CN113004665A - 一种抗菌防虫可降解农用地膜及其制备方法 - Google Patents
一种抗菌防虫可降解农用地膜及其制备方法 Download PDFInfo
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- CN113004665A CN113004665A CN202110220507.8A CN202110220507A CN113004665A CN 113004665 A CN113004665 A CN 113004665A CN 202110220507 A CN202110220507 A CN 202110220507A CN 113004665 A CN113004665 A CN 113004665A
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- Prior art keywords
- mulching film
- borate
- agricultural mulching
- parts
- antibacterial insect
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Abstract
本发明公开了一种抗菌防虫可降解农用地膜及其制备方法。所述农用地膜的组分包括PBAT、植物胶粉、硼交联剂、抗菌防虫剂、增塑剂、润滑剂、热稳定剂、抗氧剂、紫外线吸收剂、填料。本发明的农用地膜具有良好的生物可降解性，在土壤中120天可达到80％降解率，150天全部降解，不污染环境，安全环保，避免产生白色污染，符合社会可持续发展的要求；此外还具有强度高、韧性好、抗菌防虫、耐紫外性好的优点，能够展现出可延长性和高延展性，制备方法简单，充分满足农业生产需求，具有非常好的推广应用前景。
Description
技术领域
本发明属于农用地膜技术领域，具体涉及一种具有高延展性、抗菌防虫效用的可降解农用地膜及其制备方法。
背景技术
农用地膜即地面覆盖薄膜，用于地面覆盖，以提高土壤温度，保持土壤水分，维持土壤结构，防止害虫侵袭作物和某些微生物引起的病害等，促进植物生长的功能。地膜不仅能够提高地温、保水、保土、保肥提高肥效，而且还有灭草、防病虫、防旱抗涝、抑盐保苗、改进近地面光热条件，使产品卫生清洁等多项功能。对于那些刚出土的幼苗来说，农用地膜具有护根促长等作用，对于我国三北地区，低温、少雨、干旱贫脊、无霜期短等限制农业发展的因素，具有很强的针对性和适用性，对于种植二季水稻育秧及多种作物栽培上也起了作用。在全国31 个省市自治区普及和应用过程中，农用地膜用于粮、棉、油、菜、瓜果、烟、糖、药、麻、茶、林等40多种农作物上，使作物普遍增产30％-50％，增值40％-60％，深受广大农民的欢迎。
农用地膜在广泛推广应用过程中，在促进粮食和经济作物产量增加的同时，也带来了严重的环境污染问题，大量不可降解的塑料残余物逐年上升，影响了生态平衡。传统的农用地膜的主要成分是聚乙烯、聚氯乙烯等不可降解的高分子材料，废弃的农用地膜降解极为困难，越积越多的塑料碎片在土壤中形成阻隔层，劣化土壤，造成严重的白色污染。大量的残膜存在使得土壤水分养分向下运输受到阻碍，土壤间隙和通透性降低，不利于土壤空气循环和浇灌，土地质量下降，从而造成作物营养不良，产量下降。当土壤地膜残留量达60kg/公顷时，就会给农作物造成减产。大量塑料地膜的污染是我们现在不得不解决的一个问题。因此，研制可降解薄膜，对于降低白色污染、改善土壤质量、保证农作物产量具有重要意义。
目前市场上的可降解塑料地膜属于添加型可降解塑料薄膜，如在塑料基体中添加可引发塑料产生降解的成分(淀粉、碳酸钙等)。但这种可降解塑料薄膜加工工艺性能不好、制成的塑料薄膜产品物性和外观较差，且需要一定的固定条件才能降解，降解性较差，而塑料薄膜废弃后，要么是被搁在封闭的垃圾处理系统中，要么就是暴露在条件不固定的自然环境中，很难达到这种塑料薄膜降解所需要的固定条件，使得其无论是在垃圾处理系统中还是在自然环境因为受条件限制都不能很好地降解。
