CN105619985B - 接枝法永久性消雾流滴农用膜及其制备方法 - Google Patents

接枝法永久性消雾流滴农用膜及其制备方法 Download PDF

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CN105619985B
CN105619985B CN201610140379.5A CN201610140379A CN105619985B CN 105619985 B CN105619985 B CN 105619985B CN 201610140379 A CN201610140379 A CN 201610140379A CN 105619985 B CN105619985 B CN 105619985B
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plastic film
drip
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CN105619985A (zh
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房乾
房双宽
尹德军
孙美菊
孟忠志
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Shandong Kuanli New Material Co ltd
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HENAN YINFENG PLASTIC CO Ltd
Tumen City Swallow Plastics Co Ltd
ZIBO LINZI WIDE FORCE PLASTIC MANUFACTURING FACTORY
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Abstract

本发明涉及一种接枝法永久性消雾流滴农用膜及其制备方法,属于农用塑料薄膜技术领域。所述农用膜包括内层、中间层和外层三层结构,内层由EVA、LDPE、接枝母料和防老化母料制得,中间层由EVA、mLLDPE、LDPE和防老化母料制得,外层由mLLDPE、LDPE、防老化母料制得,其中,接枝母料由EVA、引发剂、丙烯酸、流滴剂和消雾剂制得;所述的制备方法是按照配方量,分别将内层、中间层和外层的原料加入到混料机内进行混合,然后将混合后的原料依次加入至各料斗中进行挤出,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。本发明的消雾流滴功能实现了与农膜使用寿命相同步的效果;其制备方法简单,设备投资少,操作方便。

