CN112341841A - 一种长效型的天然多功能添加剂制备方法及应用 - Google Patents

一种长效型的天然多功能添加剂制备方法及应用 Download PDF

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Publication number
CN112341841A
CN112341841A CN202011100828.6A CN202011100828A CN112341841A CN 112341841 A CN112341841 A CN 112341841A CN 202011100828 A CN202011100828 A CN 202011100828A CN 112341841 A CN112341841 A CN 112341841A
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Prior art keywords
shell powder
type
natural
modified
multifunctional additive
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CN202011100828.6A
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Inventor
邹智挥
孙亚丽
杨涛
陈建
鲁越
高晨
张雪梅
于永启
胡雪菲
文艺桦
葛非凡
陈治均
王若尧
甘佩文
雷燕
邹加俊
赵文彬
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Sichuan University of Science and Engineering
Sichuan Zhirenfa Biological Technology Co Ltd
Sichuan Zhixiangyi Technology Co Ltd
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Sichuan University of Science and Engineering
Sichuan Zhirenfa Biological Technology Co Ltd
Sichuan Zhixiangyi Technology Co Ltd
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Application filed by Sichuan University of Science and Engineering, Sichuan Zhirenfa Biological Technology Co Ltd, Sichuan Zhixiangyi Technology Co Ltd filed Critical Sichuan University of Science and Engineering
Priority to CN202011100828.6A priority Critical patent/CN112341841A/zh
Publication of CN112341841A publication Critical patent/CN112341841A/zh
Priority to GB2306954.5A priority patent/GB2620482A/en
Priority to PCT/CN2021/123458 priority patent/WO2022078365A1/zh
Priority to ZA2022/05085A priority patent/ZA202205085B/en
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Abstract

