to obtain a chitosan solution, take 2 g of nano-silica and add it to 50 mL of anhydrous ethanol, stir it for 30 min to obtain a mixed solution;
S2、将步骤S1所得壳聚糖溶液和混合液移至烧杯中，40℃水浴500r/min磁力搅拌24h，然后置于离心机中8000r/min离心除去上清液，依次用乙醇溶液和超纯水洗涤沉淀至上清液无色后，沉淀放置于-20℃冰箱冷冻24h，冷冻干燥得到壳聚糖/纳米二氧化硅气凝胶。S2. The chitosan solution and the mixed solution obtained in step S1 were transferred to a beaker, magnetically stirred at 500 r/min in a 40°C water bath for 24 h, and then centrifuged at 8000 r/min in a centrifuge to remove the supernatant. The precipitate was washed with ethanol solution and ultrapure water in turn until the supernatant was colorless, and the precipitate was placed in a -20°C refrigerator for 24 h, and freeze-dried to obtain chitosan/nano-silica aerogel.
本实施例提供了一种可降解复合聚乙烯塑料的制备方法，所述制备方法参照实施例1施行。This embodiment provides a method for preparing a degradable composite polyethylene plastic, and the preparation method is carried out with reference to Example 1.
实施例3Example 3
一种可降解复合聚乙烯塑料，包括如下重量份的组分：低密度聚乙烯90份、淀粉10份、多巴胺改性微晶纤维素7份、聚醚醚酮/羟基磷灰石复合材料12份、壳聚糖/纳米二氧化硅气凝胶17份、聚乙烯蜡2.5份、甘油4份。A degradable composite polyethylene plastic comprises the following components in parts by weight: 90 parts of low-density polyethylene, 10 parts of starch, 7 parts of dopamine-modified microcrystalline cellulose, 12 parts of polyetheretherketone/hydroxyapatite composite material, 17 parts of chitosan/nano-silicon dioxide aerogel, 2.5 parts of polyethylene wax and 4 parts of glycerol.
所述多巴胺改性微晶纤维素的制备方法如下：The preparation method of the dopamine-modified microcrystalline cellulose is as follows:
取1g微晶纤维素置于烧杯中，加入100mL去离子水，使用盐酸缓冲液调节pH值至8.5，加入0.35g多巴胺，30℃下搅拌4h，结束后离心取沉淀，离心的转速为4000rpm，时间为2h，干燥箱中60℃干燥10h，得到多巴胺改性微晶纤维素。Take 1g of microcrystalline cellulose and put it in a beaker, add 100mL of deionized water, use hydrochloric acid buffer to adjust the pH value to 8.5, add 0.35g of dopamine, stir at 30°C for 4h, and then centrifuge to obtain the precipitate at a speed of 4000rpm for 2h. Dry it in a drying oven at 60°C for 10h to obtain dopamine-modified microcrystalline cellulose.
所述聚醚醚酮/羟基磷灰石复合材料的制备方法如下：The preparation method of the polyetheretherketone/hydroxyapatite composite material is as follows:
取1.5g羟基磷灰石和20g聚醚醚酮加入无水乙醇中，置于超声分散器中超声分散1小时，超声分散的功率为300W，然后抽滤分离出混合物，置于烘箱中90℃干燥10h，用双螺杆挤出机混合挤出，挤出温度为380℃，转速为60r/min，得到聚醚醚酮/羟基磷灰石复合材料。Take 1.5g of hydroxyapatite and 20g of polyetheretherketone, add them to anhydrous ethanol, place them in an ultrasonic disperser for ultrasonic dispersion for 1 hour, the ultrasonic dispersion power is 300W, then filter and separate the mixture, place it in an oven at 90°C and dry it for 10h, and extrude it with a twin-screw extruder at an extrusion temperature of 380°C and a rotation speed of 60r/min to obtain a polyetheretherketone/hydroxyapatite composite material.
所述壳聚糖/纳米二氧化硅气凝胶的制备方法包括如下步骤：The preparation method of the chitosan/nano-silicon dioxide aerogel comprises the following steps:
S1、取3g壳聚糖加入50mL0.2%的乙酸溶液中，50℃下500r/min磁力搅拌30min，得到壳聚糖溶液，取1.5g纳米二氧化硅加入50mL无水乙醇中，搅拌30min，得到混合液；S1. Take 3 g of chitosan and add it to 50 mL of 0.2% acetic acid solution, stir it with magnetic force at 500 r/min at 50°C for 30 min to obtain a chitosan solution, take 1.5 g of nano-silica and add it to 50 mL of anhydrous ethanol, stir it for 30 min to obtain a mixed solution;
S2、将步骤S1所得壳聚糖溶液和混合液移至烧杯中，40℃水浴500r/min磁力搅拌24h，然后置于离心机中8000r/min离心除去上清液，依次用乙醇溶液和超纯水洗涤沉淀至上清液无色后，沉淀放置于-20℃冰箱冷冻24h，冷冻干燥得到壳聚糖/纳米二氧化硅气凝胶。S2. The chitosan solution and the mixed solution obtained in step S1 were transferred to a beaker, magnetically stirred at 500 r/min in a 40°C water bath for 24 h, and then centrifuged at 8000 r/min in a centrifuge to remove the supernatant. The precipitate was washed with ethanol solution and ultrapure water in turn until the supernatant was colorless, and the precipitate was placed in a -20°C refrigerator for 24 h, and freeze-dried to obtain chitosan/nano-silica aerogel.
