CN1193026A - Base material capable of light degeradation and biological degradation - Google Patents

Base material capable of light degeradation and biological degradation Download PDF

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CN1193026A
CN1193026A CN 97100607 CN97100607A CN1193026A CN 1193026 A CN1193026 A CN 1193026A CN 97100607 CN97100607 CN 97100607 CN 97100607 A CN97100607 A CN 97100607A CN 1193026 A CN1193026 A CN 1193026A
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starch
agent
parts
masterbatch
light
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CN 97100607
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赵小英
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赵小英
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Abstract

The environmental photobiodegradable mothor material includes polyolefin resin, modified starch, photodegradation agent, oxidation accelerent, autoxidation agent, degradation control agent and calcium carbonate. Its preparation method includes the following steps: placing general starch in high-speed stirring machine, low-speed stirring to above 60 deg.C, adding coupling agent and high-speed mixing to modify the starch, mixing modified starch with polyolefin and assistants to obtain mixed material, then using special twin-screw extruder to make extrusion and granulation to make the mixed material into said invented cylindrical mother material with length of 3-4 mm and diameter of 2 mm. Said mother material can be matched with general polyolefin, and can be made into various photobiodegradable films by using general blow moulding equipment.

Description

光和生物可环境降解母料 Biological Degradable light masterbatch

本发明涉及一种光和生物可环境降解母料。 The present invention relates to a biological light environmentally degradable masterbatch.

塑料以其优异的性能、千姿百态的设计,得到广泛的应用,为人类带来了文明,为社会带来了进步。 Plastic with its excellent performance, a mix of design, has been widely used for human civilization has brought to society has brought progress. 但是它在达到使用目的被废弃以后,几十年、上百年都不易降解和消失,又造成严重的塑料垃圾及社会公害问题,已形成了一个新的污染源。 But after reaching its intended use was abandoned for decades, centuries are resistant to degradation and disappearance has also caused serious pollution of plastic waste and social issues, has formed a new source of pollution. 它造成的环境污染,以及对生物的影响已成为世界性的社会问题。 Environmental pollution it causes, and effects on organisms has become a worldwide social problem. 目前,消除塑料垃圾的方法主要有三种方法:①回收;②堆埋;③焚烧。 Currently, the method of eliminating plastic waste There are three main methods: ① recovery; ② pile buried; ③ burning. 回收即将废旧塑实收集起来,经分类、分检、清洗、重新造粒,二次加工成低档次制品。 Recovering solid plastic waste coming collected, sorted, sorting, washing, re-granulation, secondary processing into a low-level products. 但由于回收时要求技术高,产出效益低,实际上回收很困难;堆埋由于塑料在地下长期不能分解,占地面积过大,且影响土壤结构而不切合实际;焚烧则会产生大量有害气体,造成二次污染。 However, due to the high technical requirements, low output efficiency, in fact, very difficult to recover when the recovery; heap buried because the plastic does not decompose in the ground long, too large an area, and soil structure without practical; burning will produce large amounts of harmful gas, causing secondary pollution.

从70年代起,国外有不少研究人员就从事研究能迅速溶解或自行分解或燃烧时不产生有害气体的塑料—降解塑料。 Since the 1970s, there are many foreign researchers engaged in the plastic does not produce harmful gases in the study quickly dissolve or self decomposition or burning - degradable plastics. 这是塑料工业发展的必然趋势,而可环境降解的母料是降解塑料制品的必须原母料。 This is an inevitable trend in the development of the plastics industry, and environmentally degradable masterbatch is biodegradable plastic products must be original masterbatch.

过去有专利报道,用糊化淀粉和接枝共混物及光降解剂与塑料共混,制备一种可降解塑料,但由于淀粉改性工艺复杂,设备费用高,投资大而不宜工业化生产,同时由于改性淀粉稳定性和降解可控性及降解彻底性差,很难推广应用。 Patent reports that in the past there, with gelatinized starch and grafted blend and plastic blends photodegradation agent, to prepare a biodegradable plastic, but the starch modification process complexity, high cost of equipment, a large investment should industrial production, and because modified starch degradation and stability and complete degradation of controllability is poor, it is difficult application.

本发明的目的在于为生产降解塑料制品提供一种光和生物可环境降解母料,它具有加工中的稳定性、降解过程中的可控制性和降解的彻底性,并低于普通聚烯烃的价格。 Object of the present invention is to provide a light and biologically degradable masterbatch production environment biodegradable plastic products which has the stability of the processing, degradation of controllability and complete degradation of the polyolefin and lower than the ordinary price.

