技术领域technical field
本发明涉及木塑复合材料技术领域，尤其涉及一种环保可降解木塑复合材料及其制备方法。The invention relates to the technical field of wood-plastic composite materials, in particular to an environment-friendly degradable wood-plastic composite material and a preparation method thereof.
背景技术Background technique
木塑复合材料，是指以低值或废弃的生物质材料，如木粉、稻壳、秸秆粉等为主原料，利用高分子界面化学原理和塑料填充改性的特点，配混一定比例的塑料基料，经专业工艺处理，加工成型的一种可循环加工利用的新型材料。它同时具备了天然植物与合成塑料两种基础材料的多重优点，在建材、家具和物流包装等行业得到日益广泛的应用。Wood-plastic composite materials refer to low-value or waste biomass materials, such as wood powder, rice husk, straw powder, etc. Plastic base material, processed by professional technology, is a new type of material that can be recycled and processed. It has the multiple advantages of two basic materials, natural plants and synthetic plastics, and is increasingly widely used in industries such as building materials, furniture, and logistics packaging.
但是，由于传统塑料基材的不可降解性，木塑材料制品废弃后会带来比较多的环境污染问题。However, due to the non-degradability of traditional plastic substrates, wood-plastic products will cause more environmental pollution problems after they are discarded.
发明内容Contents of the invention
有鉴于此，本申请的目的在于提供一种环保可降解木塑复合材料及其制备方法，本发明提供的木塑复合材料具有良好的使用性能，同时环保可降解。In view of this, the purpose of this application is to provide an environmentally friendly and degradable wood-plastic composite material and its preparation method. The wood-plastic composite material provided by the present invention has good performance and is environmentally friendly and degradable.
本发明提供一种环保可降解木塑复合材料，包括：The invention provides an environmentally friendly degradable wood-plastic composite material, comprising:
非降解塑料基料、秸秆粉和氧化-生物双降解添加剂；Non-degradable plastic base materials, straw powder and oxidative-biodegradable additives;
所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)；The mass ratio of the non-degradable plastic base material and straw powder is (90-20): (10-80);
所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％。The mass of the oxidative-biological double degradation additive accounts for 1% to 20% of the total mass of the non-degradable plastic base material and straw powder.
优选地，所述非降解塑料基料和秸秆粉的质量比为(80～30)：(20～70)。Preferably, the mass ratio of the non-degradable plastic base material to straw powder is (80-30): (20-70).
优选地，所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的2％～15％。Preferably, the mass of the oxidative-biological double degradation additive accounts for 2%-15% of the total mass of the non-degradable plastic base material and straw powder.
优选地，所述非降解塑料基料选自聚乙烯、聚丙烯、聚氯乙烯和聚苯乙烯中的一种或多种。Preferably, the non-degradable plastic base material is selected from one or more of polyethylene, polypropylene, polyvinyl chloride and polystyrene.
优选地，所述秸秆粉选自小麦秸秆粉、玉米秸秆粉和水稻秸秆粉中的一种或多种。Preferably, the straw powder is selected from one or more of wheat straw powder, corn straw powder and rice straw powder.
优选地，所述氧化-生物双降解添加剂包括纳米过渡金属无机物、过渡金属盐、多元有机酸和塑料基体。Preferably, the oxidation-biodegradation additive includes nano-transition metal inorganic substances, transition metal salts, polybasic organic acids and plastic matrix.
优选地，所述氧化-生物双降解添加剂按照以下方法制得：Preferably, the oxidation-biodegradation additive is prepared according to the following method:
将过渡金属盐和多元有机酸及含过渡金属的前驱体在溶剂中混合，得到混合液；Mixing transition metal salts, polybasic organic acids and transition metal-containing precursors in a solvent to obtain a mixed solution;
将所述混合液制成反胶束溶液后，依次进行保温、陈化和分离，得到多元纳米粒子；After the mixed solution is made into a reverse micellar solution, heat preservation, aging and separation are carried out in sequence to obtain multi-component nanoparticles;
将所述多元纳米粒子和塑料基体混合后进行挤出造粒，得到氧化-生物双降解添加剂。The multi-component nanometer particles are mixed with the plastic matrix and then extruded and granulated to obtain the oxidation-biodegradation additive.
本发明提供一种环保可降解木塑复合材料的制备方法，包括以下步骤：The invention provides a method for preparing an environmentally friendly degradable wood-plastic composite material, comprising the following steps:
将非降解塑料基料和秸秆粉及氧化-生物双降解添加剂共混后，进行成型加工，得到环保可降解木塑复合材料；After blending the non-degradable plastic base material with straw powder and oxidative-biological dual-degradation additives, molding processing is carried out to obtain environmentally friendly and degradable wood-plastic composite materials;
所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)；The mass ratio of the non-degradable plastic base material and straw powder is (90-20): (10-80);
所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％。The mass of the oxidative-biological double degradation additive accounts for 1% to 20% of the total mass of the non-degradable plastic base material and straw powder.
优选地，具体为：将非降解塑料基料和氧化-生物双降解添加剂混合，得到混合料；Preferably, specifically: mixing the non-degradable plastic base material with the oxidative-biological double-degradation additive to obtain a mixture;
将所述混合料与秸秆粉混合后，进行成型加工，得到环保可降解木塑复合材料。After the mixed material is mixed with the straw powder, molding processing is carried out to obtain an environment-friendly and degradable wood-plastic composite material.
优选地，所述成型加工的温度为150℃～250℃，所述成型加工的时间为10min～1h。Preferably, the temperature of the forming process is 150° C. to 250° C., and the time of the forming process is 10 minutes to 1 hour.
