CN111844923B - 一种农药盛装容器及其制备方法 - Google Patents
一种农药盛装容器及其制备方法 Download PDFInfo
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- CN111844923B CN111844923B CN202010633750.8A CN202010633750A CN111844923B CN 111844923 B CN111844923 B CN 111844923B CN 202010633750 A CN202010633750 A CN 202010633750A CN 111844923 B CN111844923 B CN 111844923B
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Abstract
本申请公开了一种农药盛装容器及其制备方法。所述盛装容器的器壁由内至外依次包括内衬层、复合层和表层,其中,所述内衬层包括重量比为(40~50):(30~40):(10~15):(7~10):(3~7):(2~5)的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡,所述复合层包括重量比为(55~62):(27~35):(5~10):(4~8)的低密度聚乙烯、聚乙烯醇、三聚氰胺和季戊四醇四硬脂酸酯,以及所述表层包括重量比为(35~45):(33~38):(15~20):(12~16):(7~10):(3~5):(1~2)的高密度聚乙烯、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂。所述盛装容器具有优异的密封性、抗渗透性、抗老化性、耐腐蚀性、机械强度、抗冲击性、稳定性、阻燃性等。
Description
技术领域
本申请涉及涂料领域,更具体地,涉及一种农药盛装容器及其制备方法。
背景技术
农药,是指用于预防、消灭或者控制危害农业、林业的病、虫、草和其他有害生物以及有目的地调节、控制、影响植物和有害生物代谢、生长、发育、繁殖过程的化学合成或者来源于生物、其他天然产物及应用生物技术产生的一种物质或者几种物质的混合物及其制剂。由此可见,农药是以用途来划分的概念,其化学组成则可以涵盖数量繁多的化合物类别,从而性质也千变万化,差异极大,例如,农药可以为pH酸性、碱性、中性、光不稳定性、热不稳定性、腐蚀性、化学活泼性等,不一而足。
众所周知,我国是农业大国,农药是农业生产中不可缺少的部分,当前我国农药的年产量也十分巨大,且其中三分之二为液体剂型,这些液体农药可以简化使用步骤,使用时只需稀释后即可对农作物进行喷施。常用的农药制剂包括杀菌剂、杀虫剂和除草剂等,其普遍浓度高且剧毒,对人体危害极大。因而,农药盛装和运输的安全性十分重要,传统对液体农药的包装方式为采用玻璃瓶进行盛装,玻璃瓶虽然抗渗透性较好,但存在易破损、成本高、自重大、内塞封口不严等缺点,这给生产运输及使用过程中带来诸多不便,且存在较大的安全隐患。
对此,目前部分液体农药已逐步开始采用塑料容器进行盛装,这就对塑料容器的材质提出了较高的要求,如优异的密封性、抗渗透性、抗老化性、耐腐蚀性、机械强度、稳定性等。但当前的农药盛装容器的上述性能仍旧存在较大的改进空间。
发明内容
[技术问题]
针对现有技术存在的不足,本申请的一个目的在于提供一种农药盛装容器,所述盛装容器可以为瓶、桶等,其在密封性、抗渗透性、抗老化性、耐腐蚀性、机械强度、抗冲击性、稳定性、阻燃性等方面均具有极其优异的表现。
本申请的另一个目的在于提供一种上述农药盛装容器的制备方法,所述制备方法将原料组分充分混炼,并同步挤出成型,从而能够充分发挥各组分的效力,制得性能优异的农药盛装容器。
[技术方案]
为了实现上述目的,根据本申请的一个实施方式提供了一种农药盛装容器,所述盛装容器的器壁由内至外依次包括内衬层、复合层和表层,其中,所述内衬层包括重量比为(40~50):(30~40):(10~15):(7~10):(3~7):(2~5)的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡,所述复合层包括重量比为(55~62):(27~35):(5~10):(4~8)的低密度聚乙烯(LDPE)、聚乙烯醇(PVA)、三聚氰胺和季戊四醇四硬脂酸酯,以及所述表层包括重量比为(35~45):(33~38):(15~20):(12~16):(7~10):(3~5):(1~2)的高密度聚乙烯(HDPE)、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂。
在本申请中,所述农药盛装容器的器壁包括内衬层、复合层和表层等,其中,所述内衬层采用特定用量的柠檬酸三乙酯和甘油酸改性SiO2相互配合,可以与聚酰胺和聚丙烯交织为致密的塑性体,再加入二苯醚和巴西棕榈蜡则可以提高分散性和加工性,从而减少了内衬层的结构缺陷和孔隙,延缓老化,增强稳定性,因而所述内衬层具有极其优异的密封性、抗渗透性、柔韧性、耐腐蚀性、稳定性等,并在与农药直接接触时能够有效阻隔农药,防止其渗透。所述表层为农药盛装容器的最外侧,其采用HDPE和ABS作为主体组分,加入山梨醇和聚乙烯吡咯烷酮以赋予HDPE与ABS之间较好的相容性,从而提高机械强度,并且还能够改善滑石粉和TiO2的分散性,充分发挥二者的补强作用,由此所述表层具有较高的机械强度以维持容器的形态,以及具有优良的阻燃性和抗紫外线性,并且也具有一定的阻隔性,能够阻止空气中氧气和水分的渗入。然而,所述内衬层与所述表层之间的复合性不佳,故本申请引入复合层来将二者复合在一起,所述复合层与内衬层和表层之间均具有良好的粘附性和相容性,从而使得三者结合为一个整体,即使经受较大的冲击也不会剥离,并展现出各自的优点以及克服缺点。此外,这种多层复合结构也赋予容器优良的抗冲击性能,在受到较大的机械冲击时也难以发生破损。