本发明光和生物可环境降解母料的组份包括聚烯烃树脂、改性淀粉、光降解剂、促氧化剂、自氧化剂、降解控制剂、碳酸钙。 The present invention may be environmentally degradable biological light masterbatch ingredients include polyolefin resins, modified starches, photodegradable agents, pro-oxidant, from the oxidant, the degradation controlling agent is calcium carbonate.

其中所述的上述的组份的配比为(以重量份计):聚烯烃树脂15-40份:改性淀粉50-80份:光降解剂0.02-0.3份:促氧化剂0.01-0.1份:自氧化剂0.1-10份:降解控制剂0.02-0.2份:碳酸钙10-40份。 Wherein the ratio of parts of the group (in parts by weight): 15 to 40 parts of polyolefin resin: 50 to 80 parts of modified starch: 0.02 to 0.3 parts by photodegradation agent: prooxidant 0.01-0.1 parts: from 0.1 to 10 parts of the oxidizing agent: 0.02 to 0.2 parts by degradation controlling agent: 10-40 parts of calcium carbonate.

其中所述的聚烯烃树脂包括LDPE、LLDPE、HDPE、PP或PS等。 Wherein the polyolefin resin include LDPE, LLDPE, HDPE, PP, or the like PS.

其中所述的改性淀粉是将普通淀粉用硅烷类、钛酸脂类、铝酸脂类偶联剂及低分子烃类处理制得,其中硅烷类、钛酸脂类、铝酸脂类偶联剂及低分子烃类用量为0.5-5%,于70-100℃下高速搅拌3-5分钟。 Wherein said modified starch is a common starch with a silane-based, titanate-lipids, lipid aluminate coupling agents and low molecular weight hydrocarbon processing prepared, wherein the silane-based, titanate lipids, lipid aluminate coupling linking agent and low molecular weight hydrocarbons in an amount of 0.5 to 5%, was stirred at high speed for 3-5 minutes at 70-100 deg.] C.

其中所述的碳酸钙是用脂肪酸类如十六酸、十八酸、二十酸等处理制得,其中脂肪酸类用量为0.5-5%,于70-100℃下高速搅拌3-5分钟。 Wherein said calcium carbonate is such as palmitic acid, stearic acid, arachidic acid and the like to obtain treated with fatty acids, wherein the fatty acid in an amount of 0.5 to 5%, was stirred at high speed for 3-5 minutes at 70-100 deg.] C.

其中所述的自氧化剂为植物油类,如大豆油、玉米油、棉籽油、菜籽油等。 Wherein said oxidizing agent is from vegetable oils such as soybean oil, corn oil, cottonseed oil, rapeseed oil and the like.

其中所述的光降解剂为铁的离子盐,如萘酸铁、硬脂酸铁、水扬酸铁、甲酸铁、乙酸铁等。 Wherein said photodegradation agent is an ionic salt of iron, such as iron naphthenate, iron stearate, iron salicylic acid, formic acid, iron acetate.

其中所述的促氧化剂为脂肪盐类,如硬脂酸锌、硬脂酸钙。 Wherein said fatty prooxidant salts such as zinc stearate, calcium stearate.

其中所述的降解控制剂为2、6-二叔丁基四甲基苯酚或2、4-二甲基六叔丁基苯酚。 Wherein the degradation controlling agent is 2,6-di-tert-tetramethyl-2,4-dimethyl phenol or -hexa-butylphenol.

