CN111087686B - 一种聚丙烯组合物及其制备方法和应用 - Google Patents
一种聚丙烯组合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种聚丙烯组合物,按重量份计,包括以下组分:聚丙烯树脂40‑99份;乙烯‑α烯烃共聚物15‑30份;抗菌剂0.2‑1份;改性聚二甲基硅氧烷1‑3份。本发明发现,通过控制弹性体的熔融指数,能够促进改性聚二甲基硅氧烷与抗菌剂的分布,促进聚丙烯组合物的抗菌效果与抗污效果。
Description
技术领域
本发明涉及高分子材料技术领域,特别是涉及一种聚丙烯组合物及其制备方法和应用。
背景技术
聚丙烯与其它通用塑料相比,具有力学性能好、密度小、刚性好、强度高以及电绝缘性能好等优点,广泛应用于家电和汽车制品中。改性聚丙烯应用在洗衣机、小家电时,当使用时间过长后,聚丙烯材料易被沾污,同时滋生细菌发霉等,限制了聚丙烯材料的应用范围。在汽车应用领域,车辆在使用过程中,驾乘人员的化妆品、食品等容易沾污内饰材料,且部分污物难以清理。随着新型出行方式(共享汽车/网约车)的推广,对汽车材料的抗菌防污性能提出需求。
中国专利申请CN 106117802 B公开了一种矿粉增强聚丙烯组合物及其制备方法,在矿粉增强聚丙烯组合物配方中添加特定含量的界面改性剂(环氧硅氧烷偶联剂)、高疏水性助剂和抗菌剂,改变矿粉增强聚丙烯组合物表面的极性,改善了矿粉增强聚丙烯组合物的疏水性能,并且提高了该矿粉增强聚丙烯组合物的抗菌防霉性。中国专利申请CN109294149A公开了一种持久抗菌聚丙烯塑料杯该塑料杯制备方法,主要是通过聚二甲基硅氧烷作为抗污剂的加入,但是由于其在聚丙烯树脂基体中的分散性不足,需要加入乙撑双硬脂酰胺来辅助。
中国专利申请CN101591443A公开了一种聚丙烯接枝亲水亲生物体的改性添加剂,其中亲水亲生物体的链段可以是聚二甲基硅氧烷。改性添加剂与聚丙烯之间具有良好的附着力,又能改善聚丙烯表面的抗凝血等生物相容性能。但是没有讨论聚丙烯接枝聚二甲基硅氧烷与聚丙烯的相容性。
发明内容
本发明的目的在于,提供一种聚丙烯组合物,具有良好的抗菌效果与抗污效果。
本发明的另一目的在于,提供上述聚丙烯组合物的制备方法与应用。
本发明是通过以下技术方案实现的:
一种聚丙烯组合物,按重量份计,包括以下组分:
聚丙烯树脂 40-99份;
乙烯-α烯烃共聚物 15-30份;
抗菌剂 0.2-1份;
聚丙烯接枝聚二甲基硅氧烷 1-3份。
优选的,按重量份计,抗菌剂的用量为0.2-0.4份。在本发明的树脂基体下,能够极大降低抗菌剂的用量。
所述的乙烯-α烯烃共聚物选自乙烯-丙烯共聚物、乙烯-己烯共聚物、乙烯-丁烯共聚物、乙烯-辛烯共聚物中的至少一种。
一般的,在聚丙烯中使用的热塑性弹性体包括苯乙烯类(包括SBS、SIS、SEBS、SEPS)、聚烯烃类(主要是乙烯-α烯烃共聚物)、PP/EPDM共混、OBC等。苯乙烯类、PP/EPDM共混、OBC都不能实现本发明的目的。
优选的,所述的乙烯-α烯烃共聚物的熔融指数为5-30g/10min(190℃,2.16kg)。
所述的抗菌剂选自氧化锌、沸石负载银离子或玻璃基负载银离子中的至少一种。
优选的,所述的聚丙烯接枝聚二甲基硅氧烷,接枝率为60%-80%,分子量为60万-80万。聚丙烯接枝聚二甲基硅氧烷添加,能够富集在材料表面,起到抗污效果,减少水分的残留也能破坏细菌的生长环境,提升抗菌效果。
聚丙烯是一种结晶型树脂,抗菌剂在聚丙烯结晶过程中排出在晶区外而主要分布在非晶区。本发明发现,在聚丙烯树脂中添加一定量的高熔指的乙烯-α烯烃共聚物,更好的在剪切作用下发生变形、破碎,均匀分散。尤其是表层,注塑过程中由于高剪切形成高度取向的显著的丝状网络结构,能够提升表层抗菌剂的暴露以提升抗菌效果。
聚硅氧烷表面张力低,具有良好的疏水特性。如果富集到材料表面,可以改善表面的防污性能,如本实验中涉及到的鞋油擦拭性能。同时由于其疏水性能,材料表层更难吸附空气中的水分子形成水膜,如此对抑制菌群的生长有一定作用。但是,聚硅氧烷在表面的富集会破坏丝状网络结构,反而降低了抗菌性能。因此,本发明采用聚丙烯接枝聚二甲基硅氧烷,富集在表面的同时也不破坏丝状网络结构,保证了良好的抗污效果与杀菌效果,协同作用之下,得到了优秀抗菌性能。
本发明的组合物中还可以加入一定量的填料来改善其他性能,按重量份计,还包括0-30份填料;所述的填料选自滑石粉、碳酸钙、硅灰石、硫酸钡、云母、硅微粉、二氧化硅、氢氧化镁、蒙脱土中的至少一种。