与现有技术相比，本发明提供的木塑复合材料中的塑料成分为普通的非降解塑料基料，木质成分以秸秆粉这种农作物植物纤维为主原料，所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)；本发明利用氧化-生物双降解技术，在木塑复合材料中加入少量氧化-生物双降解添加剂，所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％，制成一种新型环保可降解的秸秆木塑复合材料。本发明添加了一定量的氧化-生物双降解添加剂，使用氧化-生物双降解塑料技术，使木塑复合材料兼具氧化降解和生物降解的能力，且其降解时间可控；当木塑复合材料达到使用寿命后可在自然环境中进行氧化-生物降解，从而不会对环境造成污染。同时，本发明所述木塑复合材料在使用中具有与普通木塑复合材料相同的理化特性和使用性能，如吸水率低，不易变形开裂，防虫蛀霉变；具有机械性能高、质轻、防潮、耐酸碱、耐腐蚀和便于清洗等特点，可在很多领域替代原木、塑料和铝合金等使用，市场应用前景广泛。Compared with the prior art, the plastic component in the wood-plastic composite material provided by the present invention is an ordinary non-degradable plastic base material, and the wood component is mainly made of crop plant fiber such as straw powder. The non-degradable plastic base material and The mass ratio of the straw powder is (90-20): (10-80); the present invention utilizes the oxidation-biodegradation technology to add a small amount of oxidation-biodegradation additive to the wood-plastic composite material, and the oxidation-biodegradation The mass of the additive accounts for 1% to 20% of the total mass of the non-degradable plastic base material and the straw powder, and a new environment-friendly and degradable straw-wood-plastic composite material is produced. The present invention adds a certain amount of oxidation-biodegradation additives, and uses oxidation-biodegradation plastic technology, so that the wood-plastic composite material has the ability of both oxidative degradation and biodegradation, and its degradation time is controllable; when the wood-plastic composite material After reaching the service life, it can be oxidized-biodegraded in the natural environment, so that it will not pollute the environment. At the same time, the wood-plastic composite material of the present invention has the same physical and chemical properties and performance as ordinary wood-plastic composite materials in use, such as low water absorption, not easy to deform and crack, and prevents moth and mildew; it has high mechanical properties, light weight, Moisture-proof, acid-alkali-resistant, corrosion-resistant and easy to clean, it can replace logs, plastics and aluminum alloys in many fields, and has a broad market application prospect.
附图说明Description of drawings
图1为本发明实施例1制备的木塑复合材料样品降解前后的对比结果；Fig. 1 is the comparison result before and after degradation of the wood-plastic composite material sample prepared in Example 1 of the present invention;
图2为本发明实施例2制备的木塑复合材料样品降解前后的对比结果。Fig. 2 is a comparison result before and after degradation of the wood-plastic composite material sample prepared in Example 2 of the present invention.
具体实施方式detailed description
下面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 following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提供了一种环保可降解木塑复合材料，包括：The invention provides an environmentally friendly degradable wood-plastic composite material, comprising:
非降解塑料基料、秸秆粉和氧化-生物双降解添加剂；Non-degradable plastic base materials, straw powder and oxidative-biodegradable additives;
所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)；The mass ratio of the non-degradable plastic base material and straw powder is (90-20): (10-80);
所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％。The mass of the oxidative-biological double degradation additive accounts for 1% to 20% of the total mass of the non-degradable plastic base material and straw powder.
本发明提供的木塑复合材料具有普通非降解木塑复合材料所拥有的优点，如良好的加工性能、良好的强度性能、耐水和耐腐蚀性能等；并且所述木塑复合材料在达到使用寿命后可在自然环境中进行氧化-生物降解，从根本上解决了塑料污染的环保问题。The wood-plastic composite material provided by the present invention has the advantages of ordinary non-degradable wood-plastic composite materials, such as good processing performance, good strength performance, water resistance and corrosion resistance, etc.; and the wood-plastic composite material reaches the service life After that, it can be oxidized and biodegraded in the natural environment, which fundamentally solves the environmental protection problem of plastic pollution.
本发明提供的木塑复合材料包括非降解塑料基料，其属于不能被自然降解的塑料部分。所述非降解塑料基料优选自聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)和聚苯乙烯(PS)中的一种或多种，更优选为聚丙烯(PP)或聚乙烯(PE)，其中，常用的聚乙烯包括高密度聚乙烯(HDPE)和低密度聚乙烯(LDPE)。本发明对所述非降解塑料基料的来源没有特殊限制，可以采用市售产品，如常用聚丙烯材料，数均分子量范围可在5万～30万，优选为8万～15万，熔点为160℃～170℃；如常用聚乙烯材料，数均分子量范围可在5万～30万，优选为5万～15万，熔点为90℃～130℃。The wood-plastic composite material provided by the invention includes a non-degradable plastic base material, which belongs to the plastic part that cannot be naturally degraded. The non-degradable plastic base material is preferably selected from one or more of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) and polystyrene (PS), more preferably polypropylene (PP) Or polyethylene (PE), wherein commonly used polyethylene includes high-density polyethylene (HDPE) and low-density polyethylene (LDPE). The present invention has no special restrictions on the source of the non-degradable plastic base material, and commercially available products can be used, such as commonly used polypropylene materials. 160°C to 170°C; if commonly used polyethylene material, the number average molecular weight can range from 50,000 to 300,000, preferably 50,000 to 150,000, and the melting point is 90°C to 130°C.
本发明提供的木塑复合材料包括秸秆粉，其为木质成分。本发明所述的秸秆是成熟农作物茎叶部分的总称，而秸秆粉是秸秆经干燥、粉碎等处理形成的粉状物质。在本发明中，所述秸秆粉优选自小麦秸秆粉、玉米秸秆粉和水稻秸秆粉中的一种或多种，更优选为小麦秸秆粉。所述秸秆粉为本领域技术人员所熟知的，可以采用市售产品；本发明所述秸秆粉的粒度可为40～1000目，在本发明的实施例中，所述秸秆粉为过40目筛的秸秆粉。The wood-plastic composite material provided by the invention includes straw powder, which is a wood component. The straw in the present invention is a general term for the stems and leaves of mature crops, and the straw powder is a powdery substance formed by drying and crushing the straw. In the present invention, the straw powder is preferably selected from one or more of wheat straw powder, corn straw powder and rice straw powder, more preferably wheat straw powder. The straw powder is well known to those skilled in the art, and commercially available products can be used; the particle size of the straw powder in the present invention can be 40 to 1000 mesh, and in the embodiments of the present invention, the straw powder is over 40 mesh Sift the straw powder.
在本发明中，所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)，优选为(80～30)：(20～70)。在本发明的一个实施例中，所述非降解塑料基料和秸秆粉的质量比为60:40。在本发明的一个实施例中，所述非降解塑料基料为PP，所述秸秆粉为小麦秸秆粉，两者的质量比为60:40。In the present invention, the mass ratio of the non-degradable plastic base material to straw powder is (90-20):(10-80), preferably (80-30):(20-70). In one embodiment of the present invention, the mass ratio of the non-degradable plastic base material to straw powder is 60:40. In one embodiment of the present invention, the non-degradable plastic base material is PP, and the straw powder is wheat straw powder, and the mass ratio of the two is 60:40.