本实施例提供了一种可降解复合聚乙烯塑料的制备方法，所述制备方法参照实施例1施行。This embodiment provides a method for preparing a degradable composite polyethylene plastic, and the preparation method is carried out with reference to Example 1.
对比例1Comparative Example 1
本对比例提供一种可降解复合聚乙烯塑料及其制备方法，其与实施例1的区别在于所有组分中不包含多巴胺改性微晶纤维素，其余组分、组分含量与实施例1相同。This comparative example provides a degradable composite polyethylene plastic and a preparation method thereof, which is different from Example 1 in that dopamine-modified microcrystalline cellulose is not included in all components, and the remaining components and component contents are the same as those in Example 1.
对比例2Comparative Example 2
本对比例提供一种可降解复合聚乙烯塑料及其制备方法，其与实施例1的区别在于所有组分中不包含聚醚醚酮/羟基磷灰石复合材料，其余组分、组分含量与实施例1相同。This comparative example provides a degradable composite polyethylene plastic and a preparation method thereof, which is different from Example 1 in that all components do not contain polyetheretherketone/hydroxyapatite composite materials, and the remaining components and component contents are the same as those in Example 1.
对比例3Comparative Example 3
本对比例提供一种可降解复合聚乙烯塑料及其制备方法，其与实施例1的区别在于所有组分中不包含壳聚糖/纳米二氧化硅气凝胶，其余组分、组分含量与实施例1相同。This comparative example provides a degradable composite polyethylene plastic and a preparation method thereof, which is different from Example 1 in that all components do not contain chitosan/nano-silica aerogel, and the remaining components and component contents are the same as those in Example 1.
实验例Experimental example
1、对本发明实施例1-3及对比例1-3所制备的可降解复合聚乙烯塑料进行拉伸性能测试，具体方法参照GB/T 1040.1-2018，样条宽度为10mm，厚度为4mm，拉伸速度为5mm/min。1. The tensile properties of the degradable composite polyethylene plastics prepared in Examples 1-3 and Comparative Examples 1-3 of the present invention were tested. The specific method was based on GB/T 1040.1-2018. The width of the strip was 10 mm, the thickness was 4 mm, and the tensile speed was 5 mm/min.
2、对本发明实施例1-3及对比例1-3所制备的可降解复合聚乙烯塑料进行弯曲性能测试，具体方法参照GB/T 9341-2008，样条宽度为10mm，厚度为4mm，弯曲速度为2mm/min。2. The bending performance of the degradable composite polyethylene plastics prepared in Examples 1-3 of the present invention and Comparative Examples 1-3 was tested. The specific method was based on GB/T 9341-2008. The width of the strip was 10 mm, the thickness was 4 mm, and the bending speed was 2 mm/min.
3、对本发明实施例1-3及对比例1-3所制备的可降解复合聚乙烯塑料进行生物降解性分析测试，采用填埋降解方式进行生物降解，60天后取出测量其剩余质量并计算降解率。3. The biodegradability analysis test of the degradable composite polyethylene plastics prepared in Examples 1-3 of the present invention and Comparative Examples 1-3 was carried out, and biodegradation was carried out by landfill degradation. After 60 days, the remaining mass was measured and the degradation rate was calculated.
降解率=（降解前质量-剩余质量）/降解前质量×100%。Degradation rate = (mass before degradation - remaining mass) / mass before degradation × 100%.
4、对实施例1所制备的可降解复合聚乙烯塑料表面形貌以采用扫描电子显微镜观察。4. The surface morphology of the degradable composite polyethylene plastic prepared in Example 1 was observed using a scanning electron microscope.
结果分析Result analysis
图1为本发明实施例1-3和对比例1-3拉伸性能测试结果图，如图所示，实施例1-3的拉伸强度分别为10.7MPa、11.3MPa、10.1MPa，对比例1-3分别为6.2MPa、7.1MPa、8.4MPa。FIG1 is a graph showing the tensile properties test results of Examples 1-3 and Comparative Examples 1-3 of the present invention. As shown in the figure, the tensile strengths of Examples 1-3 are 10.7 MPa, 11.3 MPa, and 10.1 MPa, respectively, and those of Comparative Examples 1-3 are 6.2 MPa, 7.1 MPa, and 8.4 MPa, respectively.