进一步地,所述内衬层包括重量比为(43~46):(35~37):(12~15):(8~9):(5~6):(4~5)的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡。在上述范围内,所述内衬层可以具有更加优良的抗渗透性、耐腐蚀性和稳定性等。
进一步地,所述复合层包括重量比为(58~60):(30~33):(7~9):(5~6)的低密度聚乙烯(LDPE)、聚乙烯醇、三聚氰胺和季戊四醇四硬脂酸酯。在上述范围内,所述复合层能够更好地将内衬层与表层复合在一起。
进一步地,所述表层包括重量比为(38~40):(35~36):(16~18):(14~15):(8~9):(4~5):(1~2)的高密度聚乙烯(HDPE)、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂。在上述范围内,所述表层可以具有更高的机械强度和耐冲击性。
进一步地,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌15~20分钟,过滤烘干,然后与无水乙醇混合制得浓度为3~5重量%的分散液,加入硅烷偶联剂在55~60℃下搅拌40~50分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在70~75℃下搅拌100~120分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:(5~7):(20~25):(5~7):(2~3)。在本申请中,首先采用硅烷偶联剂来活化SiO2的表面,然后在硬脂醇和十二烷基硫酸钠的配合下引入甘油酸,由此制得的甘油酸改性SiO2具有较佳的反应活性,能够首先与柠檬酸三乙酯反应偶联,然后再与聚酰胺和聚丙烯相互交织勾连,极大地增加了聚酰胺与聚丙烯之间的亲和性和相容性,使得二者的分子排列紧密,形成致密的内衬层,因而其可以具有极佳的密封性和抗渗透性。
进一步地,所述硅烷偶联剂可以为KH550。
进一步地,所述紫外吸收剂可以为UV-531(2-羟基-4-正辛氧基二苯甲酮)。其可以有效地赋予所述表层抗紫外性能。
此外,所述盛装容器的器壁厚度可以为0.1~100mm,优选0.5~10mm,更优选1.0~5.0mm,并且,所述内衬层、复合层和表层的厚度比例可以为(20~33%):(7~10%):(60~70%),优选为25%:10%:65%。在此厚度比例关系下,本申请的农药盛装容器能够较好地平衡抗渗透性、强度等性能。
根据本申请的另一个实施方式提供了上述农药盛装容器的制备方法,其包括以下步骤:
(1)将内衬层组分在215~225℃下加热熔融,由第一螺杆压实并挤出;
(2)将复合层组分在200~210℃下加热熔融,由第二螺杆压实并挤出;
(3)将表层组分在220~230℃下加热熔融,由第三螺杆压实并挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
根据本申请的上述制备方法可以有效熔融混合各组分,最终制得性能优异的农药盛装容器。
进一步地,在所述制备方法中,所述第一螺杆的转速可以为25~35rpm,优选为30rpm,所述第二螺杆的转速可以为10~15rpm,优选为13rpm,以及所述第三螺杆的转速可以为65~70rpm,优选为68rpm。
在本申请中,通过进一步限定各个螺杆的转速,由此即可获得所需厚度比例的内衬层、复合层和表层,之后即可吹塑成型获得根据本申请的农药盛装容器。
[有益效果]
综上所述,本申请具有以下有益效果:
根据本申请的农药盛装容器具有十分优良的密封性、抗渗透性、抗老化性、耐腐蚀性、机械强度、抗冲击性、稳定性、阻燃性等性能,因而可以盛装各种农药药剂而不会与之反应,且容器优良的阻隔性能既能够防止农药的渗出造成环境污染与危害,也能够阻挡外界的氧气和水分进入而影响农药的贮存。并且,容器优良的机械强度和抗冲击性还大大减少了其在农药贮存和运输过程中的破损。
此外,根据本申请的农药盛装容器的制备方法能够将原料组分充分混炼并同步挤出成型,从而获得性能优异的农药盛装容器。
具体实施方式
为了使本领域技术人员能够更清楚地理解本申请,以下结合实施例对本申请作进一步详细说明,但应当理解的是,以下实施例仅为本申请的优选实施方式,而本申请要求保护的范围并不仅局限于此。
<实施例>
实施例1
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为46:35:15:8:6:4的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在220℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将60:30:9:5的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在200℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为40:35:18:14:9:4:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在220℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌17分钟,过滤烘干,然后与无水乙醇混合制得浓度为4重量%的分散液,加入硅烷偶联剂KH550在57℃下搅拌45分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在73℃下搅拌110分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:6:23:6:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例2
