CN108467537A - 一种防雾塑料棚膜及其制备方法 - Google Patents
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Abstract
本发明涉及一种防雾塑料棚膜及其制备方法,属于防雾膜技术领域。本发明以正硅酸乙酯、钛酸四丁酯、纳米氧化锡为原料配置成多元复合溶胶,微观上存在氧空穴,空穴具有超亲水性,因液滴尺寸远远大于空穴尺寸,故宏观上表现出超亲水性,同时通过羟丙基纤维素加入使复合溶胶颗粒的团聚程度降低、颗粒均匀分布,进而使形成的多级结构复合纳米粒子微球拥有更大的比表面积,使多级结构复合纳米粒子微球表面粗糙度增加,可有效吸附水滴,水滴会不断地铺开形成水膜,使得棚膜亲水性能得到提高,提高防雾性能。本发明中添加的多级结构复合纳米粒子微球具有较强的光散射特征,加入棚膜后对紫外线有显著阻隔作用且改善了农膜对可见光的透光性。
Description
技术领域
本发明涉及一种防雾塑料棚膜及其制备方法,属于防雾膜技术领域。
背景技术
由于气候寒冷,塑料棚内外温湿度差异较大,致使水蒸气蒸发到棚膜内壁时凝结成水滴,而普通的塑料棚膜表面能较低,水滴不能形成连续的水膜。在这种情况下,凝结成的水滴对农作物的生长产生较大危害,例如使光线发生折射及反射,造成材料的透光率大大降低,影响光合作用。若水滴聚集变大滴落到农作物上,会使其腐败、枯烂;雾滴滴落会増加棚内的湿度,为病虫害的产生提供了适宜的条件。
防雾材料是通过防雾剂来发挥作用的,防雾剂起到防雾作用的机理,可以用材料的润湿理论来解释。对于防雾剂来说,无论是内添加还是外涂覆型都具有典型的表面活性剂恃征。防雾剂的结构中多数都含有亲水及亲油基团,因此可赋予基材表面强烈的疏水并亲水的双重性质,具有比较好的界面活性。在内添加法中,表面活性剂的加入使得材料中分子的运动慢慢地迁移到材料的外表面,覆盖在高聚物的低能表面上,提高其表面能。表面活性剂自动地在材料的表面排列成亲水基向外、亲油基向内的状态,当水蒸气接触到材料表面时被亲水基吸附,借助于表面活性剂的活性所形成的低界面张力使得水滴铺展并沿材料表面流下,因此避免了水滴积聚到一定大小时,从膜面垂直降落,此性能即为防雾性。
经过三十多年的研究与实践,已由最初的功能单一逐步向多功能复合型棚膜的方向发展,树脂原料也从PE、PVC向EVA发展,抗老化剂、保温剂、防雾滴剂的研究应用也取得了一定成果,在防雾膜的有效使用上也提出了一些技术要点。PVC棚膜透光率较高,保温性和透水性较好,流滴持效期较长,但其应用受到限制。PE与PVC相比,在耐寒性、防尘、加工、价格及废膜回收、处理等方面具有一定优势,但其防雾性能及保温性能却不尽如人意。
发明内容
本发明所要解决的技术问题:针对现有棚膜防雾性能、保温性能以及透光率较差的问题,提供了一种防雾塑料棚膜及其制备方法。
为解决上述技术问题,本发明采用的技术方案是:
一种防雾塑料棚膜,由下述重量份原料制备而成:2~3份多级结构复合纳米粒子微球,0.02~0.03份硅烷偶联剂A-171,1.6~2.4份司班60,100~150份EVA塑料,0.30~0.45份聚甘油脂肪酸酯,0.10~0.15份抗氧化剂,0.30~0.45份光稳定剂。
所述多级结构复合纳米粒子微球为正硅酸乙酯、钛酸四丁酯、羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡组成的浆料,喷雾干燥成型后高温煅烧并水洗干燥制成。
所述正硅酸乙酯、钛酸四丁酯、羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡的重量份为10~20份正硅酸乙酯,8~12份钛酸四丁酯,0.3~0.5份羟丙基纤维素,1.0~1.2份聚乙二醇辛基苯基醚,2~3份纳米氧化锡。
所述喷雾干燥温度为180~240℃,所述高温煅烧温度为500~550℃。
所述抗氧化剂为抗氧化剂1010、抗氧化剂168、抗氧化剂264中的任意一种或多种。
所述光稳定剂为光稳定剂770、光稳定剂944、光稳定剂292中的任意一种或多种。
所述的一种防雾塑料棚膜的制备方法,具体步骤为:
(1)取正硅酸乙酯、钛酸四丁酯加入无水乙醇中混合均匀,再滴加质量分数为95%乙醇溶液至正硅酸乙酯质量的10~30倍,滴加完毕后在60~65℃下保温反应1~2h,得复合溶胶;
