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CN113857018A - 一种仿真植物用可降解变色材料的制备方法 - Google Patents

一种仿真植物用可降解变色材料的制备方法 Download PDF

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CN113857018A
CN113857018A CN202111164596.5A CN202111164596A CN113857018A CN 113857018 A CN113857018 A CN 113857018A CN 202111164596 A CN202111164596 A CN 202111164596A CN 113857018 A CN113857018 A CN 113857018A
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胡伟
胡涛
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Zhejiang Jiawei Crafts Co ltd
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Abstract

该发明涉及可降解材料技术领域,具体关于一种仿真植物用可降解变色材料的制备方法;将二巯基丁二酸,巯基聚乳酸,烯基木质素接枝在一起,在紫外光照射下固化,可以和聚乳酸共同使用,作为能被自然界中微生物完全降解,有利于保护环境。

Description

一种仿真植物用可降解变色材料的制备方法
技术领域
该发明涉及可降解材料技术领域,尤其是一种仿真植物用可降解变色材料的制备方法。
背景技术
仿真植物获得了快速的发展,产品更加丰富,如:仿真棕榈树系列、保鲜棕榈树系列、仿真椰子树系列、仿真海枣(藻)树系列、仿真榕树、古榕树系列、仿真树系列、PU树系列、仿真植物系列、电缆伪装藤、伪装树系列、仿真桃花树、樱花树、仿真竹子系列、仿真树皮系列、仿真叶子系列、仿真藤条系列、仿真草坪系列、保鲜植物系列、仿真水果、蔬菜系列等。仿真绿植一般采用高环保高仿真材料制作,绿植内部结构一般为钢结构,表面为环氧树脂缠绕成型,叶子和花瓣内部也是钢结构,表面采用PVC、PU、PE、绢布等材料制作。
CN111087882A公开了一种景观装饰用植物材料的加工试剂及其制备方法,所述加工试剂包括以下原料:聚丙烯酸酯乳液、钛白粉、水性丙烯酸树脂乳液、乙醇、有机硅消泡剂、分散及增稠剂、成膜助剂、润湿剂、多功能助剂、防腐剂、浓缩型有机染料、水性香精和水。本发明提供的景观装饰用植物材料加工试剂配方所用原料均无毒性,符合国际环保标准要求;试剂加工过程简单,原料成本价格低廉;采用该试剂加工出的植物材料质地柔软、气味清新、触感富有弹性、色泽鲜艳持久,具有着色均匀、色牢度好、防水、防霉、耐磨擦等特性,可用于普通的草本、木本、驯鹿地衣、苔藓等植物材料的加工处理,加工后的植物材料广泛适用于各类室内外景观装饰工程。
现有技术存在以下技术问题:
仿真植物采用PVC、PU、PE等材料,在淘汰后不易降解,造成环境污染。同时,为了提高观赏效果,有必要研究一种可变色的叶片材料,以提高仿真植物的价值。
发明内容
该发明公开了一种仿真植物用可降解变色材料的制备方法,属于仿真植物技术领域;经裁剪成仿真植物的叶片。
一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
按质量份数,采用高速搅拌机将10-18份的二巯基丁二酸,30-50份的巯基聚乙二醇聚乳酸,100-130份的烯基木质素,10-16份的质量百分比含量5-10%胆甾型液晶的石油醚溶液,300-450份聚丙烯酸乳液,2.5-5份光引发剂,30-50℃搅拌2-5h,再加入2-6份阻燃有机膨润土,搅拌2-5h,取出均匀涂敷在基膜上,厚度约1-10cm,通入氮气,用紫外光下照射2-30min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,得到一种仿真植物用可降解变色材料经裁剪成仿真植物的叶片。
进一步的,所述巯基聚乙二醇聚乳酸为市售产品,分子量200-2000;结构式为:
Figure BDA0003291264910000021
进一步的,所述高速搅拌机转速为3500-5000r/min;
进一步的,所述烯基木质素的制备方法为:
按质量份数,将20-40份乙酸木质素溶于100-200份氢氧化钠溶液,加入50-100份溴丙烯,升温反应一段时间,反应结束后冷却至室温,用盐酸调节溶液,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素;
