CN114539668B - 一种防虫母粒、其聚丙烯组合物及其制备方法 - Google Patents
一种防虫母粒、其聚丙烯组合物及其制备方法 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域,公开了一种防虫母粒、其聚丙烯组合物及其制备方法。本发明的防虫母粒按重量份数计,包括以下组分:聚丙烯载体树脂60~75份,改性二氧化硅15~25份,抗氧剂0~0.6份,润滑剂0~0.5份,耐候剂6~10份。本发明的防虫聚丙烯组合物在制备时可有效降低驱避剂在挤出机加工过程中的挥发和分解,防止驱避剂的快速挥发,保证了防虫效果的持久性;光扩散效果、防虫效果和耐辐照性好,可以广泛应用照明领域。
Description
技术领域
本发明涉及高分子材料技术领域,具体涉及一种防虫母粒、其聚丙烯组合物及其制备方法。
背景技术
蚊虫喜欢追逐光源,特别是夏天的路边的路灯,蚊虫聚集在灯罩上面,久而久之影响灯罩的照明效果,甚至蚊虫的尸体粘附在灯具上,长期有可能导致短路。目前,现有常规的改善方案一般为加入防虫类的驱避剂,如中国发明专利文献CN20191068741.7一种可驱虫的光扩散聚丙烯材料及其制备方法,通过加入氯菊酯、胺菊酯、氯腈菊酯、溴腈菊酯中一种或多种驱避剂来达到防虫效果,但是菊酯的种类多达几十种,防虫和耐热等级差异较大。且驱避剂热分解温度普遍在200℃以下,不耐高温剪切,在制备聚丙烯组合物的过程中难以保证菊酯成分不被分解和挥发,导致最终的防虫效果有限,长期辐照后防虫效果也无法维持,以及聚丙烯组合物颜色的变化没有进行评估。
因此,有必要开发一种具有防虫的光扩散材料,即不影响光扩散效果,又可以在室外长期辐照后能保持防虫的效果。
发明内容
本发明的目的在于克服现有技术的不足之处而提供一种防虫母粒、其聚丙烯组合物及其制备方法,以期克服现有防虫聚丙烯材料中驱避剂高温加工过程中易挥发和易分解、驱避率不够高效、驱避率耐久性差以及耐辐照变色的问题。
为实现上述目的,本发明采取的技术方案如下:
第一方面,本发明提供了一种防虫母粒,按重量份数计,包括以下组分:
聚丙烯载体树脂60~75份,改性二氧化硅15~25份,抗氧剂0~0.6份,润滑剂0~0.5份,耐候剂6~10份;
所述改性二氧化硅包括多孔二氧化硅粉、驱避剂和协效剂;
所述多孔二氧化硅粉、驱避剂和协效剂的质量比为(8~20):(5~10):1;
所述聚丙烯载体树脂为超低熔点无规聚丙烯。
本发明的防虫母粒中,选择多孔二氧化硅粉作为驱避剂的吸附基体,均匀的致密的孔洞达到保护趋避剂的作用,可以有效防止驱避剂的快速挥发,从而保证了防虫效果的持久性;防虫母粒中的多孔二氧化硅粉还具有良好的光扩散效果,从而不需要额外加入光扩散剂,使防虫母粒既有防虫效果又有光扩散效果;耐候剂可有效降低防虫母粒辐照后的变色性,避免防虫聚丙烯组合物长期室外放置之后的变色问题;协效剂能够有效改善驱避剂的稳定性,保证了防虫效果的长效性和持久性。
作为本发明所述防虫母粒的优选实施方式,所述超低熔点无规聚丙烯的熔点为120~140℃,熔融指数为6~10g/10min,检测条件:230℃,2.16kg。
选择超低熔点(120~140℃)的无规聚丙烯树脂(常规聚丙烯熔点为168℃)作为母粒载体,加工温度可降低30℃左右,有效降低了驱避剂在挤出机加工过程中的挥发和分解,可减少驱避剂的添加量,从而减少防虫聚丙烯组合物的气味。
作为本发明所述防虫母粒的优选实施方式,所述多孔二氧化硅粉的平均粒径为1~4微米。
通过选择特定粒径的多孔二氧化硅粉使组合物具有更加优秀光扩散效果。
作为本发明所述防虫母粒的优选实施方式,所述耐候剂为受阻胺光稳定剂、二苯甲酮光吸收剂中的至少一种;优选的,所述所述耐候剂为受阻胺光稳定剂和二苯甲酮光吸收剂;所述受阻胺光稳定剂和二苯甲酮光吸收剂的质量比为1:1。
所述驱避剂为氯菊酯、胺菊酯、氯氰菊酯、苯醚菊酯中的至少一种;所述协效剂为芝麻素,增效醚,N-异丁基-8-十一烯酰胺中的至少一种。所述抗氧剂为受阻酚、磷酸酯、硫醚类抗氧剂中的至少一种;所述润滑剂为聚乙烯蜡、EBS、硬脂酸锌、硬脂酸钙中的至少一种。
第二方面,本发明提供了上述防虫母粒的制备方法,包括以下步骤:
按比例取各组分混合,挤出,造粒,即成;所述挤成型温度为130~150℃。
作为本发明所述防虫母粒的制备方法的优选实施方式,所述改性二氧化硅的制备方法为:
将所述多孔二氧化硅粉、驱避剂和协效剂置于70~80℃搅拌,过滤,洗涤,干燥,即成。
第三方面,本发明提供一种防虫聚丙烯组合物,按百分比计,包括以下组分:聚丙烯基体树脂85%~95%,所述的防虫母粒5%~15%。
作为本发明所述防虫聚丙烯组合物的优选实施方式,所述聚丙烯基体树脂为均聚聚丙烯,熔融指数≥1g/10min,检测条件:230℃,2.16kg。
第四方面,本发明提供所述的防虫聚丙烯组合物的制备方法,包括以下步骤:
按百分比比取所述组分混合,挤出并造粒,即得。
第五方面,将所述的防虫母粒或所述的防虫聚丙烯组合物在照明或发光家电设备中应用。
与现有技术相比,本发明的有益效果为:
本发明的防虫聚丙烯组合物在制备时可有效降低驱避剂在挤出机加工过程中的挥发和分解,防止驱避剂的快速挥发,保证了防虫效果的持久性;光扩散效果、防虫效果和耐辐照性好,可以广泛应用照明领域。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。本领域技术人员应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
下述实施例和对比例中,如无特别说明,抗氧剂、润滑剂、耐候剂均通过市售获得,且平行实验中使用的是相同的抗氧剂、润滑剂、耐候剂。
下述实施例中,性能检测方法为:
(1)透光度
按照标准GB/T 2410-2008,用60mm×20mm×1mm板试验样品进行透光度测试。
(2)雾度
按照标准GB/T 2410-2008,用60mm×20mm×1mm板试验样品进行雾度测试。
(3)驱避率
在一个30cm×30cm×30cm透明密闭的箱体中,放置试验样品(直径100mm、厚度4mm的圆片),然后将20只白纹伊蚊放入箱体中,观察并记录在10min内,白纹伊蚊在试验圆片上的停留次数,试验三次取平均值。
驱避率的计算公式:(空白样停留次数-试验样的停留次数)/空白样停留次数×100%。
热老化处理方式为:
将上述4mm的圆片置于80℃烘箱2000h进行老化,老化后取出进行上述驱避率测试。
氙灯老化法:按照ISO4892-2标准进行氙灯老化;
将上述4mm的圆片按照ISO4892-2标准进行氙灯老化1000h进行老化,老化后取出进行上述驱避率测试。
(4)色差
氙灯老化法:按照ISO4892-2标准进行氙灯老化1000h;
对60mm×20mm×2mm色板试验样品进行测试,采用色差仪对比老化前后的L,A,B值,计算得到色差。热老化测试把60mm×20mm×2mm色板放置在烘箱进行老化,采用色差仪对比老化前后的L,A,B值,计算得到色差△E。
检测材料老化前颜色,白度记为L1,红绿值记为A1,黄蓝值记为B1;检测材料老化后颜色,白度记为L2,红绿值记为A2,黄蓝值记为B2。按下式计算△E:
下述实施例及对比例所用的原材料说明如下,但不限于这些材料:
聚丙烯A:无规共聚聚丙烯粒料,熔融指数为8g/10min,熔点为130℃,牌号为PP4908,燕山石化。
聚丙烯B:均聚聚丙烯粒料,熔融指数为12g/10min,熔点为168℃,牌号为HP500N,中海壳牌。
聚丙烯C:共聚聚丙烯粒料,熔融指数为30g/10min,熔点为168℃,牌号为EP548R,中海壳牌。
聚丙烯D:均聚聚丙烯粒料,熔融指数为1g/10min,熔点为168℃,牌号为B1101,燕山石化。
上述聚丙烯的熔融指数依据标准ISO 1133:2005,在230℃/2.16kg条件下检测。
多孔二氧化硅粉:平均粒径为1.5~1.9微米,牌号为AZ-204,东曹。
驱避剂1:苯醚菊酯,含量>99%,市售。
驱避剂2:氯菊酯,含量>99%,市售。
驱避剂3:氯氰菊酯,含量>99%,市售。
协效剂1:芝麻素:含量>98%,市售。
协效剂2:增效醚:含量>98%,市售。
协效剂3:N-异丁基-8-十一烯酰胺:含量>98%,市售。
抗氧剂1:抗氧剂1010,市售。
抗氧剂2:抗氧剂168,市售。
润滑剂:EBS,市售。
耐候剂1:受阻胺光稳定剂LA-402AF,市售。
耐候剂2:二苯甲酮光吸收剂UV-531,市售。
防虫母粒1~14的组成组分如表1所示。
防虫母粒1~14的制备方法为:
按比例取聚丙烯树脂、改性二氧化硅、抗氧剂、润滑剂、耐候剂混合均匀,然后加入到双螺杆挤出机中挤出并造粒得到;其中,挤出机成型温度设定在130~150℃、转速范围设定200~400转/分。