此外，现有技术中的薄膜通常很薄，延展性相对较弱，且塑料薄膜在大棚安装使用过程中，人们会对薄膜拉扯，或当风力等级较大时，塑料薄膜不耐拉扯，容易发生破损，再进一步通过张力作用导致整张薄膜的破损。同时，地膜覆盖又要求膜材料本身在使用过程中具有一定的拉伸韧性，从而达到良好的延展覆盖效果。
PBAT(己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物)是一种半结晶型聚合物，属于热塑性生物降解塑料，兼具PBA和PBT的特性，既有较好的延展性和断裂伸长率，也有较好的耐热性和冲击性能；此外，还具有优良的生物降解性，是生物降解塑料研究中非常活跃和市场应用最好的降解材料之一。PBAT是脂肪族和芳香族的共聚物，综合了脂肪族聚酯的优异降解性能和芳香族聚酯的良好力学性能。PBAT的加工性能与LDPE非常相似，可用LDPE的加工设备吹膜。PBAT材料不仅可以生物降解也可堆肥，所以使用PBAT可以对抗白色污染。作为农用地膜材料，PBAT膜具有良好的生物可降解性，但在使用过程中可延展性不足，且PBAT 本身抗虫性较差，作为农业地膜在使用过程中易受虫害，不能满足最终产品的实际物理性能需求，限制了其在地膜方面的应用。
植物胶是我国新研制开发的一类天然植物胶，从盛产植物豆中制得，主要成分是半乳甘露聚糖，还有蛋白质、纤维素、水分及少量钙、镁等无机元素。植物胶具有良好的水溶性和交联性，并且粘度很高，可广泛应用于石油、造纸、食品、纺织、建筑等工业。植物胶不溶解于乙醇、甘油、甲酰胺等任何有机溶剂，水是植物胶的唯一溶剂。植物胶粉遇水能溶胀水合形成高粘度的溶胶液，其粘度随粉剂浓度增加而显著增加，植物胶液属于非牛顿型流体，粘度随剪切速度增高而降低。水合后的植物胶可与硼砂，重铬酸盐等多种化学试剂发生交联作用，形成具有一定粘弹性的非牛顿型水基凝胶，从而赋予基材良好的延展性。除了粘度之外，植物胶还有较强的耐盐性能，不受阳离子、阴离子的影响，植物胶是一种非离子性，不会产生盐析现象。同时，植物胶本身所具有的天然性达到了80％，无毒无污染，有研究表明，植物胶在民用上，杜绝污染指数可以达到60％左右，是一种纯天然的、绿色、无害的新型环保产品，可以防止薄膜分解过程中产生有害物质。植物胶以其高分子特性广泛的应用于造纸、建筑、装修、石油化工、纺织工业，但在农用地膜行业的应用却鲜有报道。
发明内容
本发明的目的在于克服现有技术的不足之处，提供了一种具有高延展性、抗菌防虫效用的可降解农用地膜及其制备方法，解决了上述背景技术中的问题。
本发明解决其技术问题所采用的技术方案之一是：提供了一种抗菌防虫可降解农用地膜，按重量份包括如下组分：
其中，所述抗菌防虫剂由如下重量份的组分制成：
在本发明中，所述助剂包括增塑剂、润滑剂、热稳定剂、抗氧剂、紫外线吸收剂。
所述PBAT优选采用薄膜级，PBAT是一种半结晶型聚合物，通常结晶温度在110℃附近，熔点在110-130℃左右，密度在1.18-1.3g/cm3之间。PBAT的化学结构如下所示：
在本发明一较佳实施例中，所述助剂按重量份包括：
在本发明一较佳实施例中，农用地膜按重量份由如下组分组成：
其中，所述抗菌防虫剂由如下质量份的组分制成：
在本发明中，所述的植物胶粉，其选自黄原胶粉、田菁胶粉、瓜尔胶粉、胡麻胶粉、香豆胶粉、石花胶粉、刺槐豆胶粉、海藻胶粉等。
在本发明中，所述的硼交联剂，其选自硼酸铵、硼酸钠、硼酸镁、硼酸铝、硼酸钾、硼酸钙、硼酸铜、硼酸锌、硼酸铅、硼酸钡、偏硼酸铵、偏硼酸钠、偏硼酸镁、偏硼酸铝、偏硼酸钾、偏硼酸钙、偏硼酸铜、偏硼酸锌、偏硼酸钡、二硼酸镁、三硼酸钡、硼砂、四硼酸锰、五硼酸钠、五硼酸铵、五硼酸钾、六硼酸镁、八硼酸钠、四硼酸二铵、八硼酸二铵、硼砂、硼酸三甲酯、硼酸三乙酯、硼酸三异丙酯、硼酸三叔丁酯、硼酸三苯酯、硼酸三甲苯酯、硼酸三苄酯、硼酸三环己酯、硼酸三(三甲硅烷基)酯、异丙醇频哪醇硼酸酯、三乙醇胺硼酸酯等。其中，硼交联剂优选硼酸钠、硼砂、硼酸三甲酯、硼酸三乙酯、硼酸三异丙酯。