一种长效型的天然多功能添加剂制备方法，利用改性高分子对天然填料进行包覆，所述改性高分子为生物可降解高分子、水溶性高分子、聚氯乙烯、聚酰胺、聚苯硫醚、三聚氰胺树脂、聚烯烃、聚羟基脂肪酸酯、苯乙烯嵌段共聚物、氯化聚氯乙烯、尿素甲醛树脂、聚胺酯、壳聚糖中的任一种或两种以上的高分子改性而成;所述天然填料为高温煅烧后的贝壳粉或蛋壳,氧化钙、氢氧化钙、氧化镁、氢氧化镁、提纯后的黑水虻蛹壳粉中任意一种或两种以上,或纳米粒子与煅烧后的贝壳粉或蛋壳粉的复合物。采用本发明所述制备方法，成本低廉，部分原料属于废弃物回收再利用;并使天然填料的抗菌性更加持久且易于保存；可应用于各种加工工艺或保养品的添加或调节。

Description

一种长效型的天然多功能添加剂制备方法及应用
技术领域
本发明属于材料技术领域，涉及杀菌添加剂技术，具体涉及一种长效型的天然多功能添加剂制备方法及应用。
背景技术
预计2022年，全球添加剂市场市值有机会达到625亿美元。由于添加剂可以用在各种产业，全球塑料添加剂市场份额高度集中于综合型企业，他们覆盖从原料生产到塑料、建筑制造、甚至是食品行行。在全球展开经营的大型行业参与者包括杜邦、普立万、陶氏化学公司、赢创和巴斯夫等公司。由于抗菌添加剂可以赋予产品抗菌和抑菌活性，因此有相当好的市场前景。有害细菌在自然界中无处不在，生活中无时无刻都受这细菌侵扰，有害细菌的大量繁殖会威胁到人类的健康，抑制它们的生长可减少人们疾病的发生。
金属离子抗菌剂中目前研究最多的是含银离子抗菌剂，原因是金属银的杀菌能力最强。金属氧化物抗菌剂属于光触媒，是一种在光的照射下自身不起变化，却可以促进化学反应的物质，将自然界存在的光能转换成为化学反应所需的能量。常见的光催化材料有TiO2、ZnO等，其中，最具代表性的是TiO2。有机抗菌剂大多都以化学合成的方法得到的，包括有机酸类、酯类、季胺盐类，双胍类、酵类、腈类、吡啶类、酚类、醛类、醚类、过氧化物类、卤素类、咪唑类、噻唑类等，有机类的抗菌剂通常都具有高效的抑菌性能，但也有耐热性差，抗菌持久性差或有具生物毒性等缺点。天然抗菌剂是从动植物中提炼、精制得到的，大多是多糖、多肽及糖肽聚合物类物质，包括壳聚糖、鱼精蛋白、桂皮油和罗汉柏油等，具有耐候性优良、毒性低、使用安全等优点，壳聚糖要是从蟹、虾壳、贝类和昆虫的外皮精炼而得的甲壳质经脱乙酰反应后的产品。天然抗菌剂主要缺点是耐热性较差，药效持续时间短，是未来抗菌添加剂发展的主要方向。
综上所述，现有的抗菌剂大多价格高昂，部分危害环境或具生物毒性，不符合现代环保与健康理念，此外，多数抗菌剂会随着时间的变化或环境的影响而降低其原有的抗菌活性。另一方面，大部份抗菌剂都会影响产品的物理性能，这是由于抗菌剂本身的机械性质不佳及抗菌剂不易分散。
发明内容
为克服现有技术存在缺陷，本发明公开了一种长效型的天然多功能添加剂制备方法。
本发明所述长效型的天然多功能添加剂制备方法，利用改性高分子对天然填料进行包覆，所述改性高分子为生物可降解高分子、水溶性高分子、聚烯烃，聚羟基脂肪酸酯、苯乙烯嵌段共聚物、丙烯-丁二烯-苯二烯共聚物、聚对苯二甲酸酯类、聚丙烯酸酯、聚氯乙烯、聚酰胺、聚苯硫醚、三聚氰胺树脂、氯化聚氯乙烯、尿素甲醛树脂、聚胺酯、壳聚糖中的任一种或两种以上的高分子改性而成；
所述天然填料为700-1400℃高温煅烧后的贝壳粉或蛋壳粉、氧化钙、氢氧化钙、氧化镁、氢氧化镁、提纯后的黑水虻蛹壳粉中任意一种或两种以上,或纳米粒子与煅烧后的贝壳粉的复合物；或纳米粒子与煅烧后的蛋壳粉的复合物；
所述改性高分子在混合物中质量占比为5-60％，天然填料为40-95％。
优选的，所述复合物中,纳米粒子与贝壳粉或蛋壳粉的质量比例为100:1至1:100。
优选的，所述的纳米粒子为纳米银、纳米氧化锌的其中一种或两种。
优选的，还添加了混合物总质量0.5％以下的抗氧化剂。
优选的，所述包覆的具体方法为干式混炼:將天然填料与改性高分子在混炼机中进行混合造粒形成包覆物。