进一步的,所述氢氧化钠浓度为0.5-3mol/L;
进一步的,所述反应温度为70-90℃,反应压力为常压;
进一步的,所述反应时间为3-6h;
进一步的,所述盐酸浓度为0.5-3mol/L;
进一步的,所述调节溶液pH为1.8-2.2;
进一步的,所述聚丙烯酸乳液,固含量为2.5-10.5%,聚丙烯酸乳液为市售产品;如LA132牌号的聚丙烯酸乳液;
进一步的,所述光引发剂为安息香乙醚、α,α-二甲氧基-α-苯基苯乙酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基-环己基苯酮、二苯甲酮、2,4,6-三甲基苯甲酰二苯基氧化膦或双芳基膦氧化物;
进一步的,所述胆甾型液晶选自胆甾醇乙酸酯,胆甾醇丙酸酯,胆甾醇丁酸酯,胆甾醇苯甲酸酯;
进一步的,所述阻燃有机膨润土为市售产品,如V0阻燃有机膨润土;
进一步的,所述均匀涂敷在草纸上的厚度优选为2-5cm;
进一步的,所述紫外光源可以包括:低强度光源如黑光或高强度光源如中压汞灯;
进一步的,所述使用光化辐射强度范围为0.1-150毫瓦/平方厘米;
进一步的,所述使用光化辐射强度范围优化为0.5-50毫瓦/平方厘米。
进一步的,所述基膜选自EVA博膜。
反应机理:
将二巯基丁二酸,巯基聚乙二醇聚乳酸,烯基木质素通过巯基-烯基点击反应接枝在一起,具有很好的降解性能。
技术效果为:
1、本发明整个制备过程具有条件温和(紫外光电流)、节能、无污染、速度快、操作方便等优点,最重要的是其没有毒性交联剂的使用,安全性高;
2.本发明将二巯基丁二酸,巯基聚乳酸,烯基木质素通过巯基-烯基点击反应接枝在一起,在紫外光照射下固化,可以和聚乳酸共同使用,作为能被自然界中微生物完全降解,这对保护环境非常有利。EVA薄膜是由EVA原料通过流延挤出所生产的薄膜,是一种新一代绿色环保可降解材料,也具有可生物降解;
3.胆甾型液晶态变色剂的液晶分子具有特有的分子排列,其螺纹距与可见光相近,使得它对光及温度的敏感性增强,随温度的变化,胆甾型液晶态的螺旋结构变化,进而引起此类物质对光的折射、反射性变化,色泽发生变化。在日光下,随温度的升高,液晶的色彩按红、橙、黄、绿、蓝、靛、紫的顺序变化,温度下降又按相反顺序变色。
附图说明
图1为实施例1仿真植物用可降解变色材料经裁剪成仿真植物叶片。
图2为实施例1仿真植物用可降解变色材料均匀涂敷在基膜上固化后的工序。
图3为实施例1仿真植物用可降解变色材料搅拌混合设备。
具体实施方式
下面结合优选具体实施方式对本发明进行详细叙述,但本发明内容实施和保护内容不限于此:
实施例中的基膜选自EVA博膜;所述阻燃有机膨润土为如V0阻燃有机膨润土;
实施例1
采用高速搅拌机将10份的二巯基丁二酸,30份的巯基聚乙二醇聚乳酸,100份的烯基木质素,分子量600,10份的质量百分比含量5%胆甾型液晶的石油醚溶液,300份聚丙烯酸乳液,2.5份光引发剂,30℃搅拌2h,再加入2份阻燃有机膨润土,搅拌2h,取出均匀涂敷在基膜上,厚度约1cm,通入氮气,用紫外光下照射2min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将20g乙酸木质素溶于100g浓度为0.5mol/L的氢氧化钠溶液,加入50g溴丙烯,70℃下反应6h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇乙酸酯。
实施例2
在室温(25℃)下采用高速搅拌机将12g的二巯基丁二酸,35g的巯基聚乙二醇聚乳酸,分子量200,100g烯基木质素,350g乙醇,3g光引发剂α,α-二甲氧基-α-苯基苯乙酮,搅拌2h,转速为4000r/min,再加入12gV0阻燃有机膨润土,搅拌2h,取出均匀涂敷在草纸上,厚度约为3cm,通入氮气,用紫外光下照射20min,光化辐射强度为20毫瓦/平方厘米,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
采用高速搅拌机将12份的二巯基丁二酸,35份的巯基聚乙二醇聚乳酸,110份的烯基木质素,12份的质量百分比含量7%胆甾型液晶的石油醚溶液,330份聚丙烯酸乳液,3份光引发剂,35℃搅拌3h,再加入3份阻燃有机膨润土,搅拌4h,取出均匀涂敷在基膜上,厚度约5cm,通入氮气,用紫外光下照射10min,取出后水洗,干燥,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将25g乙酸木质素溶于120g浓度为1.5mol/L的氢氧化钠溶液,加入65g溴丙烯,70℃下反应6h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇丙酸酯。
实施例3