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为43:37:12:9:5:5的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在220℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将58:33:7:6的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在210℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为40:35:18:14:9:4:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在220℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌15分钟,过滤烘干,然后与无水乙醇混合制得浓度为5重量%的分散液,加入硅烷偶联剂KH550在55℃下搅拌50分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在70℃下搅拌120分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:5:25:5:3。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例3
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为46:35:15:8:6:4的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在215℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将58:33:7:6的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在200℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为38:36:16:15:8:5:1的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在225℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌20分钟,过滤烘干,然后与无水乙醇混合制得浓度为3重量%的分散液,加入硅烷偶联剂KH550在60℃下搅拌40分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在75℃下搅拌100分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:7:20:7:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例4
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为43:37:12:9:5:5的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在225℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将60:30:9:5的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在210℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为38:36:16:15:8:5:1的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在225℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌16分钟,过滤烘干,然后与无水乙醇混合制得浓度为5重量%的分散液,加入硅烷偶联剂KH550在56℃下搅拌47分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在71℃下搅拌115分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:5:24:5:3。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例5
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为46:35:15:8:6:4的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在215℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将58:33:7:6的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在205℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为40:35:18:14:9:4:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在230℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌19分钟,过滤烘干,然后与无水乙醇混合制得浓度为3重量%的分散液,加入硅烷偶联剂KH550在58℃下搅拌42分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在74℃下搅拌105分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:7:21:7:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例6