本发明所提供的光和生物可环境降解母料的制备方法包括:首先将细度在10微米以下的普通淀粉加入到已升温至70-80度的高速搅拌机内,低速搅拌至物料淀粉温度达60度以上,分三次加入0.005-0.01%偶联剂进行高速混合处理5-10分钟,使其改性后与10-20%聚烯烃及5-15%的光降解剂、促氧化剂、自氧化剂、降解控制剂、碳酸钙低速混合10-15分钟,高搅温度控制在100度以内,制成混合料;然后,将混合料通过专用双螺杆挤出机在140-200度范围内进行挤出造粒,制成直径2mm长3-4mm的园柱型光和生物可环境降解母料。 The present invention provides a biological light may be prepared environmentally degradable masterbatch comprising: first common starch fineness below 10 microns is added to the high-speed stirrer was warmed to 70-80 °, stirred at low speed until the temperature of the starch material 60 degrees, was added in three portions 0.005-0.01% coupling agent mixed at high speed for 5-10 minutes, so that the modified polyolefin and 5-15% and 10-20% photodegradation agent, a pro-oxidant, from the oxidant degradation controlling agent, calcium carbonate, mixing at low speed for 10-15 minutes, stir the high temperature controlled within 100 degrees, to prepare a mixed material; then the mixture through a twin screw extruder dedicated in the range of 140-200 degrees extrusion granulated, having a diameter of 2mm 3-4mm long cylindrical light biological garden environmentally degradable masterbatch. 该母料可与通用聚烯烃配合,并加入其它组分,采用普通吹塑设备,制成各种光和生物降解的薄膜。 The masterbatch can be used with general-purpose polyolefins, and adding the other ingredients, ordinary blow molding apparatus, be made of various light and biodegradable film.

本发明光和生物可环境降解母料除了一般光和生物双降解功能外,尤其在母料中加入了经特殊处理的不同比例的碳酸钙,使该母料在制备过程中增强了稳定性,在降解塑料制品降解过程中提高了可控性、彻底性。 The present invention is a biological light environmentally degradable masterbatch addition to the general degradation of the light-bis biological functions, in particular in the masterbatch is added a different proportion of calcium carbonate specially treated so that the masterbatch enhances the stability during the preparation process, improved controllability of biodegradable plastic products in the degradation process, thoroughness.

该发明母料在自然环境下,不仅具有一般光生物双降解功能,而且由于添加碳酸钙可在10-50%之间任意调整比例,提高了降解母料在制备过程中的稳定性和降解过程中的可控性、彻底性,同时与同类产品相比,其成本降低30%左右,可大大担高经济效益。 The invention masterbatch materials in the natural environment, not only has the general degradation of the photobioreactor dual function, since the addition of calcium carbonate and the ratio can be adjusted between 10 and 50%, to improve the stability and degradation of degradable masterbatch preparation process the controllability, thoroughness, and compared with similar products, it costs about 30%, can greatly bear high economic efficiency. 本产品运用于吹塑农用地膜、工业、食品包装、垃圾袋等。 This product is applied to agricultural plastic blow molding, industrial, food packaging, garbage bags and so on. 还可调整载体,广泛用于PP和PS包装及一次性餐具制品。 Vectors can also be adjusted, PP and PS are widely used in packaging and disposable tableware products.

本发明光和生物可环境降解母料由于自氧化剂的加入,不但提高了降解过程中生物降解功能,它还是一种很好的增塑剂,提高了降解塑料制品的物理性能。 The present invention is a biological light environmentally degradable masterbatch due to the addition of self-oxidant, not only improve the biodegradability function degradation process, it is a good plasticizer to improve the physical properties of the degradable plastic products.

本发明光和生物可环境降解母料的优点在于:生产工艺简单,采用将淀粉与偶联剂及低分子烃类在高速混合器中混炼为疏水淀粉,克服了原有改性淀粉(淀粉接枝共混物)复杂的工艺和高生产成本的缺点,尤其是加入不同比例的碳酸钙于该母料中,增强了其加工的稳定性和降解过程中的不控性、彻底性,同时大大降低了生产成本(30%左右),提高了经济效益,母料的制备按一定比例将聚烯烃树脂、改性淀粉、光降解剂、促氧化剂、自氧化剂、降解控制剂、碳酸钙经高速混合器混炼、再经双螺杆造粒机挤出成型,可获得不同型号的光和生物可环境降解母料,为可降解地膜工业、食品包装袋、垃圾袋和一次性饮食餐具具制备所必须的优质母料。 Biological light and advantages of the present invention may be environmentally degradable masterbatch in that: the production process is simple, using a coupling agent and low molecular weight starch with a high speed mixer hydrocarbons kneading a hydrophobic starch, overcomes this modified starch (Starch grafted blend of a) a complex process and high production cost disadvantages, particularly calcium carbonate was added to the different proportions of the masterbatch, the enhanced stability and controllability without degradation of its processing, thoroughness, and greatly reduces the production costs (about 30%), to improve the economic efficiency, the masterbatch prepared according to a certain percentage of the polyolefin resin, modified starches, photodegradation agent, a pro-oxidant, from the oxidant, the degradation controlling agent is calcium carbonate in high speed mixer and kneaded, and then granulated by a twin-screw extruder to obtain different types of light and biologically degradable masterbatch environment, degradable plastic film industry, food packaging bags, garbage bags, and disposable eating utensils with the preparation you must be high-quality masterbatch.