在本发明中，所述的增塑剂，其能够增加聚合物薄膜的塑性，使得聚合物薄膜的伸长率、曲挠性和柔韧性提高，其选自邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异辛酯、邻苯二甲酸二庚酯、邻苯二甲酸二异癸酯、邻苯二甲酸二异壬酯、邻苯二甲酸丁苄酯、邻苯二甲酸丁酯乙醇酸丁酯、邻苯二甲酸二环己酯、邻苯二甲酸双(十三)酯、对苯二甲酸二(2-乙基)己酯、磷酸三甲苯酯、磷酸(二苯-2-乙基)己酯、己二酸二(2-乙基)己酯、癸二酸二(2- 乙基)己酯、甘油、乙二醇、聚乙二醇、环氧甘油酯、环氧脂肪酸单酯、环氧四氢邻苯二甲酸酯、环氧大豆油、环氧亚麻仁油、环氧硬脂酸(2-乙基)己酯、环氧大豆油酸2-乙基己酯、4,5- 环氧四氢邻苯二甲酸二(2-乙基)己酯、环氧乙酰蓖麻油酸甲酯、C5～9酸乙二醇酯、C5～9酸二缩三乙二醇酯、绿化石蜡类、氯代脂肪酸酯、乙二酸1,2-丙二醇系聚酯、癸二酸1,2-丙二醇聚酯、石油磺酸苯酯、偏苯三酸酯、柠檬酸酯、季戊四醇和双季戊四醇酯等。其中，增塑剂优选邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)、磷酸三甲苯酯(TCP)、环氧大豆油、环氧亚麻仁油、甘油、乙二醇、聚乙二醇。
在本发明中，所述的润滑剂，其选自固体石蜡、微晶石蜡、液体石蜡、低分子量聚乙烯、氧化聚乙烯蜡、硬脂酸、脂肪酸低级醇酯、脂肪酸多元醇酯、天然蜡、酯蜡和皂化蜡、硬脂酰胺或硬脂酸酰胺、油酰胺或油酸酰胺、芥酸酰胺、N,N’-乙撑双硬脂酰胺、硬脂醇、鲸蜡醇、季戊四醇、硬脂酸铅、硬脂酸钙、硬脂酸钡、硬脂酸镁、硬脂酸锌等。其中，润滑剂优选固体石蜡、液体石蜡、硬脂酸、脂肪酸多元醇酯、硬脂酰胺或硬脂酸酰胺。
在本发明中，所述的热稳定剂，其选自亚磷酸三苯酯、三盐基硫酸铅、二盐基亚磷酸铅、二盐基硬脂酸铅、二盐基苯二甲酸铅、三盐基马来酸铅、硬脂酸铅、水杨酸铅、二盐基邻苯二甲酸铅、碱式碳酸铅、硬脂酸镉、硬脂酸钡、硬脂酸钙、硬脂酸铅、硬脂酸锌、二月桂酸二正丁基锡、二月桂酸二正辛基锡、马来酸二(正)丁基锡、双马来酸单辛酯二正辛基锡，二巯基乙酸异辛酯二正辛基锡、京锡C-102、二巯基乙酸异辛脂二甲基锡、二硫醇二甲基锡及其复配物、季戊四醇、木糖醇、甘露醇、山梨糖醇、三羟甲基丙烷等。其中，热稳定剂优选亚磷酸三苯酯、硬脂酸钡，硬脂酸钙、二月桂酸二正丁基锡、马来酸二(正)丁基锡。
在本发明中，所述的抗氧剂，其选自2,6-二叔丁基-4-甲基苯酚、1,1,3-三(2-甲基-4羟基-5- 叔丁基苯基)丁烷、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、2,2’-亚甲基双(4- 甲基-6-叔丁基苯酚)、4,4’-硫代双-[3-甲基-6-叔丁基苯酚]、2,2’-硫代双-[4-甲基-6-叔丁基苯酚]、1,3,5-二[β-(3,5-二叔丁基-4-羟基苯基)丙酰]-六氢均三嗪、三(3,5-二叔丁基-4-羟基苄基)-三异氰酸酯、N,N’-二(β-萘基)对苯二胺、N,N’-二苯基对苯二胺、N-苯基-N’-环己基对苯二胺、硫代二丙酸二月桂酯、2-巯基苯并咪唑、2-巯基苯并噻唑、亚磷酸三苯酯、亚磷酸三壬基苯酯、三[2.4-二叔丁基苯基]亚磷酸酯、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]等。其中，抗氧剂优选二丁基羟基甲苯(BHT)、叔丁基对苯二酚(TBHQ)、三[2.4- 二叔丁基苯基]亚磷酸酯(抗氧剂168)、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](抗氧剂245)、抗氧剂 Chinox 20N。
在本发明中，所述的紫外光吸收剂，其选自2，4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、邻羟基苯甲酸苯酯、单苯甲酸间苯二酚酯、邻硝基苯胺、对甲苯酚、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-5-甲基苯基)苯并三唑、 2,4,6-三(2-羟基-4-正丁氧基苯基)-1,3,5-均三嗪、2-氰基-3,3-二苯基丙烯酸2-乙基己酯、水杨酸对-叔丁基苯酯、双水杨酸双酚A酯、双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)、2,2’-硫代双(4-特辛基酚氧基)镍等。其中，紫外线吸收剂优选水杨酸对-叔丁基苯酯、双水杨酸双酚A 酯、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮(紫外线吸收剂UV-531)。