本发明提供的木塑复合材料包括氧化-生物双降解添加剂；本发明所谓的氧化-生物双降解是在光、热或氧等环境条件中通过氧化降解，使普通塑料如聚烯烃的分子量降低到1万以下，然后小分子量的聚合物链段被微生物利用并逐步进行生物降解。在本发明中，所述氧化-生物双降解添加剂能使木塑复合材料中不能自然降解的塑料部分实现自然降解，最终降解成二氧化碳和水，从而从根本上解决了现有木塑复合材料“塑料污染”的问题。The wood-plastic composite material provided by the present invention includes an oxidative-biological double degradation additive; the so-called oxidative-biological double degradation of the present invention is to reduce the molecular weight of common plastics such as polyolefins to Below 10,000, then the small molecular weight polymer segments are utilized by microorganisms and gradually biodegrade. In the present invention, the oxidation-biodegradation additive can make the non-naturally degradable plastic part in the wood-plastic composite material realize natural degradation, and finally degrade into carbon dioxide and water, thereby fundamentally solving the " plastic pollution”.
在本发明中，所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％，优选为2％～15％，更优选为3％～10％。在本发明中，每10g降解母料的颗粒数目可在200～600个之间。在本发明的一个实施例中，所述氧化-生物双降解添加剂为氧化-生物双降解聚丙烯母粒(EBPmas-PP)或氧化-生物双降解聚乙烯母粒(EBPmas-PE)。In the present invention, the mass of the oxidation-biodegradation additive accounts for 1%-20% of the total mass of the non-degradable plastic base material and straw powder, preferably 2%-15%, more preferably 3%-10%. In the present invention, the number of particles per 10 g of the degradation masterbatch can be between 200 and 600. In one embodiment of the present invention, the oxidative-biodegradable additive is oxidative-biodegradable polypropylene masterbatch (EBPmas-PP) or oxidative-biodegradable polyethylene masterbatch (EBPmas-PE).
在本发明中，所述氧化-生物双降解添加剂优选包括纳米过渡金属无机物、过渡金属盐、多元有机酸和塑料基体。这种氧化-生物双降解添加剂是纳米高分子多元双降解添加剂，本发明优选采用少量这种添加剂混入秸秆木塑复合材料中，能取得更好的降解效果。In the present invention, the oxidative-biological double degradation additive preferably includes nano-transition metal inorganic substances, transition metal salts, polybasic organic acids and plastic matrix. The oxidative-biological double-degradation additive is a nano-polymer multi-component double-degradation additive. In the present invention, a small amount of this additive is preferably mixed into the straw-wood-plastic composite material to achieve better degradation effect.
在本发明的实施例中，所述氧化-生物双降解添加剂包括纳米过渡金属无机物，其为紫外光催化降解成分，颗粒直径可在5nm～900nm之间。所述纳米过渡金属无机物优选自纳米过渡金属氧化物或纳米过渡金属硫化物，更优选为纳米TiO2、纳米ZnO、纳米ZnS、纳米CdS和纳米PbS中的一种无机物或多种形成的混合物或复合物(如TixZnyO2x+y，其中的x、y和2x+y为原子比)，最优选为纳米TiO2。所述氧化-生物双降解添加剂优选包括0.1wt％～10wt％的纳米过渡金属无机物，更优选包括1wt％～8wt％的纳米过渡金属无机物。In an embodiment of the present invention, the oxidative-biological double-degradation additive includes nano-transition metal inorganic substances, which are ultraviolet photocatalytic degradation components, and the particle diameter may be between 5nm and 900nm. The nano-transition metal inorganic substance is preferably selected from nano-transition metal oxides or nano-transition metal sulfides, more preferably one or more inorganic substances in nano-TiO2 , nano-ZnO, nano-ZnS, nano-CdS and nano-PbS The mixture or compound (such as Tix Zny O2x+y, where x, y and 2x+y are atomic ratios), is most preferably nano-TiO2 . The oxidation-biodegradation additive preferably includes 0.1wt%-10wt% of nano-transition metal inorganic substances, more preferably 1wt%-8wt% of nano-transition metal inorganic substances.
所述氧化-生物双降解添加剂可包括过渡金属盐，其为可见光催化氧化降解和热催化氧化降解成分。所述过渡金属盐中的过渡金属优选自钴、铁、钒、锰、铈或锌；即，所述过渡金属盐包括铁、钴、钒、锰、铈、锌等的水溶性有机酸盐或无机酸盐。在本发明的实施例中，所述过渡金属盐可选自铁、钴、钒、锰、铈或锌的甲酸盐、乙酸盐、硝酸盐、硫酸盐、盐酸盐或乙酰丙酮盐，如甲酸铁、乙酸铁、硝酸铁、硝酸钴、硫酸铁、硫酸二铵铁、乙酰丙酮铁、氯化铁等。所述氧化-生物双降解添加剂优选包括1wt％～10wt％的过渡金属盐，更优选包括3wt％～8wt％的过渡金属盐。The oxidative-biodegradable additive may include transition metal salts, which are components of visible light-catalyzed oxidative degradation and thermocatalytic oxidative degradation. The transition metal in the transition metal salt is preferably selected from cobalt, iron, vanadium, manganese, cerium or zinc; that is, the transition metal salt includes water-soluble organic acid salts of iron, cobalt, vanadium, manganese, cerium, zinc, etc. or Inorganic acid salt. In an embodiment of the present invention, the transition metal salt may be selected from formate, acetate, nitrate, sulfate, hydrochloride or acetylacetonate of iron, cobalt, vanadium, manganese, cerium or zinc, Such as ferric formate, ferric acetate, ferric nitrate, cobalt nitrate, ferric sulfate, ferric diammonium sulfate, ferric acetylacetonate, ferric chloride, etc. The oxidative-biodegradable additive preferably includes 1wt%-10wt% transition metal salt, more preferably 3wt%-8wt% transition metal salt.