下面通过表1中的配方结合三个实施例说明本发明,其技术指标,吹塑膜力学性能和降解性能如表2、表3、表4、表5所示:表1(组分的配比(重量份数表示)) The present invention will be described below in Table 1 Formulation three embodiments in conjunction with technical indicators, mechanical properties and degradation properties of blown film as shown in Table 2, Table 3, Table 4, Table 5 below: Table 1 with (component ratio (in parts by weight))

表2光和生物可环境降解母料技术指标 Table 2 light and bio-degradable masterbatch Environment Specifications

表3吹塑成降解覆膜力学性能 Table 3 Mechanical Properties of blow molded into film degradation

表4 吹塑成可降解地膜老化磷解指标 Table 4 may be blown into degradable films aging index phosphorus Solutions

表5吹塑成垃圾袋包装膜老化裂解指标 Table 5 blow molded trash bag film cracking aging index

Claims (10)

  1. 1.光和生物可环境降解母料,其中包括聚烯烃树脂、改性淀粉、光降解剂、促氧化剂、自氧化剂、降解控制剂、碳酸钙。 1. The light and biologically degradable masterbatch environment, which comprises a polyolefin resin, a modified starch, photodegradable agents, pro-oxidant, from the oxidant, the degradation controlling agent is calcium carbonate.
  2. 2.权利要求1所述的光和生物可环境降解母料,其中所述的上述的组份的配比为(以重量份计):聚烯烃树脂15-40份:改性淀粉50-80份:光降解剂0.02-0.3份:促氧化剂0.01-0.1份:自氧化剂0.1-10份:降解控制剂0.02-0.2份:碳酸钙10-40份。 The biological light according to claim 1 may be environmentally degradable masterbatch, wherein the ratio of parts of the group (in parts by weight): 15 to 40 parts of polyolefin resin: modified starch 50-80 parts: from 0.02 to 0.3 parts by photodegradation agent: prooxidant 0.01-0.1 parts: from 0.1 to 10 parts of the oxidizing agent: 0.02 to 0.2 parts by degradation controlling agent: 10-40 parts of calcium carbonate.
  3. 3.权利要求1所述的光和生物可环境降解母料,其中所述的聚烯烃树脂包括LDPE、LLDPE、HDPE、PP或PS。 The biological light according to claim 1 may be environmentally degradable masterbatch, wherein the polyolefin resin include LDPE, LLDPE, HDPE, PP or PS.
  4. 4.权利要求1所述的光和生物可环境降解母料,其中所述的改性淀粉是将普通淀粉,包括玉米淀粉、红薯淀粉、八蕉淀粉或木薯淀粉,用硅烷类、钛酸脂类、铝酸脂类偶联剂及低分子烃类处理制得,其中硅烷类、钛酸脂类、铝酸脂类偶联剂及低分子烃类用量为0.5-5%,于70-100℃下高速搅拌3-5分钟。 Light biologically degradable masterbatch according to the environment with a silane-based, titanate-fat claim 1, wherein the modified starch is a common starch, including corn starch, sweet potato starch, banana starch or tapioca starch eight, type, aluminate coupling agent, lipids and low molecular weight hydrocarbon processing prepared, wherein the silane-based, titanate lipids, lipid aluminate coupling agents and low molecular weight hydrocarbons in an amount of 0.5 to 5%, in 70-100 ℃ 3-5 minutes at high agitation.
  5. 5.权利要求1所述的光和生物可环境降解母料,其中所述的碳酸钙是用脂肪酸类如十六酸、十八酸、二十酸等处理制得,其中脂肪酸类用量为0.5-5%,于70-100℃下高速搅拌3-5分钟。 The biological light according to claim 1 may be environmentally degradable masterbatch, wherein the calcium carbonate with fatty acids such as palmitic acid, stearic acid, arachidic acid treatment and the like prepared in which fatty acids in an amount of 0.5 5%, was stirred at high speed for 3-5 minutes at 70-100 deg.] C.
  6. 6.权利要求1所述的光和生物可环境降解母料,其中所述的自氧化剂为植物油类,包括大豆油、玉米油、棉籽油或菜籽油。 The biological light according to claim 1, environmentally degradable masterbatch, wherein the oxidizing agent is from vegetable oils, including soybean oil, corn oil, cottonseed oil, or rapeseed oil.
  7. 7.权利要求1所述的光和生物可环境降解母料,其中所述的光降解剂为铁的离子盐,包括萘酸铁、硬脂酸铁、水扬酸铁、甲酸铁或乙酸铁。 The biological light according to claim 1 may be environmentally degradable masterbatch, wherein said photodegradation agent is ferric ion salts including iron naphthenate, iron stearate, iron salicylic acid, acetic acid or iron .
  8. 8.权利要求1所述的光和生物可环境降解母料,其中所述的促氧化剂为脂肪盐类,包括硬脂酸锌或硬脂酸钙。 8. The biological light according to claim 1 may be environmentally degradable masterbatch, wherein the prooxidant fat salts include zinc stearate or calcium stearate.
  9. 9.权利要求1所述的光和生物可环境降解母料,其中所述的降解控制剂为2、6-二叔丁基四甲基苯酚或2、4-二甲基六叔丁基苯酚。 Light biologically degradable masterbatch according environment butyl-1-tetramethyl-2,4-dimethyl phenol or -hexa-butylphenol claim 9, wherein the degradation controlling agent is .
  10. 10.权利要求1所述的光和生物可环境降解母料,其中制备方法包括:首先将细度在10微米以下的普通淀粉加入到已升温至70-80度的高速搅拌机内,低速搅拌至物料淀粉温度达60度以上,分三次加入0.005-0.01%偶联剂进行高速混合处理5-10分钟,使其改性后与10-20%聚烯烃及5-15%的光降解剂、促氧化剂、自氧化剂、降解控制剂、碳酸钙低速混合10-15分钟,高搅温度控制在100度以内,制成混合料;然后,将混合料通过专用双螺杆挤出机在140-200度范围内进行挤出造粒,制成直径为2mm长3-4mm的园柱型光和生物可环境降解母料。 10. The environmentally degradable biological light masterbatch according to claim 1, wherein the preparation process comprises: a first common starch fineness below 10 microns is added to the high-speed stirrer was warmed to 70-80 °, stirred at low speed until starch material temperature of 60 degrees or more, added in three portions 0.005-0.01% coupling agent mixed at high speed for 5-10 minutes, so that the modified polyolefin and 5-15% and 10-20% photodegradation agent, a pro oxidant, from the oxidant, the degradation controlling agent, calcium carbonate, mixing at low speed for 10-15 minutes, stir the high temperature controlled within 100 degrees, to prepare a mixed material; then the mixture through a twin screw extruder at a dedicated range of 140-200 degrees the extrusion pelletized into cylindrical diameter of 2mm long garden light and biologically degradable masterbatch environment of 3-4mm.
CN 97100607 1997-03-06 1997-03-06 Base material capable of light degeradation and biological degradation CN1193026A (en)