(2)取羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡,加入复合溶胶中混合均匀,再在60~65℃下保温反应1~2h,并用氨水调节pH至9~10,得浆料;
(3)将浆料喷雾干燥后煅烧,再水洗干燥得多级结构复合纳米粒子微球;
(4)取多级结构复合纳米粒子微球、硅烷偶联剂A-171、司班60、100~150gEVA塑料、聚甘油脂肪酸酯、抗氧化剂、光稳定剂,装入高速混合机中混合均匀,得混合料;
(5)将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区120~150℃,2区150~160℃,3区160~175℃,4区175~180℃,转速为30~50r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为150~180℃,螺杆转速为100~200r/min,螺杆长径比L/D为20:1~40:1,吹胀比为2:1~4:1,拉伸比为3:1~6:1,挤出吹塑成膜,膜厚度控制为0.03~0.04mm,得防雾塑料棚膜。
本发明与其他方法相比,有益技术效果是:
(1)本发明以正硅酸乙酯、钛酸四丁酯、纳米氧化锡为原料配置成多元复合溶胶,微观上存在氧空穴,空穴具有超亲水性,因液滴尺寸远远大于空穴尺寸,故宏观上表现出超亲水性,同时通过羟丙基纤维素加入使复合溶胶颗粒的团聚程度降低、颗粒均匀分布,并且粒径变小,复合溶胶晶粒纳米化,进而使形成的多级结构复合纳米粒子微球拥有更大的比表面积,使多级结构复合纳米粒子微球表面粗糙度增加,可有效吸附水滴,水滴会不断地铺开形成水膜,使得棚膜亲水性能得到提高,提高防雾性能;
(2)本发明利用复合溶胶制成的多级结构复合纳米粒子微球,加入棚膜材料中起到异相成核的作用,使 EVAC 的结晶度增加,提高棚膜的拉伸强度,且由于纳米粒子尺寸小,其它助剂可以很好地分散在棚膜表面,助剂的分散效果得到改善,使得聚甘油脂肪酸酯中的极性基团暴露出来,从而使水更易在棚膜表面润湿,防止了水蒸气在棚膜内表面凝结成雾;
(3)本发明中添加的多级结构复合纳米粒子微球具有较强的光散射特征,加入棚膜后会对紫外线有显著阻隔作用,同时细小的粒径又不妨碍可见光的透入,且纳米粒子能促进棚膜晶粒的细化,改善了农膜对可见光的透光性。
具体实施方式
取10~20g正硅酸乙酯,8~12g钛酸四丁酯,加入50~80g无水乙醇中,以300~400r/min搅拌30~40min,再以1~2g/min滴加质量分数为95%乙醇溶液至200~300g,滴加完毕后在60~65℃下保温反应1~2h,得复合溶胶,取0.3~0.5g羟丙基纤维素,1.0~1.2g聚乙二醇辛基苯基醚,2~3g纳米氧化锡,加入复合溶胶中,以300~400r/min搅拌30~40min,再在60~65℃下保温反应1~2h,并用质量分数为10%氨水调节pH至9~10,得浆料,将浆料装入喷雾干燥器中,在180~240℃下喷雾干燥,收集干燥粉末并置于管式炉中,在500~550℃下煅烧1~2h,煅烧结束后自然冷却至室温,并用去粒子水洗涤煅烧产物2~3次,再将洗涤后的涤煅烧产物转入干燥箱中,在105~110℃下干燥至恒重,得多级结构复合纳米粒子微球,取2~3g多级结构复合纳米粒子微球,0.02~0.03g硅烷偶联剂A-171,1.6~2.4g司班60混合均匀,再加入100~150gEVA塑料,0.30~0.45g聚甘油脂肪酸酯,0.10~0.15g抗氧化剂,0.30~0.45g光稳定剂,并装入高速混合机中混合均匀,得混合料,将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区120~150℃,2区150~160℃,3区160~175℃,4区175~180℃,转速为30~50r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为150~180℃,螺杆转速为100~200r/min,螺杆长径比L/D为20:1~40:1,吹胀比为2:1~4:1,拉伸比为3:1~6:1,挤出吹塑成膜,膜厚度控制为0.03~0.04mm,得防雾塑料棚膜。
实例1