所述氧化-生物双降解添加剂可包括多元有机酸，其为助氧化降解成分，用量可为添加剂总重量的1％～10％，优选为3％～8％。所述多元有机酸优选为1,3-丙二胺四乙酸(PDTA)、酒石酸、富马酸、苹果酸和柠檬酸中的一种或多种，更优选为柠檬酸。本发明对所述多元有机酸等的来源没有特殊限制，采用市售产品即可。The oxidative-biological dual degradation additive may include polybasic organic acid, which is an oxidative degradation-promoting component, and the dosage may be 1%-10% of the total weight of the additive, preferably 3%-8%. The polybasic organic acid is preferably one or more of 1,3-propylenediaminetetraacetic acid (PDTA), tartaric acid, fumaric acid, malic acid and citric acid, more preferably citric acid. In the present invention, there is no special limitation on the source of the polybasic organic acid, etc., and commercially available products can be used.
所述氧化-生物双降解添加剂包括余量的塑料基体，优选自聚烯烃、聚苯胺或聚酯，更优选为聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、乙烯-醋酸乙烯共聚物、丙烯腈-丁二烯-苯乙烯树脂、聚对苯二甲酸乙二酯和聚对苯二甲酸丁二酯中的一种或多种，最优选为聚乙烯、聚丙烯、聚苯乙烯或聚氯乙烯。本发明优选采用含有聚烯烃的氧化-生物双降解添加剂，其与木塑复合材料的相容性更好，利于应用。本发明对所述塑料基体的来源等没有特殊限制，采用市售产品即可。The oxidative-biological double-degradation additive includes the rest of the plastic matrix, preferably from polyolefin, polyaniline or polyester, more preferably polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer, One or more of acrylonitrile-butadiene-styrene resin, polyethylene terephthalate and polybutylene terephthalate, most preferably polyethylene, polypropylene, polystyrene or poly vinyl chloride. The present invention preferably adopts the oxidation-biodegradation additive containing polyolefin, which has better compatibility with the wood-plastic composite material and is favorable for application. In the present invention, there is no special limitation on the source of the plastic matrix, and commercially available products can be used.
所述氧化-生物双降解添加剂还可包括表面活性剂；其优选包括1wt％～10wt％的表面活性剂，更优选包括3wt％～5wt％的表面活性剂。所述表面活性剂包括但不限于十六烷基三甲基溴化铵(CTAB)、十六烷基三甲基氯化铵(CTAC)、十二烷基三甲基溴化铵(DTAB)、十二烷基三甲基氯化铵(DTAC)、十二烷基硫酸钠(SDS)、琥珀双异辛醋磺酸钠(AOT)、十二烷基苯磺酸钠(DBS)、脂肪醇聚氧乙烯醚(AE)和烷基酚聚氧乙烯醚(APE)。在本发明的一个实施例中，所述氧化-生物双降解添加剂包括十六烷基三甲基溴化胺。The oxidative-biodegradable additive may also include a surfactant; it preferably includes 1 wt% to 10 wt% of a surfactant, more preferably includes 3 wt% to 5 wt% of a surfactant. The surfactant includes but not limited to cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), dodecyltrimethylammonium bromide (DTAB) , Dodecyltrimethylammonium Chloride (DTAC), Sodium Dodecyl Sulfate (SDS), Sodium Succinic Diisooctylsulfonate (AOT), Sodium Dodecylbenzenesulfonate (DBS), Fatty Alcohol ethoxylates (AE) and alkylphenol ethoxylates (APE). In one embodiment of the present invention, the oxidative-biodegradable additive includes cetyltrimethylammonium bromide.
本发明实施例可将上述纳米过渡金属无机物、过渡金属盐、多元有机酸和塑料基体混合，经挤出造粒，得到氧化-生物双降解添加剂。其中，所述混合优选在高速搅拌机中进行，搅拌的时间一般为1分钟～3分钟。本发明实施例可采用双螺杆造粒机组进行挤出造粒；各挤出区段的温度一般为50℃～250℃，挤出转数可为25转/分～450转/分。In the embodiment of the present invention, the above-mentioned nano-transition metal inorganic substance, transition metal salt, polybasic organic acid and plastic matrix can be mixed, extruded and granulated to obtain an oxidation-biodegradation additive. Wherein, the mixing is preferably carried out in a high-speed mixer, and the stirring time is generally 1 minute to 3 minutes. In the embodiment of the present invention, a twin-screw granulator can be used for extrusion granulation; the temperature of each extrusion section is generally 50° C. to 250° C., and the extrusion rotation speed can be 25 rpm to 450 rpm.
本发明对所述氧化-生物双降解添加剂的来源没有特殊限制，可以采用市售产品，但优选按照以下方法制得：将过渡金属盐和多元有机酸及含过渡金属的前驱体在溶剂中混合，得到混合液；将所述混合液制成反胶束溶液后，依次进行保温、陈化和分离，得到多元纳米粒子；将所述多元纳米粒子和塑料基体混合后进行挤出造粒，得到氧化-生物双降解添加剂。In the present invention, there is no special limitation on the source of the oxidation-biodegradation additive, and commercially available products can be used, but it is preferably prepared according to the following method: mixing transition metal salts, polybasic organic acids and precursors containing transition metals in a solvent , to obtain a mixed solution; after the mixed solution is made into a reverse micellar solution, heat preservation, aging and separation are carried out successively to obtain multi-component nanoparticles; after the multi-component nanoparticles and plastic matrix are mixed, extrusion granulation is obtained to obtain Oxidative-biodegradable additive.
本发明实施例可将过渡金属盐和多元有机酸及含过渡金属的前驱体水溶液混合，然后将得到的混合液与含表面活性剂的有机溶液混合，形成反胶束体系。在上述实施例中，所述过渡金属盐和多元有机酸的内容与前文所述内容一致，在此不再赘述。所述含过渡金属的前驱体即能通过反应制得过渡金属无机物的物质，可选自水溶性过渡金属盐，包括TiCl4、Ti(NO3)4、Ti(SO4)2、TiOSO4、ZnCl2、Zn(NO3)2、ZnSO4、CdCl2、Cd(NO3)2、CdSO4、PbCl2、Pd(NO3)2或PbSO4。In the embodiment of the present invention, a transition metal salt, a polybasic organic acid and an aqueous precursor solution containing a transition metal can be mixed, and then the obtained mixed solution is mixed with an organic solution containing a surfactant to form a reverse micellar system. In the above embodiments, the content of the transition metal salt and polybasic organic acid is the same as that described above, and will not be repeated here. The transition metal-containing precursor is a substance capable of producing transition metal inorganic substances through reaction, which can be selected from water-soluble transition metal salts, including TiCl4 , Ti(NO3 )4 , Ti(SO4 )2 , TiOSO4 , ZnCl2 , Zn(NO3 )2 , ZnSO4 , CdCl2 , Cd(NO3 )2 , CdSO4 , PbCl2 , Pd(NO3 )2 or PbSO4 .