优选的，所述包覆的具体方法为湿式混炼:将改性高分子以溶剂溶解后，再将天然填料加入溶解后的改性高分子溶液中搅拌均匀,溶液烘干后对得到的固体混合物再经粉碎而成的粒子或粉末的包覆物。
优选的,所述高分子改性为高分子接枝官能基，或添加相容剂进行的改性，所述官能基或相容剂为选自环氧型、恶唑啉型、胺基型、酸酐型、羧酸型、羟基型、环氧型反应型、钛酸酯型、硅烷型、多巴胺型、醛基型、肽基酰亚胺型和异氰酸酯型中的任意一种或一种以上。
本发明进而公开了一种长效型的天然多功能添加剂应用，可应用于各种塑料加工工艺，或保养品的添加或调节。
采用本发明所述长效型的天然多功能添加剂制备方法，具有以下积极效果：
(一)成本低廉，原材料中部分属于废弃物回收再利用。
(二)使天然填料的抗菌性更加持久，并且易于保存。
(三)使天然填料剂的在产品工艺中更易于分散，不易团聚。
(四)可以提升产品的机械强度。
(五)可以提升产品的热耐性质。
(六)产品无生物毒性。
(七)存放安全，人体可以直接触碰，包覆造粒后天然填料颗粒尺寸变大，不易随气流随意漂浮散落，应用于生产工艺更加方便。
附图说明
图1为本发明所述湿法混炼的一个具体实施方式流程示意图；
图2为本发明所述干法混炼的一个具体实施方式流程示意图；
图3为本发明所述湿法混炼下得到的产物形态示意图；真实产品中产物形态一般呈不规则形状；
图4为本发明所述干法混炼下得到的产物形态示意图；
图3和图4中圆形小颗粒表示贝壳粉、蛋壳粉、氧化钙、氢氧化钙、氧化镁、氢氧化镁、提纯后的黑水虻蛹壳粉中的任意一种,被包覆或附着在改性高分子内部或表面。
具体实施方式
下面对本发明的具体实施方式作进一步的详细说明。
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合具体实施方式对本发明作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于下述实施例。在不脱离本发明上述技术思想情况下，根据本领域普通技术知识和惯用手段，做出各种替换和变更，均应包括在本发明的范围内。
本发明所述长效型的天然多功能添加剂制备方法，具体为利用改性高分子对天然填料进行包覆，所述改性高分子为生物可降解高分子、水溶性高分子、聚烯烃，聚羟基脂肪酸酯、苯乙烯嵌段共聚物、丙烯-丁二烯-苯二烯共聚物、聚对苯二甲酸酯类、聚丙烯酸酯、聚氯乙烯、聚酰胺、聚苯硫醚、三聚氰胺树脂、尿素甲醛树脂、聚胺酯、壳聚糖中所述的任一种或两种以上的高分子改性而成；所述天然填料为700-1400℃高温煅烧后的贝壳粉、氧化钙、氢氧化钙、氧化镁、氢氧化镁、提纯后的黑水虻蛹壳粉中任意一种,或纳米粒子与煅烧后的贝壳粉的复合物；所述改性高分子在混合物中质量占比为5-60％，天然填料为40-95％。
高分子改性为高分子接枝官能基，或添加相容剂进行的改性，所述官能基或相容剂为选自环氧型、恶唑啉型、胺基型、酸酐型、羧酸型、羟基型、多巴胺型、醛基型、环氧型反应型、钛酸酯型、硅烷型、肽基酰亚胺型和异氰酸酯型中的任意一种或一种以上。
采用上述改性方式后的高分子,由于具有更多的官能基，可以与天然天加剂如：贝壳粉或蛋壳,氧化钙、提纯后的黑水虻蛹壳粉形成键结反应，提高了高分子材料的相容性与分散性。
本发明中，所述的长效型的天然多功能添加剂可以应用于作为提升塑料的拉伸性能、热性能，以及赋予其优异的抗菌性能。并且可以长时间保存不易受环境的影响。
以下给出本发明的多个具体实施例。
实施例1：长效型的天然多功能添加剂制备方法及应用于聚丙烯
将高温煅烧后的1000目贝壳粉与改性聚丙烯(丙烯酸接枝聚丙烯)在180-200℃混炼机具共混后造粒，造粒直径为2-4mm即得到本发明所述天然多功能添加剂，贝壳粉与改性聚丙烯质量比例为1:1，另加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
将实施例1制得的天然填料以不同质量比例添加到聚丙烯中，并以传统的贝壳粉以对应质量比例添加至聚丙烯中作为对照例，添加后的混合材料性能如表一所示。