Description

接枝法永久性消雾流滴农用膜及其制备方法
技术领域
本发明涉及一种接枝法永久性消雾流滴农用膜及其制备方法,属于农用塑料薄膜技术领域。
背景技术
农用大棚膜作为园艺设施的重要覆盖材料之一,其消雾流滴的功能性对能否满足植物生长的需要尤为重要。目前我国农膜企业生产的农用大棚膜,大都采取两种生产工艺:一种是内添加法聚乙烯/EVA消雾流滴膜,即把小分子量的流滴剂、消雾剂通过母料法加入到大棚膜内,其中的流滴剂、消雾剂均是表面活性剂,短时间内会迁移到薄膜的表面,由于棚内水气的产生会不断地冲刷薄膜的表面,致使消雾剂、流滴剂被逐渐冲刷掉,这是导致农用功能性大棚膜消雾期和流滴期时间短的主要原因;另一种是外涂覆PO膜,即用涂液的方法,把涂液通过电晕后涂覆到薄膜的表层,在实际应用过程中,大棚骨架与涂覆层的摩擦会导致涂层脱落,棚内产生的水滴滴落在作物上,由此失去了消雾流滴效果,容易给菜农造成极大的损失,也会因产品质量问题造成菜农与企业之间产生纠纷。
发明内容
本发明的目的是提供一种接枝法永久性消雾流滴农用膜,解决了现有农用大棚膜存在的消雾期短、流滴期短、质量差的问题,具有使用寿命长、消雾流滴期长的特点;本发明同时提供其制备方法。
本发明所述的接枝法永久性消雾流滴农用膜,包括内层、中间层和外层三层结构:
以质量百分数计,内层由以下组分制成:
以质量百分数计,中间层由以下组分制成:
以质量百分数计,外层由以下组分制成:
mLLDPE 40-60%
LDPE 30-40%
防老化母料 10-15%
其中,所述的接枝母料由以下质量百分数的原料制成:
其中:
所述的内层和中间层中的EVA的型号为443,生产厂家为韩国现代。
所述的中间层和外层中的mLLDPE的型号为1018HA或2101HA。
所述的内层、中间层和外层中的LDPE的型号为2426F或2420D。
所述的内层、中间层和外层中的防老化母料的制备过程如下:
将5wt%的光稳定剂944与95wt%的聚乙烯树脂进行混合,经挤出、塑化和造粒后,得到防老化母料。
所述的接枝母料中EVA的型号为443,生产厂家为韩国现代。
所述的接枝母料中引发剂的型号为R1,生产厂家为德国朗盛;流滴剂的型号为LY-6,生产厂家为杭州临安涂料助剂化工有限公司;消雾剂的型号为TS-403,生产厂家为台湾丰笙;丙烯酸优选的型号为AA,生产厂家为上海甲美精细化工有限公司。
所述的接枝母料的制备过程包括以下步骤:
(1)将配方量的EVA、引发剂、丙烯酸加入到搅拌机内搅拌10min,然后放入料斗中;
(2)开启双螺杆挤出机,对料斗中的物料在140-190℃下进行挤出造粒,同时在双螺杆挤出机塑化段的侧向喂料斗内加入配方量的流滴剂和消雾剂进行均化反应,经机头成型、热切造粒后,得到接枝母料。
本发明所述的接枝法永久性消雾流滴膜的制备方法,包括以下步骤:
(1)按照配方量,分别将内层、中间层和外层的原料加入到混料机内进行混合;
(2)对应共挤机机组结构的内层料斗、中间层料斗和外层料斗,将混合后的原料依次加入至各料斗中进行挤出,待管泡稳定后,调整薄膜的宽度及厚度,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。
其中,优选的技术方案如下:
步骤(1)中混合时间为10min。
步骤(2)中吹膜时的吹胀比为2.5-3.5,层比为3:4:3。
改性基础树脂是基础树脂通过采用不同的工艺操作条件来改变或赋予基础树脂不同的树脂而得到的。本发明的接枝法永久性消雾流滴农用膜是将改性基础树脂的官能团和消雾剂、流滴剂的分子结构相结合,从而实现长效消雾流滴功能的持效期,改性后的永久性消雾流滴农用膜,其基础树脂与消雾剂、流滴剂分子之间形成稳定的共价键,作用力增强,在薄膜表面形成稳定的极性基团,即达到荷叶仿生结构。
本发明中:
接枝法永久性消雾流滴农用膜是将流滴剂功能性官能团与高分子材料中的官能团通过接枝反应相结合,形成稳固的极性的官能团,有序的排列在农用膜表面,使其达到抗耐磨与农膜制品寿命同步和永久性消雾流滴的效果。其制备方法与外涂覆PO膜相比的显著特点是:生产流程短,设备投资少,操作方便,能够消除因工艺流程长、不可控的因素多导致出现产品质量问题。
与内添加法聚乙烯/EVA消雾流滴膜相比,本发明解决了农膜消雾流滴期短的问题,满足了植物生长周期的需求。另外,由于接枝法永久性消雾流滴农用膜实现了与农膜使用寿命的同步,农膜可连续使用2-3年或更长的时间,结束每年必换农膜的历史,为国家节约了大量的能源与资源,为菜农节约了蔬菜大棚的投资,具有显著的经济效益和社会效益。
接枝母料制备过程中的反应机理如下:EVA、引发剂R1和丙烯酸在高速搅拌机内进行密炼密炼,引发剂R1受热产生自由基R1·,自由基R1·与EVA树脂进行反应,夺取EVA树脂支链结构中的H原子,生成带有EVA树脂结构的自由基EVA·,此阶段为链引发过程;EVA·与丙烯酸进行反应,生成带有EVA和丙烯酸分子结构的自由基EVA-AA·,AA为丙烯酸,该自由基夺取临近EVA树脂分子结构中的H原子,生成EVA树脂与丙烯酸的接枝聚合物EVA-AA以及自由基EVA·,此阶段为链增长过程,直至化学反应链终止。
本发明的有益效果如下:
本发明的接枝法永久性消雾流滴农用膜中的消雾流滴功能实现了与农膜使用寿命相同步的效果,能够连续使用2-3年或更长的时间,荷叶仿生学的应用为企业产品更新换代、产品质量提升奠定了良好的基础;其制备方法简单,生产流程短,设备投资少,操作方便,为菜农节约了对于蔬菜大棚的投资。
附图说明
图1是本发明的工艺流程图。