本发明实施例采用含表面活性剂的有机溶液，使混合液制成反胶束溶液。所述表面活性剂的内容与前文所述内容一致；所述含表面活性剂的有机溶液中有机溶剂为常用的即可，如正己烷、甲苯、环己烷、异辛烷和煤油中的一种或多种，优选为煤油；而其中表面活性剂的浓度可为0.02mol/L～1.0mol/L，优选为0.1mol/L～0.8mol/L。在形成的反胶束混合液中，所述过渡金属盐中过渡金属离子的溶度可为0.01mol/L～200mol/L，优选为1mol/L～100mol/L；所述多元有机酸的浓度可为0.01mol/L～200mol/L，优选为1mol/L～100mol/L；所述含过渡金属的前驱体的浓度可为0.01mol/L～200mol/L，优选为1mol/L～100mol/L。In the embodiment of the present invention, an organic solution containing a surfactant is used to make the mixed solution into a reverse micellar solution. The content of the surfactant is consistent with the content described above; the organic solvent in the organic solution containing the surfactant is commonly used, such as one of n-hexane, toluene, hexanaphthene, isooctane and kerosene. One or more kinds, preferably kerosene; and the concentration of the surfactant can be 0.02mol/L-1.0mol/L, preferably 0.1mol/L-0.8mol/L. In the formed reverse micelles mixture, the solubility of the transition metal ion in the transition metal salt can be 0.01mol/L to 200mol/L, preferably 1mol/L to 100mol/L; the concentration of the polybasic organic acid It can be 0.01mol/L～200mol/L, preferably 1mol/L～100mol/L; the concentration of the transition metal-containing precursor can be 0.01mol/L～200mol/L, preferably 1mol/L～100mol/L L.
得到反应胶束溶液后，本发明实施例可将其在一定温度保温一定时间，然后进行陈化，得到含多元纳米粒子的悬浊液。在上述实施例中，所述保温的温度可为80℃～90℃，优选为90℃；所述保温的时间可为6h～8h，优选为6h。所述陈化可在高压反应釜中且有惰性气体保护的条件下进行；所述陈化的温度可为140℃～150℃，优选为145℃；所述陈化的时间可为40h～50h，优选为45h～48h，更优选为48h。After the reaction micelle solution is obtained, in the embodiment of the present invention, it can be kept at a certain temperature for a certain period of time, and then aged to obtain a suspension containing multi-component nanoparticles. In the above embodiment, the temperature of the heat preservation may be 80°C-90°C, preferably 90°C; the time of heat preservation may be 6h-8h, preferably 6h. The aging can be carried out in a high-pressure reactor under the protection of an inert gas; the aging temperature can be 140°C to 150°C, preferably 145°C; the aging time can be 40h to 50h , preferably 45h to 48h, more preferably 48h.
得到含多元纳米粒子的悬浊液后，本发明实施例可将其依次进行离心分离、干燥，得到多元纳米粒子粉末。其中，所述离心分离和干燥为本领域技术人员熟知的技术手段，本发明没有特殊限制。After the suspension containing multi-component nanoparticles is obtained, in the embodiment of the present invention, it can be centrifuged and dried in sequence to obtain a multi-component nano particle powder. Wherein, the centrifugal separation and drying are technical means well known to those skilled in the art, and the present invention is not particularly limited.
本发明实施例将得到的多元纳米粒子粉末和塑料基体混合后，进行挤出造粒，得到氧化-生物双降解添加剂。其中，所述混合优选在高速搅拌机中进行，搅拌的时间一般为1分钟～3分钟。本发明实施例可采用双螺杆造粒机组进行挤出造粒；各挤出区段的温度一般为50℃～250℃，挤出转数可为25转/分～450转/分。In the embodiment of the present invention, after mixing the obtained multi-component nanoparticle powder with a plastic matrix, extrusion granulation is performed to obtain an oxidation-biodegradation additive. Wherein, the mixing is preferably carried out in a high-speed mixer, and the stirring time is generally 1 minute to 3 minutes. In the embodiment of the present invention, a twin-screw granulator can be used for extrusion granulation; the temperature of each extrusion section is generally 50° C. to 250° C., and the extrusion rotation speed can be 25 rpm to 450 rpm.
另外，本发明实施例还可将过渡金属盐和多元有机酸水溶液混合，然后将得到的混合液与含表面活性剂的有机溶液混合，再将形成的反胶束体系与含过渡金属的前驱体有机溶液混合，得到反应胶束溶液。在本实施例中，所述含过渡金属的前驱体可选自油溶性过渡金属有机物，包括Ti(OC4H9)4、钛酸四异丙酯、异辛醇钛、异丙基三油酸酰氧基钛酸酯、乙酰丙酮氧化钛、钛酸四乙酯、钛酸四丙酯、四叔丁基钛酸酯或三异硬脂酸钛酸异丙酯。所述含过渡金属的前驱体有机溶液中有机溶剂为常用的即可，如正己烷、甲苯、环己烷、异辛烷和煤油中的一种或多种，优选为煤油。本发明实施例将形成的反胶束体系与含过渡金属的前驱体有机溶液混合，优选搅拌0.5h～5h、更优选搅拌1h～4h。In addition, in the embodiment of the present invention, the transition metal salt and the polybasic organic acid aqueous solution can also be mixed, and then the obtained mixed solution is mixed with an organic solution containing a surfactant, and then the formed reverse micelle system is mixed with a transition metal-containing precursor The organic solutions are mixed to obtain a reaction micellar solution. In this embodiment, the transition metal-containing precursor can be selected from oil-soluble transition metal organics, including Ti(OC4 H9 )4 , tetraisopropyl titanate, titanium isooctoxide, isopropyl trioil Acyloxytitanate, titanium oxide acetylacetonate, tetraethyl titanate, tetrapropyl titanate, tetra-tert-butyl titanate, or isopropyl titanate triisostearate. The organic solvent in the transition metal-containing precursor organic solution is commonly used, such as one or more of n-hexane, toluene, cyclohexane, isooctane and kerosene, preferably kerosene. In the embodiment of the present invention, the formed reverse micelle system is mixed with the transition metal-containing precursor organic solution, preferably stirred for 0.5 h to 5 h, more preferably stirred for 1 h to 4 h.