表一中各个实施例括号内的百分比表示本发明所述天然多功能添加剂中贝壳粉在聚丙烯中的质量比,各个对照例括号内的百分比表示贝壳粉在聚丙烯中的质量比,以下其余各表类似。
表一
Figure BDA0002725285700000061
Figure BDA0002725285700000071
由表一结果表明，聚丙烯随着天然填料贝壳粉含量的增加，其拉伸强度就愈低，由于天然填料与塑料不相容，易造成填料的团聚或材料的分相。而本实施例的天然填料，不但不会降低塑料的性能，反而能有效提升其拉伸强度。另外，表一表明了两种添加剂在抗菌活性的效能接近，天然填料更佳，这是由于天然填料更易于分散于聚丙烯塑料中。
实施例2：长效型的天然多功能添加剂制备方法及应用于聚对苯二甲酸乙二醇酯。
将高温煅烧后1200目贝壳粉与改性聚乙烯(马来酸酐接枝聚乙烯)在180-195℃混炼机具共混后造粒，造粒直径为2-4mm，即得到本发明所述天然多功能添加剂。贝壳粉与改性聚乙烯质量比例为1.2:1，另外加总量之外的0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例2括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚对苯二甲酸乙二醇酯中的质量比，并以传统的贝壳粉以对应质量比例添加至聚对苯二甲酸乙二醇酯中作为对照例，添加后的混合材料性能如表二所示(添加时的温度为260-280℃)：
表二
Figure BDA0002725285700000081
实施例3：长效型的天然多功能添加剂制备方法及应用于聚酰胺。
将高温煅烧后800目贝壳粉与改性聚酰胺6(乙二胺接枝聚酰胺)在230-240℃混炼机具共混后造粒，造粒直径为2-4mm，即得到本发明所述天然多功能添加剂。贝壳粉与改性聚酰胺6质量比例为1:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例3括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚酰胺6中的质量比，并以传统的贝壳粉以对应质量比例添加至聚酰胺6中作为对照例，添加后的混合材料性能如表三所示：
表三
Figure BDA0002725285700000091
实施例4：长效型的天然多功能添加剂制备方法及应用于生物可降解材料
将高温煅烧后800目贝壳粉与改性聚乳酸(马来酸接枝聚乳酸)在180-195℃混炼机具共混后造粒即得到本发明所述天然多功能添加剂；贝壳粉与改性聚乳酸比例为0.8:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例4括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚乳酸材料中的质量比，并以传统的贝壳粉以对应质量比例添加至聚乳酸中作为对照例，添加后的混合材料性能如表四所示：
表四
Figure BDA0002725285700000101
实施例5：长效型的天然多功能添加剂制备方法及应用于聚乙烯
将2000目氧化钙与改性聚乙烯(马来酸酐接枝聚乙烯)在180-195℃混炼机具共混后造粒后得到本发明所述天然多功能添加剂。氧化钙与改性聚乙烯比例为1:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例5括号内的百分比表示本发明的天然多功能添加剂中的氧化钙在聚乙烯材料中的质量比，并以传统的氧化钙以对应质量比例添加至聚乙烯中作为对照例，添加后的混合材料性能如表五所示：
表五
Figure BDA0002725285700000111
实施例6：长效型的天然多功能添加剂制备方法及应用于苯硫醚