取10g正硅酸乙酯,8g钛酸四丁酯,加入50g无水乙醇中,以300r/min搅拌30min,再以1g/min滴加质量分数为95%乙醇溶液至200g,滴加完毕后在60℃下保温反应1h,得复合溶胶,取0.3g羟丙基纤维素,1.0g聚乙二醇辛基苯基醚,2g纳米氧化锡,加入复合溶胶中,以300r/min搅拌30min,再在60℃下保温反应1h,并用质量分数为10%氨水调节pH至9,得浆料,将浆料装入喷雾干燥器中,在180℃下喷雾干燥,收集干燥粉末并置于管式炉中,在500℃下煅烧1h,煅烧结束后自然冷却至室温,并用去粒子水洗涤煅烧产物2次,再将洗涤后的涤煅烧产物转入干燥箱中,在105℃下干燥至恒重,得多级结构复合纳米粒子微球,取2g多级结构复合纳米粒子微球,0.02g硅烷偶联剂A-171,1.6g司班60混合均匀,再加入100gEVA塑料,0.30g聚甘油脂肪酸酯,0.10g抗氧化剂,0.30g光稳定剂,并装入高速混合机中混合均匀,得混合料,将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区120℃,2区150℃,3区160℃,4区175℃,转速为30r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为150℃,螺杆转速为100r/min,螺杆长径比L/D为20:1,吹胀比为2:1,拉伸比为3:1,挤出吹塑成膜,膜厚度控制为0.03mm,得防雾塑料棚膜。
实例2
取15g正硅酸乙酯,10g钛酸四丁酯,加入65g无水乙醇中,以350r/min搅拌35min,再以1g/min滴加质量分数为95%乙醇溶液至250g,滴加完毕后在62℃下保温反应1h,得复合溶胶,取0.4g羟丙基纤维素,1.1g聚乙二醇辛基苯基醚,2g纳米氧化锡,加入复合溶胶中,以350r/min搅拌35min,再在62℃下保温反应1h,并用质量分数为10%氨水调节pH至9,得浆料,将浆料装入喷雾干燥器中,在210℃下喷雾干燥,收集干燥粉末并置于管式炉中,在520℃下煅烧1h,煅烧结束后自然冷却至室温,并用去粒子水洗涤煅烧产物2次,再将洗涤后的涤煅烧产物转入干燥箱中,在108℃下干燥至恒重,得多级结构复合纳米粒子微球,取2g多级结构复合纳米粒子微球,0.02g硅烷偶联剂A-171,2.0g司班60混合均匀,再加入120gEVA塑料,0.35g聚甘油脂肪酸酯,0.12g抗氧化剂,0.40g光稳定剂,并装入高速混合机中混合均匀,得混合料,将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区135℃,2区155℃,3区165℃,4区178℃,转速为40r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为165℃,螺杆转速为150r/min,螺杆长径比L/D为30:1,吹胀比为3:1,拉伸比为5:1,挤出吹塑成膜,膜厚度控制为0.03mm,得防雾塑料棚膜。
实例3
取20g正硅酸乙酯,12g钛酸四丁酯,加入80g无水乙醇中,以400r/min搅拌40min,再以2g/min滴加质量分数为95%乙醇溶液至300g,滴加完毕后在65℃下保温反应2h,得复合溶胶,取0.5g羟丙基纤维素,1.2g聚乙二醇辛基苯基醚,3g纳米氧化锡,加入复合溶胶中,以400r/min搅拌40min,再在65℃下保温反应2h,并用质量分数为10%氨水调节pH至10,得浆料,将浆料装入喷雾干燥器中,在240℃下喷雾干燥,收集干燥粉末并置于管式炉中,在550℃下煅烧2h,煅烧结束后自然冷却至室温,并用去粒子水洗涤煅烧产物3次,再将洗涤后的涤煅烧产物转入干燥箱中,在110℃下干燥至恒重,得多级结构复合纳米粒子微球,取3g多级结构复合纳米粒子微球,0.03g硅烷偶联剂A-171,2.4g司班60混合均匀,再加入150gEVA塑料,0.45g聚甘油脂肪酸酯,0.15g抗氧化剂,0.45g光稳定剂,并装入高速混合机中混合均匀,得混合料,将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区150℃,2区160℃,3区175℃,4区180℃,转速为50r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为180℃,螺杆转速为200r/min,螺杆长径比L/D为40:1,吹胀比为4:1,拉伸比为6:1,挤出吹塑成膜,膜厚度控制为0.04mm,得防雾塑料棚膜。