在本发明实施例这种方法中，其余步骤可如前所述。即，将最后制成的反胶束溶液依次进行保温、陈化和分离，得到多元纳米粒子；将所述多元纳米粒子和塑料基体混合后进行挤出造粒，得到氧化-生物双降解添加剂。In this method of the embodiment of the present invention, other steps may be as described above. That is, heat preservation, aging and separation of the finally prepared reverse micelles solution are performed sequentially to obtain multi-component nanoparticles; the multi-component nanoparticles are mixed with a plastic matrix and then extruded and granulated to obtain an oxidative-biodegradable additive.
本发明实施例制备得到的氧化-生物双降解添加剂可以称为环境普适性降解塑料母粒(降解塑料母粒)，这种氧化-生物双降解母粒具有纳米高分子多元复合结构，添加到木塑复合材料中的降解效果更好，复合材料的使用性能也不受影响。本发明实施例可以采用山东天壮环保科技有限公司的型号为EBPmas-PP-1502、EBPmas-PP-1501或EBPmas-PE-1501的氧化-生物双降解母粒。The oxidation-biodegradation additive prepared in the embodiment of the present invention can be called environmental universal degradable plastic masterbatch (degradable plastic masterbatch). The degradation effect in the wood-plastic composite material is better, and the performance of the composite material is not affected. The embodiment of the present invention can use the oxidation-biodegradation masterbatch of Shandong Tianzhuang Environmental Protection Technology Co., Ltd. whose model is EBPmas-PP-1502, EBPmas-PP-1501 or EBPmas-PE-1501.
除了氧化-生物双降解添加剂，本发明提供的木塑复合材料优选还包括抗氧剂。根据性能需求不同，所述木塑复合材料可以不加抗氧剂，也可以添加少量抗氧剂。在本发明的一个实施例中，所述木塑复合材料包括抗氧剂；所述抗氧剂的质量占非降解塑料基料和秸秆粉总质量的0.1％～10％，优选为0.5％～5％。本发明对所述抗氧剂没有特殊限制，如可以采用受阻酚类抗氧剂BHT、1010和1076，或采用受阻胺类抗氧剂944和622，还可以采用抗氧剂168、抗氧剂215和抗氧剂225等。此外，本发明提供的木塑复合材料也可以包括用于普通木塑复合材料的一些添加剂；本发明对此没有特殊限制。In addition to the oxidative-biodegradable additive, the wood-plastic composite material provided by the present invention preferably further includes an antioxidant. According to different performance requirements, the wood-plastic composite material may not be added with an antioxidant, or may be added with a small amount of antioxidant. In one embodiment of the present invention, the wood-plastic composite material includes an antioxidant; the quality of the antioxidant accounts for 0.1% to 10% of the total mass of the non-degradable plastic base material and straw powder, preferably 0.5% to 5%. The present invention has no special restrictions on the antioxidant, such as hindered phenolic antioxidants BHT, 1010 and 1076, or hindered amine antioxidants 944 and 622, antioxidant 168, antioxidant 215 and antioxidant 225 etc. In addition, the wood-plastic composite material provided by the present invention may also include some additives used in ordinary wood-plastic composite materials; the present invention has no special limitation on this.
相应的，本发明提供了一种环保可降解木塑复合材料的制备方法，包括以下步骤：Correspondingly, the present invention provides a method for preparing an environmentally friendly degradable wood-plastic composite material, comprising the following steps:
将非降解塑料基料和秸秆粉及氧化-生物双降解添加剂共混后，进行成型加工，得到环保可降解木塑复合材料；After blending the non-degradable plastic base material with straw powder and oxidative-biological dual-degradation additives, molding processing is carried out to obtain environmentally friendly and degradable wood-plastic composite materials;
所述非降解塑料基料和秸秆粉的质量比为(90～20)：(10～80)；The mass ratio of the non-degradable plastic base material and straw powder is (90-20): (10-80);
所述氧化-生物双降解添加剂的质量占非降解塑料基料和秸秆粉总质量的1％～20％。The mass of the oxidative-biological double degradation additive accounts for 1% to 20% of the total mass of the non-degradable plastic base material and straw powder.
本发明实施例将上述配比的非降解塑料基料、秸秆粉和氧化-生物双降解添加剂等共混后，进行成型加工，制得可降解秸秆木塑复合材料。本发明优选具体为：将非降解塑料基料和氧化-生物双降解添加剂混合，得到混合料；将所述混合料与秸秆粉混合后，进行成型加工，得到环保可降解木塑复合材料。In the embodiment of the present invention, after blending the above-mentioned non-degradable plastic base material, straw powder and oxidation-biodegradation additives, etc., molding processing is carried out to obtain a degradable straw-wood-plastic composite material. The present invention preferably specifically comprises: mixing a non-degradable plastic base material with an oxidative-biological double-degradation additive to obtain a mixture; mixing the mixture with straw powder, and performing molding processing to obtain an environmentally friendly and degradable wood-plastic composite material.