在本发明中，所述的填料，其选自淀粉、木粉及壳粉、碳酸钙、硫酸钡、硫酸钙和亚硫酸钙、滑石粉、白炭黑、石英、云母粉、粘土、石灰石、重晶石粉、石膏、硅藻土、赤泥、硅灰石、氢氧化铝、氢氧化镁等；所述的淀粉包括玉米淀粉、木薯淀粉、马铃薯淀粉、高粱淀粉、小麦淀粉、红薯淀粉、改性淀粉中的一种或多种。所述的填料可以降低农用地膜的制作成本。
本发明解决其技术问题所采用的技术方案之二是：提供了上述抗菌防虫可降解农用地膜的制备方法，包括如下步骤：
(1)干燥：对PBAT原料、植物胶粉进行干燥处理。其中，PBAT的干燥温度为50-60℃，干燥时间为20-60min；
(2)混料：利用混合设备将PBAT、植物胶粉按照配比充分混合搅拌均匀，制得初级混合料；向初级混合料中加入硼交联剂、抗菌防虫剂、助剂和填料，在一定温度下进行搅拌，得到次级混合料。其中，初级混合料混合温度为室温，搅拌转速为300-3000r/min，混合时间为 5-20min；次级混合料混合温度为100-160℃，搅拌转速为2000-6000r/min，混合时间为5-10min；
(3)挤出造粒：将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒。其中，共混挤出造粒的工艺条件为：使用同向双旋转螺杆挤出机，螺旋转速为100-300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa；
(4)吹塑：将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜。其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为8-12m3/min，风压为0.3-0.5Mpa；牵引和卷绕成膜时膜的厚度控制在20-300μm。
本技术方案与背景技术相比，它具有如下优点：
1.本发明PBAT原料具有良好的生物可降解性，能被自然界中微生物完全降解，不污染环境，安全环保，避免产生白色污染：
选用植物胶作为增韧改性剂既保证了塑料成膜性能，又使得薄膜在自然条件下可达到全降解，降解条件简单，降解程度高；所述农用地膜绿色环保，在土壤中120天可达到80％降解率， 150天全部降解，不会造成塑胶污染，符合社会可持续发展的要求；
2.本发明的抗菌防虫可降解农用地膜不仅易于降解，还具有强度高、韧性好等优点：
薄膜中的植物胶粉与PBAT具有较好的相容性，增加了PBAT薄膜的韧性的同时，在一定条件下还能够实现薄膜的可延长性和高延展性，可以使得制得的农用地膜兼具有强度和韧性，在室温干燥条件下具有良好的拉伸强度和一定的韧性，将其浸渍于50-80℃的热水中10-60min，或者置于50-80℃蒸汽环境中，或者利用50-80℃热水进行冲淋之后，其能够展现出高延展性，具有十分优良的拉伸韧性，将其进行延展拉伸覆盖之后，其又能够重新定型；
3.本发明的抗菌防虫可降解农用地膜还具有良好的抗菌性能：
添加本发明配比的抗菌防虫剂，能够使薄膜具有杀菌驱虫性能，防止细菌滋生和虫蛀，提高了薄膜的防虫抗菌性能；
4.本发明农用地膜综合性能好，充分满足了农业生产需求，有利于蔬菜水果等农作物的生长发育，提高农作物产量，适于蔬菜大棚保护栽培，具有非常好的推广应用前景；
5.本发明制备工艺简单、生产效率高、工业化实施容易，具有良好的经济效益，采用吹塑机的制备方式避免了工厂对产线的大幅改造，降低成本，可以大范围推广应用，对制备环境友好型塑料具有重要意义。
具体实施方式
下述实施例中，PBAT原料可以通过购买商品化产品获得，如BASF公司的EcoflexTM，C1200，EastmanChemical公司Easter
以及意大利Novamont公司的Origo-
中国新疆蓝山屯河TH801T，THJS-5801等。其余组分如无特别注明，均可于市面购得。
下述实施例中，薄膜的降解实验通过如下方式进行：采集农田表层土壤，用32目的筛子细筛土壤，剔除明显的植物、石头等物质。调节土壤中含水量为40％-60％，调节土壤pH值为6.0-8.0，并将土壤放置在容器中。将测试薄膜裁成50mmx50mm的填埋样品，上下各垫一层尼龙窗纱，埋于土壤中，埋土深度为8-10cm，置于露天自然条件下进行考察，每隔15天取出称量，考察不同掩埋时间的失重率作为降解率数据。