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为43:37:12:9:5:5的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在225℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将60:30:9:5的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在205℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为40:35:18:14:9:4:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在230℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌15分钟,过滤烘干,然后与无水乙醇混合制得浓度为3重量%的分散液,加入硅烷偶联剂KH550在60℃下搅拌50分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在70℃下搅拌100分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:7:25:5:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例7
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为40:40:10:10:3:5的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在220℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将62:27:10:4的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在200℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为35:38:15:16:7:5:1的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在225℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌20分钟,过滤烘干,然后与无水乙醇混合制得浓度为5重量%的分散液,加入硅烷偶联剂KH550在55℃下搅拌40分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在75℃下搅拌120分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:5:20:7:3。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例8
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为50:30:15:7:7:2的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在220℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将55:35:5:8的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在210℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为35:38:15:16:7:5:1的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在230℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌17分钟,过滤烘干,然后与无水乙醇混合制得浓度为4重量%的分散液,加入硅烷偶联剂KH550在57℃下搅拌45分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在73℃下搅拌110分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:6:23:6:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例9
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为40:40:10:10:3:5的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在215℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将55:35:5:8的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在205℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为45:33:20:12:10:3:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在220℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌15分钟,过滤烘干,然后与无水乙醇混合制得浓度为5重量%的分散液,加入硅烷偶联剂KH550在55℃下搅拌50分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在70℃下搅拌120分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:5:25:5:3。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
实施例10
采用以下根据本申请的制备方法来制备所述农药盛装容器:
(1)将重量比为50:30:15:7:7:2的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分在225℃下加热熔融,由第一螺杆压实并以30rpm的转速挤出;
(2)将62:27:10:4的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分在210℃下加热熔融,由第二螺杆压实并以13rpm的转速挤出;
(3)将重量比为45:33:20:12:10:3:2的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分在205℃下加热熔融,由第三螺杆压实并以68rpm的转速挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
其中,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌20分钟,过滤烘干,然后与无水乙醇混合制得浓度为3重量%的分散液,加入硅烷偶联剂KH550在60℃下搅拌40分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在75℃下搅拌100分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:7:20:7:2。
由此,即制得根据本申请的农药盛装容器,其中容器的容量为120mL,器壁的厚度为1.0mm,内衬层、复合层和表层的厚度比例为25%:10%:65%。
对比实施例1
除了在步骤(1)中采用重量比为35:45:7:13:2:7的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例2
除了在步骤(1)中采用重量比为55:25:18:5:10:1的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡的内衬层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例3
除了在步骤(2)中采用重量比为50:40:3:10的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例4
除了在步骤(2)中采用重量比为65:25:13:3的LDPE、PVA、三聚氰胺和季戊四醇四硬脂酸酯的复合层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例5
除了在步骤(3)中采用重量比为30:42:12:20:5:7:0.5的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例6
除了在步骤(3)中采用重量比为50:30:25:10:12:2:3的HDPE、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂UV-531的表层组分之外,以与实施例1相同的方式制得了农药盛装容器。
对比实施例7
除了在步骤(1)中采用普通SiO2来代替甘油酸改性SiO2之外,以与实施例1相同的方式制得了农药盛装容器。
<测试实施例>
对实施例1至10中根据本申请的制备方法制得的农药盛装容器以及对比实施例1至7中制得的农药盛装容器,或由这些容器制得的试样进行下述性能的测定,其中,试样可由上述容器裁切制得。结果显示于以下表1中。
(I)拉伸强度(MPa):根据国家标准《GB/T 1040.1-2018塑料拉伸性能的测定第1部分:总则》来进行测定;
(II)弯曲强度(MPa):根据国家标准《GB/T 9341-2008塑料弯曲性能的测定》来进行测定;
(III)缺口冲击强度(MPa):根据国家标准《GB/T 1843-2008塑料悬臂梁冲击强度的测定》来进行测定;
(IV)最大跌落高度(m):根据国家标准《GB/T 4857.5-1992包装运输包装件跌落试验方法》来进行测定;
(V)抗老化性:根据国家标准《GB/T 16422.3-2014塑料实验室光源暴露试验方法第3部分荧光紫外灯》来进行测定,其中采用UVA-340灯和8h干燥+4h凝露的方式进行人工气候老化循环72小时后,测定容器的断裂伸长率保持率(%);
(VI)抗渗透性(抗有机气体透过性):根据国家标准《GB/T28765-2012包装材料塑料薄膜、片材和容器的有机气体透过率试验方法》来进行测定容器的有机气体透过率,单位为毫克每包装物每天mg/(pkg·d);
(VII)抗渗透性(抗氧气透过性):根据国家标准《GB/T31354-2014包装件和容器氧气透过性测试方法库仑计检测法》来进行测定容器的氧气透过率,单位为立方厘米每天cm3/d;
(VIII)抗渗透性(抗水蒸气透过性):根据国家标准《GB/T31355-2014包装件和容器水蒸气透过性测试方法红外传感器法》来进行测定容器的水蒸气透过率,单位为毫克每天mg/d;以及
(X)阻燃性:采用塑料阻燃等级UL94进行评价。
[表1]
测定项目 | I | II | III | VI | V | VI | VII | VIII | X |
实施例1 | 54.7 | 33.9 | 152.1 | 5.66 | 93.8 | 0.25 | 0.0012 | 0.18 | V0 |
实施例2 | 53.9 | 34.8 | 153.5 | 5.89 | 92.5 | 0.24 | 0.0011 | 0.19 | V0 |
实施例3 | 54.1 | 33.4 | 151.9 | 5.63 | 91.8 | 0.27 | 0.0014 | 0.19 | V0 |
实施例4 | 55.2 | 34.7 | 154.0 | 5.50 | 94.2 | 0.25 | 0.0012 | 0.16 | V0 |
实施例5 | 53.5 | 35.2 | 153.4 | 5.74 | 93.4 | 0.22 | 0.0013 | 0.17 | V0 |
实施例6 | 54.4 | 34.1 | 152.8 | 5.77 | 92.1 | 0.29 | 0.0014 | 0.17 | V0 |