本发明对于填料的粒径没有特别的限制。
为了提高加工性能或者得到其他性能,按重量份计,还包括0-10份的助剂;所述的助剂选自润滑剂、色粉中的至少一种。
所述的润滑剂可以是:硬脂酸盐类和酰胺类,如硬脂酸锌、硬脂酸酸钙、乙撑双硬脂酸酰胺等。
所述的色粉可以是:钛白、碳黑、酞青蓝、铁红、钛黄等。
上述的聚丙烯组合物的制备方法,按重量配比称取各组分,加入到高混机中混合1~3分钟,转速为1000~2000转/分钟,得到预混料;预混料经双螺杆挤出机熔融挤出,螺杆各区温度为190~230℃,真空造粒即得产品。
以上所述的聚丙烯组合物的应用,用在仪表板、副仪表板、立柱、手套箱、门板、门槛、空调壳体等汽车用内饰件的应用。
本发明具有如下有益效果:
本发明通过采用乙烯-α烯烃共聚物、聚丙烯接枝聚二甲基硅氧烷的抗菌体系,注塑过程中由于高剪切形成高度取向的显著的丝状网络结构,能够提升表层抗菌剂的暴露以提升抗菌效果,协同聚丙烯接枝聚二甲基硅氧烷富集在表面后的抗污性能,在低的抗菌剂添加量下得到一种抗菌效果好的聚丙烯组合物。
附图说明
图1:具有丝状网络结构的材料表面电镜照片。
图2:不具有丝状网络结构的材料表面电镜照片。
具体实施方式
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。
本发明所用原料来下:
聚丙烯:N-Z30S;
抗菌剂:银离子抗菌剂BM-502FA,玻璃载体;
乙烯-辛烯共聚物,熔融指数为8g/10min(190℃,2.16kg),POE 8137;
乙烯-丁烯共聚物,熔融指数为5g/10min(190℃,2.16kg),牌号POE LC565;
SEBS,熔融指数为10g/10min(230℃,2.16kg),G1657 MS;
OBC,熔融指数为5g/10min(190℃,2.16kg),Infuse 9507;
聚丙烯接枝聚二甲基硅氧烷A:接枝率为63%,分子量约为68万;
聚丙烯接枝聚二甲基硅氧烷B:接枝率为78%,分子量约为76万;
聚丙烯接枝聚二甲基硅氧烷C:接枝率为43%,分子量约为57万;
聚二甲基硅氧烷:TP-200,分子量约为60万;
滑石粉:TYT-777A;
润滑剂:硬脂酸锌;BS-2818;
色粉:碳黑;M717;
实施例和对比例聚丙烯组合物的制备方法:按重量配比称取各组分,加入到高混机中混合1~3分钟,转速为1000~2000转/分钟,得到预混料;预混料经双螺杆挤出机熔融挤出,螺杆各区温度为190~230℃,真空造粒即得聚丙烯组合物。
各项性能测试方法:
将聚丙烯组合物在注塑机中注塑成100cm*100cm*3mm方板,测试样板表面防污性能和抗菌性能。
(1)防污性能测试:在样板表面滴上2滴老人头液体鞋油,常温干燥24h后用纱布擦拭,按如下方法评价:完全擦拭不留痕迹为3级;部分擦拭为2级;完全擦拭不掉为1级。
(2)抗菌性能测试:根据JIS Z 2801:2012,按如下方法评价:明显抑菌为A,一般抑菌为B,不抑菌为C。
表1:实施例聚丙烯组合物各组分配比(重量份)及各项性能测试结果
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | |
聚丙烯 | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
抗菌剂 | 0.2 | 0.2 | 0.2 | 0.4 | 1 | 0.2 | 0.2 |
乙烯-辛烯共聚物 | 20 | 20 | 20 | 20 | 15 | 30 | |
乙烯-丁烯共聚物 | 20 | ||||||
聚丙烯接枝聚二甲基硅氧烷A | 1 | 1 | 1 | 2 | 3 | ||
聚丙烯接枝聚二甲基硅氧烷B | 1 | ||||||
聚丙烯接枝聚二甲基硅氧烷C | 1 | ||||||
滑石粉 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
润滑剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
色粉 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
防污性能 | 3 | 3 | 2 | 3 | 3 | 3 | 3 |
抗菌性能 | A | A | B | A | A | A | A |