实施例1
称取100份PBAT原料(德国BASF C1200)、5份石花胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、石花胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.1份硼酸三甲酯、2份抗菌除虫剂(抗菌防虫剂成分为：4份氯菊酯、2份白芥子提取物、1份艾蒿、2份辣椒籽油、1份薄荷油、0.1份八氯二丙醚)、1份甘油、1.5份硬脂酸、2份亚磷酸三苯酯、1份抗氧剂Chinox 20N、0.05份2-羟基-4-甲氧基二苯甲酮，在120-150℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为 8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为220-230μm，拉伸强度为35MPa，断裂伸长率为506％，在土壤中掩埋120天后，地膜降解率达到82％，掩埋150天后，地膜能够完全降解。
实施例2
称取100份PBAT原料(中国新疆蓝山屯河TH801T)、10份石花胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、石花胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.05份硼酸三甲酯、3份抗菌除虫剂(抗菌防虫剂成分为：3份氯菊酯、3份白芥子提取物、0.5份艾蒿、2份辣椒籽油、0.5份薄荷油、0.5份八氯二丙醚)、1.5份乙二醇、 1份石蜡、3份二月桂酸二正丁基锡、0.8份抗氧剂1010、0.08份2,4-二羟基二苯甲酮，在120-150 ℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为 8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为160-170μm，拉伸强度为22MPa，断裂伸长率为778％，在土壤中掩埋120天后，地膜降解率达到81％，掩埋150天后，地膜能够完全降解。
实施例3
称取100份PBAT原料(德国BASF C1200)、10份瓜儿胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、瓜儿胶粉在500r/min条件下混合搅拌10min，制得初级混合料；向初级混合料中加入0.1份硼酸钠、5份抗菌除虫剂(抗菌防虫剂成分为：5份氯菊酯、2份白芥子提取物、0.5份艾蒿、1份辣椒籽油、2份薄荷油、0.2份八氯二丙醚)、4份甘油、1份硬脂酸、 1份亚磷酸三苯酯、0.8份抗氧剂168、0.08份2,4-二羟基二苯甲酮、5份碳酸钙，在120-150 ℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为 8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为120-130μm，拉伸强度为24MPa，断裂伸长率为718％，在土壤中掩埋120天后，地膜降解率达到83％，掩埋150天后，地膜能够完全降解。
实施例4
称取100份PBAT原料(中国新疆蓝山屯河THJS-5801)、10份海藻胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、海藻胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.1份硼砂、1份抗菌除虫剂(抗菌防虫剂成分为：3份氯菊酯、3份白芥子提取物、0.5份艾蒿、2份辣椒籽油、0.5份薄荷油、0.5份八氯二丙醚)、1份甘油、2份硬脂酰胺、2份亚磷酸三苯酯、0.8份抗氧剂1010、0.05份2,4-二羟基二苯甲酮、0.5份粘土，在 120-150℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为 300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为 150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为180-200μm，拉伸强度为32MPa，断裂伸长率为590％，在土壤中掩埋120天后，地膜降解率达到83％，掩埋150天后，地膜能够完全降解。