高温煅烧后1000目贝壳粉与改性聚苯硫醚(聚苯硫醚30％质量比与马来酸酐接枝聚乙烯共聚物70％质量比)在285-300℃混炼机具共混后造粒即得到本发明所述天然多功能添加剂。贝壳粉与改性聚苯硫醚比例为1:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例6括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚苯硫醚材料中的质量比，并以传统的贝壳粉以对应质量比例添加至聚苯硫醚中作为对照例，添加后的混合材料性能如表六所示：
表六
Figure BDA0002725285700000121
由表六结果表明，聚苯硫醚随着两种添加剂含量的增加，其拉伸强度都有所提高，而本发明所得到的添加剂比普通添加剂提高更多。另外，表中也表明了两种添加剂在抗菌活性的效能接近。
实施例7：长效型的天然多功能添加剂制备方法及应用于高密度聚乙烯(HDPE)。
以十氢化萘作为溶剂将改性超高分子量聚乙烯(马来酸酐接枝聚乙烯50％与超高分子量聚乙烯50％共混物)溶解，然后将高温煅烧后的1200目贝壳粉加入改性聚乙烯溶液，以快速搅拌机以500rpm进行搅拌分散，
然后将溶液烘干后，剩余固体物质进行粉碎并过50目筛，即为本发明所述添加剂。贝壳粉与改性聚乙烯的质量比例为9:1，无须另外添加抗氧化剂。
实施例7括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在高密度聚乙烯中的质量比，并以传统的贝壳粉以对应质量比例添加至高密度聚乙烯中作为对照例，添加后的混合材料性能如表七所示,抗张强度本发明的改善效果显著优于贝壳粉：
表七
Figure BDA0002725285700000131
Figure BDA0002725285700000141
实施例8：将添加剂添加后模拟长时间存放后的抗菌性能比较
将高温煅烧后1000目贝壳粉与改性聚丙烯(马来酸酐接枝聚丙烯)在180-195℃混炼机具共混后造粒，造粒直径2-4mm，得到本发明所述添加剂。贝壳粉与改性聚丙烯质量比例为1:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
将上述得到的添加剂与单一的贝壳粉同时都经过在相对湿度为80％，温度为30℃的恒温恒湿箱放置1周后，再放置于紫外光照射7天后，以3％质量含量分别添加至聚丙烯后所制备的材料性能如表八所示，本发明的天然多功能添加剂中的贝壳粉质量比掺入聚丙烯作为实施例8，贝壳粉掺入聚丙烯作为对照例8：
表八
Figure BDA0002725285700000142
Figure BDA0002725285700000151
可见本发明的杀菌性能在一定保存时间后的杀菌率降低比例低于贝壳粉，本发明中贝壳粉可以更长效的保存与使用，且不受环境影响，而且易于分散于塑料中，易于分散所以在塑料中会有更好效果，并且与塑料相容性更好，可以提升材料的机械强度；由于存在有改性聚丙烯的包覆在外层的保护，经过了恒温恒湿紫外后，几乎不潮解、也不易光老化，杀菌率衰减极小。
实施例9：模拟长时间存放后的抗菌性能比较
将高温煅烧后1000目贝壳粉/纳米氧化锌粒子与改性聚丙烯(马来酸酐接枝聚丙烯)在180-195℃混炼机具共混后造粒，造粒直径2-4mm即得到本发明所述添加剂。贝壳粉/纳米氧化锌粒子与改性聚丙烯质量比为1:1，另外加总量0.3％的抗氧化剂。其中贝壳粉与纳米氧化锌粒子的质量比为1:1。
将上述得到的添加剂与贝壳粉/纳米氧化锌粒子复合物同时都经过在相对湿度为80％，温度为30℃的恒温恒湿箱放置1周后，再放置于紫外光照射7天，以5％质量含量分别添加至聚丙烯后所制备的材料性能如表八所示，本发明的天然多功能添加剂中的贝壳粉质量比掺入聚丙烯作为实施例9，贝壳粉掺入聚丙烯作为对照例9：：
表九
Figure BDA0002725285700000161
由表八、九表明，普通添加剂在恒温恒湿箱以及UV光照射各7天后所导致裂解、热交联或是潮解等原因造成的杀菌率退化现象。本发明由于采用改性高分子对天然填料进行包覆，可以延缓添加剂因时间的变化或环境的影响所造成的热氧老化，而使其抗菌活性的时效更长。