图2为本发明实施例1-3和对比例1-3弯曲性能测试结果图，如图所示，实施例1-3的拉伸强度分别为7.9MPa、8.2MPa、7.6MPa，对比例1-3分别为5.7MPa、5.8MPa、6.1MPa。FIG2 is a graph showing the bending performance test results of Examples 1-3 and Comparative Examples 1-3 of the present invention. As shown in the figure, the tensile strengths of Examples 1-3 are 7.9 MPa, 8.2 MPa, and 7.6 MPa, respectively, and those of Comparative Examples 1-3 are 5.7 MPa, 5.8 MPa, and 6.1 MPa, respectively.
图3为本发明实施例1-3和对比例1-3生物降解性测试结果图，如图所示，实施例1-3的降解率分别为56.2%、57.1%、56.8%，对比例1-3分别为38.2%、41.1%、34.7%。FIG3 is a graph showing the biodegradability test results of Examples 1-3 and Comparative Examples 1-3 of the present invention. As shown in the figure, the degradation rates of Examples 1-3 are 56.2%, 57.1%, and 56.8%, respectively, while those of Comparative Examples 1-3 are 38.2%, 41.1%, and 34.7%, respectively.
综合图1、图2和图3可见加入多巴胺改性微晶纤维素、聚醚醚酮/羟基磷灰石复合材料、壳聚糖/纳米二氧化硅气凝胶对于聚乙烯塑料的力学性能和降解性有显著的提升。From Figures 1, 2 and 3, it can be seen that the addition of dopamine-modified microcrystalline cellulose, polyetheretherketone/hydroxyapatite composite materials, and chitosan/nano-silica aerogel significantly improves the mechanical properties and degradability of polyethylene plastics.
图4为本发明实施例1所制备的可降解复合聚乙烯塑料的扫描电镜图。FIG. 4 is a scanning electron microscope image of the degradable composite polyethylene plastic prepared in Example 1 of the present invention.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型。While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention.
以上对本发明及其实施方式进行了描述，这种描述没有限制性，附图中所示的也只是本发明的实施方式之一，实际的应用并不局限于此。总而言之如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的方式及实施例，均应属于本发明的保护范围。The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.
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| CN202410188206.5ACN118006019B (en) | 2024-02-20 | 2024-02-20 | A kind of degradable composite polyethylene plastic and preparation method thereof |
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| CN119264589A (en)* | 2024-12-10 | 2025-01-07 | 安徽紫金新材料科技股份有限公司 | A method for preparing biodegradable polyvinyl alcohol resin packaging material |
| CN119798933A (en)* | 2024-12-16 | 2025-04-11 | 江门江东华普塑料容器有限公司 | Degradable plastic, container made of the same and preparation method thereof |
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| WO2012004637A1 (en)* | 2010-07-09 | 2012-01-12 | Indian Institute Of Technology Kanpur | Hydroxyapatite poly(etheretherketone) nanocomposities and method of manufacturing same |
| CN107556516A (en)* | 2017-07-27 | 2018-01-09 | 广西中烟工业有限责任公司 | A kind of Nano-meter SiO_22The preparation method of chitosan three-dimensional gel and the application in cigarette filter |
| CN110152068A (en)* | 2019-05-31 | 2019-08-23 | 武汉理工大学 | A kind of polyether ether ketone/nanometer hydroxyapatite composite material and its preparation method and application |
| CN114539639A (en)* | 2022-03-24 | 2022-05-27 | 江苏金世缘乳胶制品股份有限公司 | A kind of preparation method of dopamine-modified microcrystalline cellulose reinforced natural rubber |
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012004637A1 (en)* | 2010-07-09 | 2012-01-12 | Indian Institute Of Technology Kanpur | Hydroxyapatite poly(etheretherketone) nanocomposities and method of manufacturing same |
| CN107556516A (en)* | 2017-07-27 | 2018-01-09 | 广西中烟工业有限责任公司 | A kind of Nano-meter SiO_22The preparation method of chitosan three-dimensional gel and the application in cigarette filter |
| CN110152068A (en)* | 2019-05-31 | 2019-08-23 | 武汉理工大学 | A kind of polyether ether ketone/nanometer hydroxyapatite composite material and its preparation method and application |
| CN114539639A (en)* | 2022-03-24 | 2022-05-27 | 江苏金世缘乳胶制品股份有限公司 | A kind of preparation method of dopamine-modified microcrystalline cellulose reinforced natural rubber |
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| CN119264589A (en)* | 2024-12-10 | 2025-01-07 | 安徽紫金新材料科技股份有限公司 | A method for preparing biodegradable polyvinyl alcohol resin packaging material |
| CN119798933A (en)* | 2024-12-16 | 2025-04-11 | 江门江东华普塑料容器有限公司 | Degradable plastic, container made of the same and preparation method thereof |
| CN119798933B (en)* | 2024-12-16 | 2025-08-12 | 江门江东华普塑料容器有限公司 | Degradable plastic, container made of the same and preparation method thereof |
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