实施例5
称取100份PBAT原料(德国BASF C1200)、15份田菁胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、田菁胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.1份硼砂、3份抗菌除虫剂(抗菌防虫剂成分为：4份氯菊酯、2份白芥子提取物、 1份艾蒿、2份辣椒籽油、1份薄荷油、0.1份八氯二丙醚)、2份环氧大豆油、2份硬脂酰胺、2份亚磷酸三苯酯、0.5份抗氧剂168、0.5份抗氧剂1010、0.05份2,4-二羟基二苯甲酮、10 份碳酸钙，在120-150℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为 10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为135-150μm，拉伸强度为32MPa，断裂伸长率 368％，在土壤中掩埋120天后，地膜降解率达到86％，掩埋150天后，地膜能够完全降解。
实施例6
称取100份PBAT原料(德国BASF C1200)、10份黄原胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、黄原胶粉在500r/min条件下混合搅拌10min，制得初级混合料；向初级混合料中加入0.05份硼砂、2份抗菌除虫剂(抗菌防虫剂成分为：4份氯菊酯、2份白芥子提取物、1份艾蒿、2份辣椒籽油、1份薄荷油、0.1份八氯二丙醚)、1份甘油、0.5份硬脂酸、 1份亚磷酸三苯酯、0.8份抗氧剂168、0.05份2-羟基-4-甲氧基二苯甲酮、10份玉米淀粉，在120-150℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55 °，风量为8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为140-145μm，拉伸强度为27MPa，断裂伸长率为669％，在土壤中掩埋120天后，地膜降解率达到85％，掩埋150天后，地膜能够完全降解。
实施例7
称取100份PBAT原料(中国新疆蓝山屯河TH801T)、25份瓜尔胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、瓜尔胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.25份硼酸钠、5份抗菌除虫剂(抗菌防虫剂成分为：5份氯菊酯、2份白芥子提取物、0.5份艾蒿、1份辣椒籽油、2份薄荷油、0.2份八氯二丙醚)、2份环氧大豆油、1 份石蜡、2份亚磷酸三苯酯、0.5份抗氧剂Chinox 20N、0.05份2,4-二羟基二苯甲酮，在120-150 ℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为 8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为60-70μm，拉伸强度为25MPa，断裂伸长率为 760％，在土壤中掩埋120天后，地膜降解率达到91％，掩埋150天后，地膜能够完全降解。
实施例8