实施例10：长效型的天然多功能添加剂制备方法及应用于聚己内酯生物可降解材料
将高温煅烧后800目蛋壳粉与改性聚己内酯(即丙烯酸接枝聚己内酯)在75-85℃混炼机具共混后造粒即得到本发明所述天然多功能添加剂；贝壳粉与改性聚己内酯比例为1:1，另外加总量0.3％的抗氧化剂,抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例10括号内的百分比表示本发明的天然多功能添加剂中的蛋壳粉在聚己内酯材料中，并以传统的蛋壳粉以对应质量比例添加至聚己内酯中作为对照例，添加后的混合材料性能如表四所示：
表十
Figure BDA0002725285700000171
实施例11：长效型的天然多功能添加剂制备方法及应用于聚氯乙烯
将高温煅烧后800目贝壳粉与改性氯化聚乙烯在85-90℃混炼机具共混后造粒即得到本发明所述天然多功能添加剂；贝壳粉与改性氯化聚乙烯比例为1:1，另外加总量0.3％的抗氧化剂。
实施例11括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚氯乙烯材料中的质量比，并以传统的贝壳粉以对应质量比例添加至聚氯乙烯中作为对照例，添加后的混合材料性能如表十一所示：
表十一
Figure BDA0002725285700000181
实施例12：长效型的天然多功能添加剂制备方法及应用于聚乙烯醇
将800目氧化钙与改性聚乙烯醇(以戊二醛为相容剂)在200-225℃混炼机具共混后造粒后得到本发明所述天然多功能添加剂。1300℃高温煅烧后的贝壳粉(以2000目筛选)与改性聚乙烯醇比例为0.8:1，另外加总量0.4％的抗氧化剂，抗氧化剂为0.2％质量分数的1010抗氧化剂以及0.2％的168抗氧化剂混合物。另外加总量5％的甘油作为塑化剂。
实施例12括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉在聚乙烯醇材料中的质量比，并以贝壳粉末对应质量比例添加至聚乙烯中作为对照例，添加后的混合材料性能如表十二所示：
表十二
Figure BDA0002725285700000191
实施例13：长效型的天然多功能添加剂制备方法及应用于聚乙烯
将800目氧化钙与改性聚乙烯(马来酸酐接枝聚乙烯)在180-195℃混炼机具共混后造粒后得到本发明所述天然多功能添加剂。1200℃高温煅烧后的贝壳粉(1000目)、黑水虻蛹壳提取物粉末(1000目)与改性聚乙烯比例为0.6:0.2:1，另外加总量0.4％的抗氧化剂，抗氧化剂为0.2％质量分数的1010抗氧化剂以及0.2％的168抗氧化剂混合物。
实施例13括号内的百分比表示本发明的天然多功能添加剂中的贝壳粉加上黑水虻蛹壳提取物贝壳粉在聚乙烯材料中的质量比，并以贝壳粉末加上黑水虻蛹壳提取物对应质量比例添加至聚乙烯中作为对照例，添加后的混合材料性能如表十三所示：
表十三
Figure BDA0002725285700000201
实施例14：长效型的天然多功能添加剂制备方法及应用于聚乙烯
将1600目氢氧化钙与改性聚乙烯(马来酸酐接枝聚乙烯)在180-195℃混炼机具共混后造粒后得到本发明所述天然多功能添加剂。氧化镁与改性聚乙烯比例为1:1，另外加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
实施例14括号内的百分比表示本发明的天然多功能添加剂中的氢氧化钙在聚乙烯材料中的质量比，并以传统的氧化镁以对应质量比例添加至聚乙烯中作为对照例，添加后的混合材料性能如表五所示：
表十四
Figure BDA0002725285700000211
实施例15：长效型的天然多功能添加剂制备方法及应用于聚丙烯
将1600目的氧化镁与改性聚丙烯(丙烯酸接枝聚丙烯)在180-200℃混炼机具共混后造粒，造粒直径为2.5-4mm即得到本发明所述天然多功能添加剂，氧化镁与改性聚丙烯质量比例为1:1，另加总量0.3％的抗氧化剂，抗氧化剂可以为0.15％质量分数的1010抗氧化剂以及0.15％的168抗氧化剂混合物。