其中,改性二氧化硅的制备方法为:
将多孔二氧化硅粉、驱避剂、协效剂、无水酒精置于70~80℃水浴锅中,通过搅拌、过滤、洗涤、干燥制得。
防虫母粒1~14的组成组分如表1所示。
表1:不同防虫母粒的配方组成
实施例1~7和对比例1~8防虫聚丙烯组合物的组分如表2所示。
实施例1~7和对比例1~8防虫聚丙烯组合物的制备方法为:
按比例将聚丙烯树脂、防虫母粒混合均匀,然后加入到双螺杆挤出机中挤出并造粒得到;其中,挤出机成型温度设定在130~180℃、转速范围设定200~400转/分。
表2:实施例和对比例防虫聚丙烯组合物测试结果:
续表2:实施例和对比例防蟑螂聚丙烯组合物测试结果
可知,实施例1~7的防虫聚丙烯组合物光扩散好,驱避率高,热老化和光老化后的驱避率仍保持良好,能够有效防止驱避剂在高温老化过程中的挥发导致的驱避失效。
与实施例1相比,对比例1和对比例2的防虫聚丙烯组合物中,防虫母粒分别采用熔点为168℃的共聚聚丙烯粒料和均聚聚丙烯粒料作为载体树脂,加工温度高导致菊酯降解和挥发,组合物的驱避率较低。
与实施例1相比,对比例3的防虫聚丙烯组合物中,防虫母粒未添加耐候剂,组合物氙灯老化后的驱避率保持率较低,色差过大。
与实施例1相比,对比例4~7的防虫聚丙烯组合物中,防虫母粒中改性二氧化硅的多孔二氧化硅粉、驱避剂和协效剂的质量比不满足(8~20):(5~10):1,组合物的驱避率不高。
与实施例1相比,对比例8的防虫聚丙烯组合物中,聚丙烯的质量分数为75,组合物的透光率偏低,驱避率不高。
另设置对比例9,与实施例1的组分相同,但未预制母粒,直接将各组分按比例将聚丙烯A、聚丙烯B、多孔二氧化硅粉、驱避剂、协效剂、抗氧剂、润滑剂、耐候剂混合均匀,然后加入到双螺杆挤出机中挤出并造粒得到;其中,挤出机成型温度设定在130~150℃、转速范围设定200~400转/分,所得防虫聚丙烯组合物的1mm透光率为90%,1mm雾度为94%,驱避率为75%,80℃,2000h热老化后驱避率为50%,氙灯老化1000h后驱避率为66%,氙灯老化1000h后色差为1.3。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (9)
1.一种防虫母粒,其特征在于,按重量份数计,包括以下组分:
聚丙烯载体树脂60~75份,改性二氧化硅15~25份,抗氧剂0~0.6份,润滑剂0~0.5份,耐候剂6~10份;
所述改性二氧化硅包括多孔二氧化硅粉、驱避剂和协效剂;
所述多孔二氧化硅粉、驱避剂和协效剂的质量比为(8~20):(5~10):1;
所述聚丙烯载体树脂为超低熔点无规聚丙烯;
所述超低熔点无规聚丙烯的熔点为120~140℃,熔融指数为6~10g/10min,检测条件:230℃,2.16kg;
所述驱避剂为氯菊酯、胺菊酯、氯氰菊酯、苯醚菊酯中的至少一种;所述协效剂为芝麻素,增效醚,N-异丁基-8-十一烯酰胺中的至少一种。
2.根据权利要求1所述的防虫母粒,其特征在于,所述多孔二氧化硅粉的平均粒径为1~4微米。
3.根据权利要求1所述的防虫母粒,其特征在于,所述耐候剂为受阻胺光稳定剂、二苯甲酮光吸收剂中的至少一种。
4.一种权利要求1~3任一项所述防虫母粒的制备方法,其特征在于,包括以下步骤:
按比例取各组分混合,挤出,造粒,即成;所述挤出温度为130~150℃。
5.根据权利要求4所述的防虫母粒的制备方法,其特征在于,所述改性二氧化硅的制备方法为:
将所述多孔二氧化硅粉、驱避剂和协效剂置于70~80℃搅拌,过滤,洗涤,干燥,即成。
6.一种防虫聚丙烯组合物,其特征在于,按百分比计,包括以下组分:聚丙烯基体树脂85%~95%,权利要求1~3任一项权利要求所述的防虫母粒5%~15%。
7.根据权利要求6所述的防虫聚丙烯组合物,其特征在于,所述聚丙烯基体树脂为均聚聚丙烯,熔融指数≥1g/10min,检测条件:230℃,2.16kg。
8.一种权利要求6或7所述的防虫聚丙烯组合物的制备方法,其特征在于,包括以下步骤:
按百分比取所述组分混合,挤出并造粒,即得;
其中,所述挤出的温度为130~150℃。
9.权利要求1~3任一项的防虫母粒或权利要求6或7所述的防虫聚丙烯组合物在发光家电设备中的应用。
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