称取100份PBAT原料(中国新疆蓝山屯河THJS-5801)、30份黄原胶粉进行干燥处理。利用高速混合机将干燥后的PBAT、黄原胶粉在800r/min条件下混合搅拌5min，制得初级混合料；向初级混合料中加入0.3份硼酸三甲酯、5份抗菌除虫剂(抗菌防虫剂成分为：4份氯菊酯、2份白芥子提取物、1份艾蒿、2份辣椒籽油、1份薄荷油、0.1份八氯二丙醚)、0.5份乙二醇、1 份石蜡、2份二月桂酸二正丁基锡、1份抗氧剂245、0.08份水杨酸对-叔丁基苯酯，在120-150 ℃温度条件，3000r/min转速下搅拌5min，得到次级混合料。将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；其中，挤出造粒的工艺条件为：螺旋转速为300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑的工艺条件为：吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为 8-12m3/min，风压为0.3-0.5Mpa。
经测试，本实施例的可降解农用地膜厚度为20-25μm，拉伸强度为17MPa，断裂伸长率为 865％，在土壤中掩埋120天后，地膜降解率达到95％，掩埋150天后，地膜能够完全降解。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种抗菌防虫可降解农用地膜，其特征在于：按重量份包括如下组分：
其中，所述抗菌防虫剂由如下重量份的组分制成：
2.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：所述助剂按重量份包括：
3.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：按重量份由如下组分组成：
4.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：所述抗菌防虫剂由如下质量份的组分制成：
5.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：所述植物胶粉包括黄原胶粉、田菁胶粉、瓜尔胶粉、胡麻胶粉、香豆胶粉、石花胶粉、刺槐豆胶粉、海藻胶粉中的至少一种。
6.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：所述硼交联剂包括硼酸铵、硼酸钠、硼酸镁、硼酸铝、硼酸钾、硼酸钙、硼酸铜、硼酸锌、硼酸铅、硼酸钡、偏硼酸铵、偏硼酸钠、偏硼酸镁、偏硼酸铝、偏硼酸钾、偏硼酸钙、偏硼酸铜、偏硼酸锌、偏硼酸钡、二硼酸镁、三硼酸钡、硼砂、四硼酸锰、五硼酸钠、五硼酸铵、五硼酸钾、六硼酸镁、八硼酸钠、四硼酸二铵、八硼酸二铵、硼砂、硼酸三甲酯、硼酸三乙酯、硼酸三异丙酯、硼酸三叔丁酯、硼酸三苯酯、硼酸三甲苯酯、硼酸三苄酯、硼酸三环己酯、硼酸三(三甲硅烷基)酯、异丙醇频哪醇硼酸酯、三乙醇胺硼酸酯中的至少一种。
7.根据权利要求1所述的一种抗菌防虫可降解农用地膜，其特征在于：农用地膜的厚度为20～300μm。
8.根据权利要求1～7任一项所述的一种抗菌防虫可降解农用地膜的制备方法，其特征在于：包括如下步骤：
(1)干燥：对PBAT的原料、植物胶粉进行干燥处理；
(2)混料：利用混合设备将PBAT、植物胶粉充分混合搅拌均匀，制得初级混合料；向初级混合料中加入硼交联剂、抗菌防虫剂、助剂和填料，再次搅拌得到次级混合料；
(3)挤出造粒：将次级混合料加入到双螺杆挤出机中进行共混挤出造粒，制得母料颗粒；
(4)吹塑：将母料颗粒干燥除水处理后，加入吹膜机的料仓，吹塑，牵引和卷绕成膜；其中，吹塑机温度为130-160℃，风口环模距离为50-60mm，冷风从风环吹出角度为40-55°，风量为8-12m3/min，风压为0.3-0.5Mpa。
9.根据权利要求8所述的一种抗菌防虫可降解农用地膜的制备方法，其特征在于：所述步骤(2)中，初级混合料混合温度为室温，搅拌转速为300-3000r/min，混合时间为5-20min；次级混合料混合温度为100-160℃，搅拌转速为2000-6000r/min，混合时间为5-10min。
10.根据权利要求8所述的一种抗菌防虫可降解农用地膜的制备方法，其特征在于：所述步骤(3)中，使用同向双旋转螺杆挤出机，螺旋转速为100-300r/min，一区温度为50-80℃，二区温度为110-130℃，三区温度为140-160℃，四区温度为150-160℃，五区温度为130-150℃，物料在螺杆中停留时间为3-5min，压力为10-15Mpa。
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