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CN1074435C (en) * 1999-06-22 2001-11-07 沈阳南阳经贸集团有限公司 Multi-component degradable resin composition and its preparing process
CN1081203C (en) * 1999-02-11 2002-03-20 天津丹海股份有限公司 Mother material for biodegradable plastics and preparation thereof
WO2002042378A1 (en) * 2000-11-23 2002-05-30 Hao Xu A biodegradable composition for preparing table-ware, mulching film and package and method for preparing the same
CN102408612A (en) * 2011-11-23 2012-04-11 吴江明峰聚氨酯制品有限公司 Photodegradable and biodegradable polyethylene plastic bag
CN102796285A (en) * 2011-05-27 2012-11-28 上海杰事杰新材料(集团)股份有限公司 Double-degradation starch masterbatch and preparation method thereof
US8383702B2 (en) 2006-12-20 2013-02-26 Saint-Gobain Ceramics & Plastics, Inc. Composite materials having improved thermal performance
CN104031302A (en) * 2013-03-04 2014-09-10 中国科学院过程工程研究所 Controllable oxidative-biological degradation plastic master batch and preparation method thereof
US8846088B2 (en) 2005-02-03 2014-09-30 Takeda Nycomed As Melt granulation of a composition containing a calcium-containing compound
CN104369509A (en) * 2014-12-11 2015-02-25 昆山加浦包装材料有限公司 Degradable foamed and co-extruded PA barrier thin film
CN104385698A (en) * 2014-12-11 2015-03-04 昆山市张浦彩印厂 Degradable PO foaming co-extruded composite thin film
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