对照例:浙江某公司生产的防雾塑料棚膜。
将实例及对照例的防雾塑料棚膜进行检测,具体检测如下:
接触角测试:裁取长宽分别为8cm×2cm的薄膜试样。取防雾薄膜试样固定在载玻片上,于J-150型接触角测定仪上进行测定。在测定膜材接触角的过程中,需要将裁剪好的试样平整的固定在载玻片上,保持膜面的平整和洁净,用注射器将水滴滴到薄膜表面,待水滴稳定后开始在接触角仪的虽微镜孔下观察,并通过旋转角度盘读取相应数值,计算出接触角的数值。测试时,在薄膜的不同地方测量五次,取其平均值。
透光率测试:按照《GB/T2410-2008透明塑料透光率和雾度的测定》进行实验,使用WGT—S透光率与雾度测定仪对薄膜进行透光率实验。
力学性能测试:根据《GB/T13022-1991塑料薄膜拉伸性能试验方法》进行实验。
具体检测结果如表1。
表1性能表征对比表
检测项目 | 实例1 | 实例2 | 实例3 | 对照例 |
接触角/° | 26.22 | 25.82 | 24.98 | 35.11 |
透光率/% | 95.1 | 94.3 | 94.5 | 87.0 |
拉伸强度/MPa | 41 | 40 | 41 | 28.9 |
由表1可知,本发明制备的防雾塑料棚膜具有良好的透光率、拉伸强度和防雾性能。
Claims (7)
1.一种防雾塑料棚膜,其特征在于,由下述重量份原料制备而成:2~3份多级结构复合纳米粒子微球,0.02~0.03份硅烷偶联剂A-171,1.6~2.4份司班60,100~150份EVA塑料,0.30~0.45份聚甘油脂肪酸酯,0.10~0.15份抗氧化剂,0.30~0.45份光稳定剂。
2.如权利要求1所述的一种防雾塑料棚膜,其特征在于,所述多级结构复合纳米粒子微球为正硅酸乙酯、钛酸四丁酯、羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡组成的浆料,喷雾干燥成型后高温煅烧并水洗干燥制成。
3.如权利要求2所述的一种防雾塑料棚膜,其特征在于,所述正硅酸乙酯、钛酸四丁酯、羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡的重量份为10~20份正硅酸乙酯,8~12份钛酸四丁酯,0.3~0.5份羟丙基纤维素,1.0~1.2份聚乙二醇辛基苯基醚,2~3份纳米氧化锡。
4.如权利要求1所述的一种防雾塑料棚膜,其特征在于,所述喷雾干燥温度为180~240℃,所述高温煅烧温度为500~550℃。
5.如权利要求1所述的一种防雾塑料棚膜,其特征在于,所述抗氧化剂为抗氧化剂1010、抗氧化剂168、抗氧化剂264中的任意一种或多种。
6.如权利要求1所述的一种防雾塑料棚膜,其特征在于,所述光稳定剂为光稳定剂770、光稳定剂944、光稳定剂292中的任意一种或多种。
7.如权利要求1~6任意一项所述的一种防雾塑料棚膜的制备方法,其特征在于,具体步骤为:
(1)取正硅酸乙酯、钛酸四丁酯加入无水乙醇中混合均匀,再滴加质量分数为95%乙醇溶液至正硅酸乙酯质量的10~30倍,滴加完毕后在60~65℃下保温反应1~2h,得复合溶胶;
(2)取羟丙基纤维素、聚乙二醇辛基苯基醚、纳米氧化锡,加入复合溶胶中混合均匀,再在60~65℃下保温反应1~2h,并用氨水调节pH至9~10,得浆料;
(3)将浆料喷雾干燥后煅烧,再水洗干燥得多级结构复合纳米粒子微球;
(4)取多级结构复合纳米粒子微球、硅烷偶联剂A-171、司班60、100~150gEVA塑料、聚甘油脂肪酸酯、抗氧化剂、光稳定剂,装入高速混合机中混合均匀,得混合料;
(5)将混合料放入双螺杆挤出装置中挤出造粒,挤出装置各加热区温度控制为1区120~150℃,2区150~160℃,3区160~175℃,4区175~180℃,转速为30~50r/min,造粒完成后转入单螺杆吹膜机中,控制单螺杆挤出温度为150~180℃,螺杆转速为100~200r/min,螺杆长径比L/D为20:1~40:1,吹胀比为2:1~4:1,拉伸比为3:1~6:1,挤出吹塑成膜,膜厚度控制为0.03~0.04mm,得防雾塑料棚膜。
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