在本发明中，所述非降解塑料基料、秸秆粉和氧化-生物双降解添加剂等原料的内容与前文所述的内容一致，在此不再赘述。本发明实施例将非降解塑料基料和氧化-生物双降解添加剂均匀混合；所述混合的时间优选为1min～20min，更优选为10min～20min。本发明实施例将得到的混合料与秸秆粉混合，经热压复合或熔融挤出等不同方式的成型加工，制成兼具氧化降解和生物降解的木塑复合材料。在本发明的实施例中，所述成型加工的温度为150℃～250℃，优选为170℃～220℃；所述成型加工的时间为10min～1h，优选为20min～50min。对于PP，成型加工的温度通常为150～190℃，优选为175℃；成型时间优选为15min～90min，更优选为45min～60min。对于PE，成型加工的温度通常为150～190℃，优选为165℃；成型时间优选为15min～90min，更优选为45min～60min。本发明的具体实施例采用挤出造粒的方式制备，长径比为25:1；挤出机各挤出区段温度为50～250℃，挤出机温度可设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为25～450转/分。In the present invention, the content of the raw materials such as the non-degradable plastic base material, straw powder and oxidative-biodegradable additive is the same as that described above, and will not be repeated here. In the embodiment of the present invention, the non-degradable plastic base material and the oxidative-biodegradable additive are uniformly mixed; the mixing time is preferably 1 min to 20 min, more preferably 10 min to 20 min. In the embodiment of the present invention, the obtained mixture is mixed with straw powder, and processed in different ways such as hot-compression compounding or melt extrusion to make a wood-plastic composite material with both oxidative degradation and biodegradation. In an embodiment of the present invention, the molding process temperature is 150°C-250°C, preferably 170°C-220°C; the molding process time is 10min-1h, preferably 20min-50min. For PP, the molding temperature is usually 150-190°C, preferably 175°C; the molding time is preferably 15min-90min, more preferably 45min-60min. For PE, the molding process temperature is usually 150-190°C, preferably 165°C; the molding time is preferably 15min-90min, more preferably 45min-60min. The specific embodiment of the present invention is prepared by extrusion granulation, and the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the temperature of the extruder can be set: the first zone is 170°C ℃～175℃, the second zone is 175℃～180℃, the third zone is 180℃～185℃, the head temperature is 180℃; the rotation speed of the extruder is 25～450 rpm.
制得可降解秸秆木塑复合材料后，本发明对其进行性能测试，其中采用万能试验机测试木塑复合材料的机械性能。结果表明，本发明所述木塑复合材料在使用中具有与普通木塑复合材料相同的理化特性和使用性能，如吸水率低(吸水率＜2％)，不易变形开裂，防虫蛀霉变；具有机械性能高、质轻、防潮、耐酸碱、耐腐蚀和便于清洗等特点，可在很多领域替代原木、塑料和铝合金等使用，市场应用前景广泛。After the degradable straw wood-plastic composite material is prepared, the present invention conducts performance tests on it, wherein a universal testing machine is used to test the mechanical properties of the wood-plastic composite material. The results show that the wood-plastic composite material of the present invention has the same physical and chemical properties and performance as ordinary wood-plastic composite materials in use, such as low water absorption (water absorption <2%), not easily deformed and cracked, and resistant to moths and mildew; It has the characteristics of high mechanical performance, light weight, moisture resistance, acid and alkali resistance, corrosion resistance and easy cleaning. It can replace logs, plastics and aluminum alloys in many fields, and has a broad market application prospect.
本发明将可降解秸秆木塑复合材料置于热压机中，在温度为180℃的条件下热压成片状试样，然后将试样置于70℃烘箱中进行热降解试验。结果显示，经过3个月时间，试样发生明显降解，丧失力学强度。表明本发明所述木塑复合材料达到使用寿命后可在自然环境中进行氧化-生物降解，从而不会对环境造成污染。In the present invention, the degradable straw wood-plastic composite material is placed in a hot press, and hot-pressed into a sheet-like sample at a temperature of 180°C, and then the sample is placed in an oven at 70°C to perform a thermal degradation test. The results showed that after 3 months, the sample degraded obviously and lost its mechanical strength. It shows that the wood-plastic composite material of the present invention can be oxidized-biodegraded in the natural environment after reaching the service life, so that it will not pollute the environment.
为了进一步理解本发明，下面结合实施例对本发明提供的环保可降解木塑复合材料及其制备方法进行具体地描述。In order to further understand the present invention, the environment-friendly degradable wood-plastic composite material provided by the present invention and its preparation method are specifically described below in conjunction with examples.
实施例1Example 1
将60质量份的聚丙烯(数均分子量为10万)和15质量份的EBPmas-PP-1502(购自山东天壮环保科技有限公司)混合，10min后得到混合料；60 parts by mass of polypropylene (the number average molecular weight is 100,000) and 15 parts by mass of EBPmas-PP-1502 (purchased from Shandong Tianzhuang Environmental Protection Technology Co., Ltd.) were mixed, and the mixture was obtained after 10 minutes;
将所述混合料与40质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到可降解木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。After mixing the mixture with 40 parts by mass of wheat straw powder (passed through a 40-mesh sieve), extruding and granulating through a twin-screw extruder to obtain a degradable wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。本发明木塑复合材料的拉伸强度为15.1MPa，吸水率＜2％。经过3个月时间，本发明试样发生明显降解，试样极易粉碎，丧失力学强度；样品降解前后的状态对比如图1所示，图1为本发明实施例1制备的木塑复合材料样品降解前后的对比结果。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material of the invention is 15.1 MPa, and the water absorption rate is less than 2%. After 3 months, the sample of the present invention was obviously degraded, and the sample was easily crushed and lost its mechanical strength; the state comparison of the sample before and after degradation is shown in Figure 1, and Figure 1 is the wood-plastic composite material prepared in Example 1 of the present invention Comparison results of samples before and after degradation.
实施例2Example 2
将60质量份的聚丙烯(数均分子量为10万)、0.5质量份的抗氧剂1010和15质量份的EBPmas-PP-1502(购自山东天壮环保科技有限公司)混合，20min后得到混合料；将所述混合料与40质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到可降解木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。60 mass parts of polypropylene (number average molecular weight is 100,000), 0.5 mass parts of antioxidant 1010 and 15 mass parts of EBPmas-PP-1502 (purchased from Shandong Tianzhuang Environmental Protection Technology Co., Ltd.) were mixed, and obtained after 20min Mixed material; after mixing the mixed material with 40 parts by mass of wheat straw powder (passed through a 40-mesh sieve), extruding and granulating through a twin-screw extruder to obtain a degradable wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。本发明木塑复合材料的拉伸强度为14.8MPa，吸水率＜2％。经过3个月时间，本发明试样发生明显降解，拉伸强度降为1.2MPa，基本丧失力学强度；样品降解前后的状态对比如图2所示，图2为本发明实施例2制备的木塑复合材料样品降解前后的对比结果。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material of the invention is 14.8 MPa, and the water absorption rate is less than 2%. After 3 months, the sample of the present invention obviously degrades, the tensile strength drops to 1.2MPa, and the mechanical strength is basically lost; the state comparison before and after the sample degradation is shown in Figure 2, and Figure 2 is the wood prepared by Example 2 of the present invention Comparison results of plastic composite samples before and after degradation.
