摘要 塑料及其制品与工业农业生产、人民生活紧密联系,但塑料添加剂(增塑剂)如 邻苯二甲酸酯引起的环境、食品安全问题已受到广泛重视。以低毒或无毒增塑剂替代 现有塑料制品(包括地膜)中的邻苯二甲酸酯,可以从塑料制品的源头控制污染,实 现清洁生产。本文以两种邻苯二甲酸酯替代品和一种国控邻苯二甲酸酯为研究对象, 探讨了两种邻苯二甲酸二辛酯替代品的技术、环境和经济可行性。研究方法及结果如 下: (1)通过幵展PVC地膜合成配方的筛选试验,以邻苯二甲酸二正辛酯(DOP)传 统配方为对照,对合成的地膜进行力学性能测试,XRD衍射分析和SEM扫描分析。 薄膜物理性能从优到次的结果:乙酰柠檬酸三丁酯(ATBC)组:配方3>配方4>配方 2>配方1,环氧大豆油(ESO)组:配方7>配方8>配方6>配方5;当ATBC用量为35 和30及DOP用量为35时,PVC地膜符合力学标准(GBT13735-1992)。 (2)在实验室条件下,通过真菌、大豆和蚯蚓生长试验,幵展三种增塑剂对生物 毒性研究。结果:三种增塑剂对真菌棒束梗霉属(/wr/flsp.)的毒性从大到小表现为: ESO >ATBC >DOP; DOP对大豆生长表现出很强的毒性,ESO、ATBC对大豆没有表 现出显著的毒性;ESO、ATBC对蚯蚓没有表现出明显的毒性,高浓度DOP对蚯蚓表 现出了显著的毒性。 (3)在纯菌降解条件下,测定三种增塑剂含量。结果:真菌棒束梗霉属(Jsarfa sp.) 对3种增塑剂降解率的大小为ATBC>ESO>DOP。 (4)以大蒜为试验作物,幵展新型和传统地膜的田区试验,以未覆盖地膜为对照。 并以覆盖用配方3 (ATBC)和配方7 (ESO)合成地膜做比较,结果:1.通过对土壤温 度水分的测试,不同种类地膜保温保墒效果从优到次为:ESO>DOP>ATBC>CK (未覆 膜);2.通过对土壤酶活性和微生物量碳的测试,土壤微生物和酶活性从高到低: ATBC>CK>ESO>DOP; 3.通过对试验种植作物的发芽率、株高、叶绿素、生物量和可 溶性蛋白含量的测定,作物品质从优到次:ESO>CK>ATBC>DOP。 综合田间试验的结果,薄膜从优到次为:ESO>ATBC>DOP。 (5)与DOP合成的传统地膜相比较,如果使用ATBC合成的新型地膜,每亩耕地 的费用将提高1.1元钱,而使用ESO合成的新型地膜,每亩地的费用将降低1.4元钱。 综合本文的试验结果,两种邻苯二甲酸二辛酯代用品都具有经济、技术和环境可 行性。 I 湖南农业大学硕士学位报告 关键词:乙酰柠檬酸三丁酯;环氧大豆油;邻苯二甲酸二辛酯;影响 II Abstract Abstract Plastic products have been concern with people's life, agriculture production and industry closely, but plastic additives (plasticizers), such as phthalate esters or phthalates caused the food and environment safety issues have attracted much attention. To achieve cleaner production by using low or no toxicity plasticizer plastics (including film) to replace the existing Dioctyl o-phthalate in plastics can control pollution from the source of plastic products manufacture. This paper has done the research about three kinds of plasticizer and investigated the feasibility of two Dioctyl o-phthalate substitutes. The research methods and results are as follows: (1) Compared with tradition process formula of film, by adding different amount of plasticizer in the processing of film. Through mechanical testing, X-ray diffraction and scanning electron microscope, the results showed that ATBC groups: formula 3 >formula 4 > formula 2 >formula 1, ESO groups: formula 7 > formula 8 >formula 6 >formula 5; Only if adding 35 and 30 phr ATBC and the using amount of DOP is 35,the PVC plastic can reach the standard of mechanics (GBT13735-1992). (2) Under the condition of laboratory simulation, by measuring the biomass of microorganism {Isaria sp.),soybean seed germination rate and the earthworm survival rate, studied the toxicity of different plasticizer to organism. The results indicated that the toxicity of three plasticizers to Isaria sp. was: ESO > ATBC > DOP. DOP shows obvious toxicity on soybean sprout and earthworm survival, but the ESO and ATBC shows little toxicity on soybean sprout