从实施例1-3可知,聚丙烯接枝聚二甲基硅氧烷的接枝率也会影响材料表面丝状网络结构的形成,在优选的接枝率范围内,抗菌效果更好。
表2:对比例聚丙烯组合物各组分配比(重量份)及各项性能测试结果
对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | |
聚丙烯 | 80 | 80 | 80 | 80 | 80 | 80 |
抗菌剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
乙烯-辛烯共聚物 | 20 | 20 | 10 | |||
SEBS | 20 | 20 | ||||
OBC | 20 | |||||
聚丙烯接枝聚二甲基硅氧烷A | 1 | 1 | 1 | |||
聚二甲基硅氧烷 | 1 | 2 | 1 | |||
滑石粉 | 15 | 15 | 15 | 15 | 15 | 15 |
润滑剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
色粉 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
防污性能 | 2 | 2 | 2 | 3 | 1 | 2 |
抗菌性能 | C | C | C | C | C | C |
续表2
对比例7 | 对比例8 | |
聚丙烯 | 80 | 80 |
抗菌剂 | 0.2 | 0.2 |
乙烯-辛烯共聚物 | 20 | 20 |
SEBS | ||
OBC | ||
聚丙烯接枝聚二甲基硅氧烷A | 0.3 | 5 |
聚二甲基硅氧烷 | ||
滑石粉 | 15 | 15 |
润滑剂 | 0.2 | 0.2 |
色粉 | 0.5 | 0.5 |
防污性能 | 1 | 3 |
抗菌性能 | C | C |
从对比例1/2/5可知,其他种类的弹性体不能让材料表面具有显著的丝状网络结构,因此抗菌效果差。
从对比例3/4可知,未用聚丙烯接枝的聚二甲基硅氧烷,通过提高用量虽然能够得到好的防污性能,但是抗菌性能很差。
从对比例6可知,乙烯-α烯烃共聚物的用量也会影响材料表面丝状网络结构的形成,影响抗菌剂的杀菌效果。
从对比例7/8可知,聚丙烯接枝聚二甲基硅氧烷的用量太低,材料表面抗污性能差,细菌易滋生,综合降低了抗菌性能,而聚丙烯接枝聚二甲基硅氧烷用量太大,容易破坏材料表面的丝状网络结构,反而降低了抗菌性能。
Claims (10)
1.一种聚丙烯组合物,其特征在于,按重量份计,包括以下组分:
聚丙烯树脂 40-99份;
乙烯-α烯烃共聚物 15-30份;
抗菌剂 0.2-1份;
聚丙烯接枝聚二甲基硅氧烷 1-3份。
2.根据权利要求1所述的聚丙烯组合物,其特征在于,按重量份计,抗菌剂的用量为0.2-0.4份。
3.根据权利要求1所述的聚丙烯组合物,其特征在于,所述的乙烯-α烯烃共聚物选自乙烯-丙烯共聚物、乙烯-己烯共聚物、乙烯-丁烯共聚物、乙烯-辛烯共聚物中的至少一种。
4.根据权利要求3所述的聚丙烯组合物,其特征在于,所述的乙烯-α烯烃共聚物的熔融指数为5-30g/10min,190℃,2.16kg。
5.根据权利要求1所述的聚丙烯组合物,其特征在于,所述的抗菌剂选自氧化锌、沸石负载银离子或玻璃基负载银离子中的至少一种。
6.根据权利要求1所述的聚丙烯组合物,其特征在于,所述的聚丙烯接枝聚二甲基硅氧烷,接枝率为60%-80%,分子量为60万-80万。
7.根据权利要求1所述的聚丙烯组合物,其特征在于,按重量份计,还包括0-30份填料;所述的填料选自滑石粉、碳酸钙、硅灰石、硫酸钡、云母、硅微粉、二氧化硅、氢氧化镁、蒙脱土中的至少一种。
8.根据权利要求1所述的聚丙烯组合物,其特征在于,按重量份计,还包括0-10份的助剂;所述的助剂选自润滑剂、色粉中的至少一种。
9.权利要求1-8任一项所述的聚丙烯组合物的制备方法,其特征在于,按重量配比称取各组分,加入到高混机中混合1~3分钟,转速为1000~2000转/分钟,得到预混料;预混料经双螺杆挤出机熔融挤出,螺杆各区温度为190~230℃,真空造粒即得聚丙烯组合物。
10.权利要求1-8任一项所述的聚丙烯组合物的应用,其特征在于,用在仪表板、副仪表板、立柱、手套箱、门板、门槛、空调壳体汽车用内饰件的应用。
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