图2是本发明中接枝母料的工艺流程图。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
接枝法永久性消雾流滴农用膜的原料配方组成见表1。
表1原料配方组成
其中,接枝母料的配方组成见表2。
表2接枝母料配方组成
原料名称 重量/kg 生产厂家
EVA-443 73 韩国现代
引发剂R1 4 德国朗盛
丙烯酸-AA 7 上海甲美
流滴剂LY-6 15 杭州临安助剂
消雾剂TS-403 1 台湾丰笙
接枝母料的制备方法如下:
(1)将EVA-443、引发剂R1、丙烯酸-AA加入到搅拌机内搅拌10min,然后放入料斗中;
(2)开启双螺杆挤出机,对料斗中的物料在机筒各加温区按照140-190℃的温度进行挤出造粒,同时在双螺杆挤出机塑化段的侧向喂料斗内加入流滴剂LY-6和消雾剂TS-403进行均化反应,经机头成型、热切造粒后,得到接枝母料,其中,双螺杆挤出机的长径比为1:48。
接枝法永久性消雾流滴农用膜的制备方法如下:
(1)将表1中内层、中间层和外层的原料分别加入到混料机内混合10min;
(2)对应共挤机机组结构的内层料斗、中间层料斗和外层料斗,将混合后的原料依次加入至各料斗中进行挤出,待管泡稳定后,调整薄膜的宽度及厚度,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。其中,吹膜时的吹胀比为2.5-3.5;内层、外层和中间层的厚度之比为3:4:3;共挤机的螺杆长径比为1:30,机头直径为0.5-3m。
按照国家标准GB/4455-2006和GB/T20202-2006,对于本实施例中得到的产品进行质量检测与分析,所用实验检测仪器如下:
分析结果见表3。
表3实施例1产品性能检测指标
项目 单位 国家标准 实测结果
拉伸强度(纵向/横向) MPa≥ 16 24.10/26.85
断裂伸长率(纵向/横向) %≥ 320-350 824/1125
直角撕裂强度(纵向/横向) KN/m≥ 60 103.44/117.37
可见光透光率 %≥ 85 91.5
雾度 %≤ 35 10.5
实施例2
接枝法永久性消雾流滴农用膜的原料配方组成见表4。
表4原料配方组成
其中,接枝母料的配方组成见表5。
表5接枝母料配方组成
接枝母料的制备方法如下:
(1)将EVA-443、引发剂R1、丙烯酸-AA加入到搅拌机内搅拌10min,然后放入料斗中;
(2)开启双螺杆挤出机,对料斗中的物料在机筒各加温区按照140-190℃的温度进行挤出造粒,同时在双螺杆挤出机塑化段的侧向喂料斗内加入流滴剂LY-6和消雾剂TS-403进行均化反应,经机头成型、热切造粒后,得到接枝母料,其中,双螺杆挤出机的长径比为1:48。
接枝法永久性消雾流滴农用膜的制备方法如下:
(1)将表4内层、中间层和外层的原料分别加入到混料机内混合10min;
(2)对应共挤机机组结构的内层料斗、中间层料斗和外层料斗,将混合后的原料依次加入至各料斗中进行挤出,待管泡稳定后,调整薄膜的宽度及厚度,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。其中,吹膜时的吹胀比为2.5-3.5;内层、外层和中间层的厚度之比为3:4:3;共挤机的螺杆长径比为1:30,机头直径为0.5-3m。
按照国家标准GB/4455-2006和GB/T20202-2006,对于本实施例中得到的产品进行质量检测与分析,所用实验检测仪器同实施例1,分析结果见表6。
表6实施例2产品性能检测指标
项目 单位 国家标准 实测结果
拉伸强度(纵向/横向) MPa≥ 16 24.40/26.2
断裂伸长率(纵向/横向) %≥ 320-350 844/1122
直角撕裂强度(纵向/横向) KN/m≥ 60 105.48/118.95
可见光透光率 %≥ 85 91.2
雾度 %≤ 35 11.2
实施例3
接枝法永久性消雾流滴农用膜的原料配方组成见表7。
表7原料配方组成
其中,接枝母料的配方组成见表8。
表8接枝母料配方组成
原料名称 重量/kg 生产厂家
EVA-443 71 韩国现代
引发剂R1 4.5 德国朗盛
丙烯酸-AA 8.5 上海甲美
流滴剂LY-6 15 杭州临安助剂
消雾剂TS-403 1 台湾丰笙
接枝母料的制备方法如下:
(1)将EVA-443、引发剂R1、丙烯酸-AA加入到搅拌机内搅拌10min,然后放入料斗中;
(2)开启双螺杆挤出机,对料斗中的物料在机筒各加温区按照140-190℃的温度进行挤出造粒,同时在双螺杆挤出机塑化段的侧向喂料斗内加入流滴剂LY-6和消雾剂TS-403进行均化反应,经机头成型、热切造粒后,得到接枝母料,其中,双螺杆挤出机的长径比为1:48。
接枝法永久性消雾流滴农用膜的制备方法如下:
(1)将表4内层、中间层和外层的原料分别加入到混料机内混合10min;
(2)对应共挤机机组结构的内层料斗、中间层料斗和外层料斗,将混合后的原料依次加入至各料斗中进行挤出,待管泡稳定后,调整薄膜的宽度及厚度,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。其中,吹膜时的吹胀比为2.5-3.5;内层、外层和中间层的厚度之比为3:4:3;共挤机的螺杆长径比为1:30,机头直径为0.5-3m。
按照国家标准GB/4455-2006和GB/T20202-2006,对于本实施例中得到的产品进行质量检测与分析,所用实验检测仪器同实施例1,分析结果见表9。
表9实施例3产品性能检测指标