and earthworms survival. (3) By determining different plasticizer content in the liquid culture condition. Results showed that the degradation rate of three plasticizer which was degraded by flingus {Isaria sp.) was ATBC > ESO > DOP. (4) Planting garlic by using different film in farm. Through measuring the soil temperature and moisture, the effect of water and heat preservation from good to poor were in the order of ESO〉DOP> ATBC> CK ( do not cover film ).Through the test of soil enzyme activities and microbial biomass carbon, the soil microbial activity from high to low were in the order of ATBC> CK> ESO> DOP. By measuring the test crops germination rate, in 沏南农业大学硕士学位报告 plant height, chlorophyll, biomass and soluble protein content, the quality of crop from high to poor were in the order of ESO>CK>ATBC>DOP. According to the results of field experiment, the effect of film from good to poor in the order of ESO〉ATBC>DOP. (5) Compared with DOP synthesis of traditional film,if use ATBC synthetic of new film will increase the cost of 1.1 yuan per acre, while use of the ESO synthetic of new film will reduce the cost of 1.4 yuan per acre. Above all the results of this paper, two kinds of dioctyl phthalate substitutes have economic, technical and environmental feasibility. Key words: Acetyl tributyl citrate esters; The epoxy soybean oil; Dioctyl phthalate; Affect IV 目 录 m m i 第一章绪论 i 1.1 土壤PAEs污染现状 1 1.1.1 PAEs 介绍 1 1.1.2 土壤PAEs污染现状 1 1.2 土壤PAEs污染的危害 2 1.2.1 PAEs对土壤微生物的影响 2 1.2.2 PAEs对植物的影响 3 1.2.3 PAEs对动物和人的影响 3 1.3国内外研究现状 4 1.4农用地膜发展现状 4 1.4.1 PVC 4 1.4.2 PE 地膜 5 1.4.3可降解地膜 5 1.4.4液态地膜 6 1.5增塑剂(塑化剂)发展现状 6 1.5.1增塑剂的发展趋势 6 1.5.2柠檬酸酯系列 7 1.5.3聚合物型增塑剂 8 1.5.4植物油基增塑剂 8 1.5.5环已烷二酯系列 8 III 湖南农业大学硕上学位报告 1.5.6离子液体 9 1.6不同类型增塑剂对塑料(地膜)性能的影响研究 9 1.7不同增塑剂在环境中的毒性和迁移研究 10 1.8报告的选题意义 10 1.9两种邻苯二甲酸二辛酯代用品的选择 11 1.10技术路线 12 第二章几种合成地膜的物理性能 14 2.1试验材料与仪器 14 2.1试验材料 14 2.2试验仪器 14 2.2试验方法 14 2.2.1塑料地膜合成试验 14 2.2.2测试与表征 15 2.3结果与分析 16 2.3.1几种农用地膜的力学性能 16 2.3.2 X射线衍射分析(XRD) 17 2.3.3扫描电子显微镜分析(SEM) 21 2.4 /J、g 25 第三章酞酸酯替代品的生物毒性研究 27 3.1试验材料与仪器 27 3.1.1试验材料 27 3.1.2试验仪器 28 目录 3.2试验方法 28 3.2.1微生物生长试验(真菌棒束梗霉属/■sar/a sp培养实验) 28 3.2.2大豆种子发芽试验 28 3.2.3蚯蚓急性毒性试验 29 3.3结果与分析 29 3.3.1三种增塑剂对真菌/.sp.生长的影响 29 3.3.2三种增塑剂对大豆种子发芽的影响 30 3.3.3三种增塑剂对姬蚓生长的影响 32 3.4 /J、@ 33 第四章酞酸酯替代品降解研究 34 4.1试验材料与仪器 34 4.1.1试验材料 34 4.1.2试验仪器 34 4.2试验方法 35 4.2.1微生物生长试验(真菌Zsar/a sp培养实验) 35 4.2.2检测方法 35 4.2.3质量控制 35 4.3结果与分析 36 4.3.1 ATBC降解结果 36 4.3.2 DOP降解结果 37 4.3.3 ESO降解结果 38 4.4小结 39 V 湖南农业大学硕士学位报告 第五章新型地膜的农田应用研究 40 5.1试验材料与仪器 40 5.1.1试验材料 40 5.1.2试验仪器 41 5.2试验方法 41 5.2.1试验设计 41 5.2.2样品采集 42 5.2.3检测方法 42 5.3结果与讨论 45 5.3.1地膜覆盖对土壤物理性质的影响 45 5.3.2地膜覆盖对土壤生物的影响 47 5.3.3对土壤植物生长影响结果 50 5.4 /J、@ 53 第六章总结与展望 54 6.1总结 54 6.2仓丨衞点、 55 6.3展望 55