实施例7 | 52.8 | 32.5 | 150.8 | 5.51 | 91.8 | 0.31 | 0.0016 | 0.20 | V1 |
实施例8 | 51.9 | 31.5 | 150.4 | 5.45 | 92.5 | 0.29 | 0.0014 | 0.22 | V1 |
实施例9 | 51.5 | 33.2 | 151.5 | 5.62 | 93.1 | 0.34 | 0.0015 | 0.20 | V0 |
实施例10 | 53.1 | 31.9 | 152.0 | 5.49 | 90.9 | 0.30 | 0.0015 | 0.21 | V1 |
对比实施例1 | 46.8 | 28.9 | 148.7 | 5.13 | 89.1 | 0.89 | 0.0124 | 0.73 | V2 |
对比实施例2 | 48.9 | 29.3 | 146.8 | 5.02 | 88.4 | 0.93 | 0.0112 | 0.69 | V1 |
对比实施例3 | 44.5 | 27.1 | 138.5 | 4.31 | 85.3 | 0.31 | 0.0015 | 0.23 | 5VB |
对比实施例4 | 42.7 | 27.8 | 134.3 | 4.18 | 87.2 | 0.29 | 0.0016 | 0.25 | 5VA |
对比实施例5 | 35.8 | 24.3 | 118.4 | 3.22 | 75.8 | 0.38 | 0.0038 | 0.45 | V2 |
对比实施例6 | 33.2 | 22.5 | 111.9 | 3.57 | 78.2 | 0.36 | 0.0042 | 0.40 | 5VA |
对比实施例7 | 49.2 | 30.4 | 141.6 | 5.19 | 88.4 | 0.97 | 0.0105 | 0.92 | V0 |
参见上述表1,可以看出,根据本申请的农药盛装容器在拉伸强度、弯曲强度、缺口冲击强度、最大跌落高度、抗老化性、抗渗透性、阻燃性等方面具有非常优异的表现。
相比之下,对比实施例1和2中的内衬层的组分配比在本申请的范围之外,其抗渗透性明显低于本申请实施例,且性状变化也影响了其与复合层的粘附,进而其机械强度和抗冲击性也受到了一定的影响。对比实施例3和4中的复合层的组分配比在本申请的范围之外,其机械强度和抗冲击性有了明显下降,表明该复合层的复合能力不足。对比实施例5和6中的表层的组分配比在本申请的范围之外,其机械强度和抗冲击性大幅度下降,且抗渗透性和抗老化性均有不足。对比实施例7未采用改性的SiO2,其抗渗透性也出现了明显的降低。
本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (10)
1.一种农药盛装容器,其特征在于,所述盛装容器的器壁由内至外依次包括内衬层、复合层和表层,其中,所述内衬层包括重量比为(40~50):(30~40):(10~15):(7~10):(3~7):(2~5)的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡,所述复合层包括重量比为(55~62):(27~35):(5~10):(4~8)的低密度聚乙烯、聚乙烯醇、三聚氰胺和季戊四醇四硬脂酸酯,以及所述表层包括重量比为(35~45):(33~38):(15~20):(12~16):(7~10):(3~5):(1~2)的高密度聚乙烯、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂。
2.根据权利要求1所述的农药盛装容器,其特征在于,所述内衬层包括重量比为(43~46):(35~37):(12~15):(8~9):(5~6):(4~5)的聚酰胺、聚丙烯、柠檬酸三乙酯、甘油酸改性SiO2、二苯醚和巴西棕榈蜡。
3.根据权利要求1所述的农药盛装容器,其特征在于,所述复合层包括重量比为(58~60):(30~33):(7~9):(5~6)的低密度聚乙烯、聚乙烯醇、三聚氰胺和季戊四醇四硬脂酸酯。
4.根据权利要求1所述的农药盛装容器,其特征在于,所述表层包括重量比为(38~40):(35~36):(16~18):(14~15):(8~9):(4~5):(1~2)的高密度聚乙烯、ABS、滑石粉、TiO2、山梨醇、聚乙烯吡咯烷酮和紫外吸收剂。
5.根据权利要求1所述的农药盛装容器,其特征在于,所述甘油酸改性SiO2采用以下方法制得:将SiO2用10%的硫酸分散搅拌15~20分钟,过滤烘干,然后与无水乙醇混合制得浓度为3~5重量%的分散液,加入硅烷偶联剂在55~60℃下搅拌40~50分钟,然后加入甘油酸、硬脂醇和十二烷基硫酸钠在70~75℃下搅拌100~120分钟,过滤烘干,其中,SiO2、硅烷偶联剂、甘油酸、硬脂醇和十二烷基硫酸钠的重量比为100:(5~7):(20~25):(5~7):(2~3)。
6.根据权利要求5所述的农药盛装容器,其特征在于,所述硅烷偶联剂为KH550。
7.根据权利要求1所述的农药盛装容器,其特征在于,所述紫外吸收剂为UV-531。
8.根据权利要求1所述的农药盛装容器,其特征在于,所述盛装容器的器壁厚度为0.1~100mm,所述内衬层、复合层和表层的厚度比例为(20~33%):(7~10%):(60~70%)。
9.一种权利要求1至8任一项所述的农药盛装容器的制备方法,其特征在于,包括以下步骤:
(1)将内衬层组分在215~225℃下加热熔融,由第一螺杆压实并挤出;
(2)将复合层组分在200~210℃下加热熔融,由第二螺杆压实并挤出;
(3)将表层组分在220~230℃下加热熔融,由第三螺杆压实并挤出;以及
(4)将步骤(1)、(2)和(3)获得的熔融体同时匀速挤出,由模头复合形成料胚,进而吹塑成型。
10.根据权利要求9所述的制备方法,其特征在于,所述第一螺杆的转速为25~35rpm,所述第二螺杆的转速为10~15rpm,以及所述第三螺杆的转速为65~70rpm。
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