在室温(25℃)下采用高速搅拌机将14g的二巯基丁二酸,40g的巯基聚乙二醇聚乳酸,分子量2000,110g烯基木质素,350g乙醇,3.5g光引发剂2-羟基-2-甲基-1-苯基-1-丙酮,搅拌3h,转速为4000r/min,再加入14gV0阻燃有机膨润土,搅拌3h,取出均匀涂敷在草纸上,厚度约为3cm,通入氮气,用紫外光下照射20min,光化辐射强度为30毫瓦/平方厘米,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
采用高速搅拌机将16份的二巯基丁二酸,40份的巯基聚乙二醇聚乳酸,117份的烯基木质素,14份的质量百分比含量8%胆甾型液晶的石油醚溶液,400份聚丙烯酸乳液,4份光引发剂,42℃搅拌4h,再加入4份阻燃有机膨润土,搅拌5h,取出均匀涂敷在基膜上,厚度约8cm,通入氮气,用紫外光下照射25min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将30g乙酸木质素溶于150g浓度为1.5mol/L的氢氧化钠溶液,加入80g溴丙烯,80℃下反应5h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇丁酸酯。
实施例4
一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
按质量份数,采用高速搅拌机将16份的二巯基丁二酸,47份的巯基聚乙二醇聚乳酸,128份的烯基木质素,15份的质量百分比含量9%胆甾型液晶的石油醚溶液,410份聚丙烯酸乳液,4.2份光引发剂,50℃搅拌4h,再加入5份阻燃有机膨润土,搅拌5h,取出均匀涂敷在基膜上,厚度约10cm,通入氮气,用紫外光下照射30min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将35g乙酸木质素溶于150g浓度为2.0mol/L的氢氧化钠溶液,加入85g溴丙烯,80℃下反应5h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇苯甲酸酯。
实施例5
一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
采用高速搅拌机将18份的二巯基丁二酸,48份的巯基聚乙二醇聚乳酸,130份的烯基木质素,15份的质量百分比含量9%胆甾型液晶的石油醚溶液,440份聚丙烯酸乳液,4.5份光引发剂,50℃搅拌5h,再加入5份阻燃有机膨润土,搅拌5h,取出均匀涂敷在基膜上,厚度约10cm,通入氮气,用紫外光下照射30min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将35g乙酸木质素溶于180g浓度为2.5mol/L的氢氧化钠溶液,加入90g溴丙烯,90℃下反应3h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇乙酸酯。
实施例6
一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
采用高速搅拌机将18份的二巯基丁二酸,50份的巯基聚乙二醇聚乳酸,130份的烯基木质素,16份的质量百分比含量10%胆甾型液晶的石油醚溶液,450份聚丙烯酸乳液,5份光引发剂,50℃搅拌5h,再加入6份阻燃有机膨润土,搅拌5h,取出均匀涂敷在基膜上,厚度约10cm,通入氮气,用紫外光下照射30min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,经裁剪成仿真植物的叶片。
所述烯基木质素的制备方法为:
将40g乙酸木质素溶于200g浓度为3mol/L的氢氧化钠溶液,加入100g溴丙烯,90℃下反应3h。反应结束后冷却至室温,用盐酸调节溶液pH至2左右,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
所述胆甾型液晶选自胆甾醇乙酸酯。
对比例1
不加入二巯基丁二酸,其余与实施例1相同。
对比例2
不加入巯基聚乙二醇聚乳酸,其余与实施例1相同。
对比例3
不加入烯基木质素,其余与实施例1相同。
测试方法:
(1)将聚乳酸在60℃下烘干6~8小时后,与实施例及对比例所得仿真植物用可降解材料与按质量比70:30熔融共混,挤出造粒后,再次熔融共混,造粒,得到目标材料,挤出加工温度为:一段温度170~175℃,二段温度170~180℃,三段温度175~185℃,四段温度175~180℃。
材料性能见表1。拉伸强度及断裂伸长率按GBT1040.2-2006进行测试。
表1实施例及对比例材料性能表
Figure BDA0003291264910000071
Figure BDA0003291264910000081
(2)在日光下,实施例1-6的仿真植物的叶子,在24-40℃的范围,随温度的升高,颜色按顺序变化,温度下降又按相反顺序变色。