将实施例15制得的天然填料以不同质量比例添加到聚丙烯中，并以传统的氧化镁以对应质量比例添加至聚丙烯中作为对照例，添加后的混合材料性能如表一所示。
表15中各个实施例括号内的百分比表示本发明的天然多功能添加剂中的氧化镁在聚丙烯中的质量比,各个对照例括号内的百分比表示添加氧化镁在聚丙烯中的质量比,以下其余各表类似。
表十五
Figure BDA0002725285700000221
实施例16：保养品用的天然添加剂制备方法
脱乙酰度60％的壳聚糖凝胶配制：称取0.1克的壳聚糖。在100mL干净烧杯中,加入约50mL水,利用乳酸调整水溶液pH值为5。在搅拌条件下,将称好的壳聚糖投至烧杯中直到溶解，完成凝胶配制。称取3克的3000目牡蛎壳粉慢慢的加入到壳聚糖凝胶中，使其均匀分散至凝胶中。利用冷冻干燥脱去水份，然后经粉碎或研磨后即完成保养品用的天然添加剂制备方法。除了使保养品具抗菌防霉性质，提升保存期限，并且可作为保养品的吸湿调节与pH调节。
如表十六所示，对照例16为不含本发明所述添加剂的乳液，乳液由橄榄油和乳化剂所配制得到，实施例为将上述方法制得的添加剂以0.3％质量比添加到乳液，可得知含天然添加剂的乳液具有优异的抑菌性能。
表十六
样品 杀菌率(％)
实施例16(0.3％) 99.99
对照例16(0％) 32.6
前文所述的为本发明的各个优选实施例，各个优选实施例中的优选实施方式如果不是明显自相矛盾或以某一优选实施方式为前提，各个优选实施方式都可以任意叠加组合使用，所述实施例以及实施例中的具体参数仅是为了清楚表述发明人的发明验证过程，并非用以限制本发明的专利保护范围，本发明的专利保护范围仍然以其权利要求书为准，凡是运用本发明的说明书内容所作的等同结构变化，同理均应包含在本发明的保护范围内。

Claims (8)

1.一种长效型的天然多功能添加剂制备方法，其特征在于，利用改性高分子对天然填料进行包覆，所述改性高分子为生物可降解高分子、水溶性高分子、聚烯烃，聚羟基脂肪酸酯、苯乙烯嵌段共聚物、丙烯-丁二烯-苯二烯共聚物、聚对苯二甲酸酯类、聚丙烯酸酯、聚氯乙烯、聚酰胺、聚苯硫醚、三聚氰胺树脂、氯化聚氯乙烯、尿素甲醛树脂、聚胺酯、壳聚糖中的任一种或两种以上的高分子改性而成;
所述天然填料为700-1400℃高温煅烧后的贝壳粉或蛋壳粉、氧化钙、氢氧化钙、氧化镁、氢氧化镁、提纯后的黑水虻蛹壳粉中任意一种或两种以上,或纳米粒子与煅烧后的贝壳粉的复合物；或纳米粒子与煅烧后的蛋壳粉的复合物；
所述改性高分子在混合物中质量占比为5-60%，天然填料为40-95%。
2.如权利要求1所述的制备方法，其特征在于，所述复合物中,纳米粒子与贝壳粉或蛋壳粉的质量比例为100:1 至 1:100。
3.如权利要求1所述的制备方法，其特征在于，所述的纳米粒子为纳米银、纳米氧化锌的其中一种或两种。
4.如权利要求1所述的制备方法，其特征在于，还添加了混合物总质量0.5%以下的抗氧化剂。
5.如权利要求1所述的制备方法，其特征在于，所述包覆的具体方法为干式混炼:將天然填料与改性高分子在混炼机中进行混合造粒形成包覆物。
6.如权利要求1所述的制备方法，其特征在于，所述包覆的具体方法为湿式混炼: 将改性高分子以溶剂溶解后，再将天然填料加入溶解后的改性高分子溶液中搅拌均匀,溶液烘干后对得到的固体混合物再经粉碎而成的粒子或粉末的包覆物。
7.如权利要求1所述的制备方法,其特征在于, 所述高分子改性为高分子接枝官能基，或添加相容剂进行的改性，所述官能基或相容剂为选自环氧型、恶唑啉型、胺基型、酸酐型、羧酸型、羟基型、环氧型反应型、钛酸酯型、硅烷型、多巴胺型、醛基型、肽基酰亚胺型和异氰酸酯型中的任意一种或一种以上。
8.一种长效型的天然多功能添加剂应用，其特征在于，可应用于各种塑料加工工艺，或保养品的添加或调节。
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