Claims (10)

1.一种接枝法永久性消雾流滴农用膜,包括内层、中间层和外层三层结构,其特征在于:
以质量百分数计,内层由以下组分制成:
EVA 10-20%
LDPE 10-30%
接枝母料 50-70%
防老化母料 10-15%
以质量百分数计,中间层由以下组分制成:
EVA 30-50%
mLLDPE 20-50%
LDPE 20-40%
防老化母料 10-15%
中间层所有原料的总和为100%
以质量百分数计,外层由以下组分制成:
mLLDPE 40-60%
LDPE 30-40%
防老化母料 10-15%
外层所有原料的总和为100%
其中,所述的接枝母料由以下质量百分数的原料制成:
EVA 65-75%
引发剂 3.5-4.5%
丙烯酸 7-9%
流滴剂 15-18%
消雾剂 0.9-1.2%
接枝母料所有原料的总和为100%。
2.根据权利要求1所述的接枝法永久性消雾流滴农用膜,其特征在于:内层和中间层中的EVA的型号为443,生产厂家为韩国现代;中间层和外层中的mLLDPE的型号为1018HA或2101HA;内层、中间层和外层中的LDPE的型号为2426F或2420D。
3.根据权利要求1所述的接枝法永久性消雾流滴农用膜,其特征在于:接枝母料中EVA的型号为443,生产厂家为韩国现代;接枝母料中引发剂的型号为R1,生产厂家为德国朗盛。
4.根据权利要求1所述的接枝法永久性消雾流滴农用膜,其特征在于:内层、中间层和外层中的防老化母料的制备过程如下:
将5wt%的光稳定剂944与95wt%的聚乙烯树脂进行混合,经挤出、塑化和造粒后,得到防老化母料。
5.根据权利要求1所述的接枝法永久性消雾流滴农用膜,其特征在于:接枝母料中流滴剂的型号为LY-6,生产厂家为杭州临安涂料助剂化工有限公司;消雾剂的型号为TS-403,生产厂家为台湾丰笙。
6.根据权利要求1所述的接枝法永久性消雾流滴农用膜,其特征在于:接枝母料的制备过程包括以下步骤:
(1)将配方量的EVA、引发剂、丙烯酸加入到搅拌机内进行搅拌,然后放入料斗中;
(2)开启双螺杆挤出机,对料斗中的物料进行挤出造粒,同时在双螺杆挤出机塑化段的侧向喂料斗内加入配方量的流滴剂和消雾剂进行均化反应,经机头成型、热切造粒后,得到接枝母料。
7.根据权利要求6所述的接枝法永久性消雾流滴农用膜,其特征在于:步骤(1)中搅拌时间为10min;步骤(2)中挤出温度为140-190℃。
8.一种权利要求1-7任一所述的接枝法永久性消雾流滴农用膜的制备方法,其特征在于:包括以下步骤:
(1)按照配方量,分别将内层、中间层和外层的原料加入到混料机内进行混合;
(2)对应共挤机机组结构的内层料斗、中间层料斗和外层料斗,将混合后的原料依次加入至各料斗中进行挤出,待管泡稳定后,调整薄膜的宽度及厚度,经吹膜、上牵引、导辊至下牵引、收卷、计量称重后,得到接枝法永久性消雾流滴膜。
9.根据权利要求8所述的接枝法永久性消雾流滴农用膜的制备方法,其特征在于:步骤(1)中混合时间为10min。
10.根据权利要求8所述的接枝法永久性消雾流滴农用膜的制备方法,其特征在于:步骤(2)中吹膜时的吹胀比为2.5-3.5,层比为3:4:3。
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