Claims (10)

1.一种仿真植物用可降解变色材料的制备方法,其特征在于包括以下步骤:
按质量份数,采用高速搅拌机将10-18份的二巯基丁二酸,30-50份的巯基聚乙二醇聚乳酸,100-130份的烯基木质素,10-16份的质量百分比含量5-10%胆甾型液晶的石油醚溶液,300-450份聚丙烯酸乳液,2.5-5份光引发剂,30-50℃搅拌2-5h,再加入2-6份阻燃有机膨润土,搅拌2-5h,取出均匀涂敷在基膜上,厚度约1-10cm,通入氮气,用紫外光下照射2-30min,取出后水洗,干燥,得到一种仿真植物用可降解变色材料,表面再塑封一层PET透明膜,得到一种仿真植物用可降解变色材料经裁剪成仿真植物的叶片。
2.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述高速搅拌机转速为3500-5000r/min。
3.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述烯基木质素的制备方法为:
按质量份数,将20-40份乙酸木质素溶于100-200份氢氧化钠溶液,加入50-100份溴丙烯,升温反应时间为3-6h,反应结束后冷却至室温,用盐酸调节溶液pH,析出固体,过滤固体,用去离子水、乙醇洗涤除去过量无机盐和溴丙烯化合物,干燥后得烯基木质素。
4.根据权利要求3所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述氢氧化钠浓度为0.5-3mol/L;所述反应温度为70-90℃,反应压力为常压。
5.根据权利要求3所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述;所述盐酸浓度为0.5-3mol/L;所述调节溶液pH为1.8-2.2。
6.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述溶剂为无水乙醇或三氯甲烷。
7.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述光引发剂为安息香乙醚、α,α-二甲氧基-α-苯基苯乙酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基-环己基苯酮、二苯甲酮、2,4,6-三甲基苯甲酰二苯基氧化膦或双芳基膦氧化物。
8.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述紫外光源可以包括:低强度光源如黑光或高强度光源如中压汞灯。
9.根据权利要求1所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述使用光化辐射强度范围为0.1-150毫瓦/平方厘米。
10.根据权利要求9所述的一种仿真植物用可降解变色材料的制备方法,其特征在于:所述胆甾型液晶选自胆甾醇乙酸酯,胆甾醇丙酸酯,胆甾醇丁酸酯,胆甾醇苯甲酸酯。
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