实施例3Example 3
将80质量份的聚丙烯(数均分子量为10万)和20质量份的EBPmas-PP-1501(购自山东天壮环保科技有限公司)混合，15min后得到混合料；将所述混合料与20质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到可降解木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。The polypropylene (number average molecular weight is 100,000) of 80 mass parts and the EBPmas-PP-1501 (purchased from Shandong Tianzhuang Environmental Protection Technology Co., Ltd.) of 20 mass parts are mixed, obtain compound after 15min; 20 parts by mass of wheat straw powder (passed through a 40-mesh sieve) were mixed, extruded and granulated by a twin-screw extruder to obtain a degradable wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。本发明木塑复合材料的拉伸强度为16.5MPa，吸水率＜2％。经过3个月时间，本发明试样发生明显降解，拉伸强度降为8.5MPa。本发明试样降解前(原始样)的机械性能参见表1，表1为实施例3试样降解前的机械性能。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material of the invention is 16.5 MPa, and the water absorption rate is less than 2%. After 3 months, the sample of the present invention was obviously degraded, and the tensile strength was reduced to 8.5 MPa. The mechanical properties of the sample of the present invention before degradation (original sample) are shown in Table 1, and Table 1 is the mechanical properties of the sample of Example 3 before degradation.
表1实施例3试样降解前的机械性能The mechanical properties of table 1 embodiment 3 samples before degradation
实施例4Example 4
将90质量份的聚丙烯(数均分子量为10万)和10质量份的EBPmas-PP-1501(购自山东天壮环保科技有限公司)混合，10min后得到混合料；90 parts by mass of polypropylene (the number average molecular weight is 100,000) and 10 parts by mass of EBPmas-PP-1501 (purchased from Shandong Tianzhuang Environmental Protection Technology Co., Ltd.) were mixed, and the mixture was obtained after 10 minutes;
将所述混合料与10质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到可降解木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。After mixing the mixture with 10 parts by mass of wheat straw powder (passed through a 40-mesh sieve), extruding and granulating through a twin-screw extruder to obtain a degradable wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。本发明木塑复合材料的拉伸强度为18.5MPa，吸水率＜2％。经过3个月时间，本发明试样发生降解，拉伸强度降为12.5MPa。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material of the invention is 18.5 MPa, and the water absorption rate is less than 2%. After 3 months, the sample of the present invention degrades, and the tensile strength drops to 12.5 MPa.
实施例5Example 5
将50质量份的HDPE(数均分子量为10万)和5质量份的EBPmas-PE-1501(购自山东天壮环保科技有限公司)混合，10min后得到混合料；Mix 50 parts by mass of HDPE (the number average molecular weight is 100,000) and 5 parts by mass of EBPmas-PE-1501 (purchased from Shandong Tianzhuang Environmental Protection Technology Co., Ltd.), and obtain the mixture after 10 minutes;
将所述混合料与50质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到可降解木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。After mixing the mixture with 50 parts by mass of wheat straw powder (passed through a 40-mesh sieve), extruding and granulating through a twin-screw extruder to obtain a degradable wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。本发明木塑复合材料的拉伸强度为10.4MPa，吸水率＜2％。经过3个月时间，本发明试样发生降解，拉伸强度降为5.1MPa。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material of the invention is 10.4 MPa, and the water absorption rate is less than 2%. After 3 months, the sample of the present invention degrades, and the tensile strength drops to 5.1 MPa.
对比例comparative example
将60质量份的聚丙烯(数均分子量为10万)和0.5质量份的抗氧剂1010混合，20min后得到混合料；The polypropylene (number average molecular weight is 100,000) of 60 mass parts is mixed with the antioxidant 1010 of 0.5 mass part, obtains compound after 20min;
将所述混合料与40质量份的小麦秸秆粉(过40目筛)混合后，经双螺杆挤出机进行挤出造粒，得到木塑复合材料。其中，长径比为25:1；挤出机各挤出区段温度为50～250℃，具体的温度设为：一区为170℃～175℃，二区为175℃～180℃，三区为180℃～185℃，机头温度为180℃；挤出机转数为450转/分。After mixing the mixture with 40 parts by mass of wheat straw powder (passed through a 40-mesh sieve), extruding and granulating through a twin-screw extruder to obtain a wood-plastic composite material. Among them, the length-to-diameter ratio is 25:1; the temperature of each extrusion section of the extruder is 50-250°C, and the specific temperature is set as: 170°C-175°C for the first zone, 175-180°C for the second zone, and 175-180°C for the second zone. The zone is 180°C to 185°C, the head temperature is 180°C; the rotation speed of the extruder is 450 rpm.
按照上文所述的方法，将制得的木塑复合材料试验进行性能测试。所述木塑复合材料的拉伸强度为14.4MPa，吸水率＜2％。经过3个月时间，试样未发生明显降解，拉伸强度为12.5MPa。According to the method described above, the prepared wood-plastic composite material was tested for performance. The tensile strength of the wood-plastic composite material is 14.4 MPa, and the water absorption rate is less than 2%. After 3 months, the sample did not degrade significantly, and the tensile strength was 12.5MPa.
由以上实施例可知，本发明添加了一定量的氧化-生物双降解添加剂，使用氧化-生物双降解塑料技术，使木塑复合材料兼具氧化降解和生物降解的能力，且其降解时间可控；当木塑复合材料达到使用寿命后可在自然环境中进行氧化-生物降解，从而不会对环境造成污染。同时，本发明所述木塑复合材料在使用中具有与普通木塑复合材料相同的理化特性。It can be seen from the above examples that the present invention adds a certain amount of oxidative-biodegradable additives and uses oxidative-biodegradable plastic technology to make wood-plastic composite materials have both oxidative degradation and biodegradable capabilities, and its degradation time is controllable ; When the wood-plastic composite material reaches the service life, it can be oxidized-biodegraded in the natural environment, so that it will not pollute the environment. At the same time, the wood-plastic composite material of the present invention has the same physical and chemical properties as ordinary wood-plastic composite materials in use.
| Application Number | Priority Date | Filing Date | Title |
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| CN201511031779.4ACN105419105A (en) | 2015-12-31 | 2015-12-31 | Environment-friendly degradable wood-plastic composite and preparation method thereof |
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| CN201511031779.4ACN105419105A (en) | 2015-12-31 | 2015-12-31 | Environment-friendly degradable wood-plastic composite and preparation method thereof |
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| Date | Code | Title | Description |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20160323 |