CN112940403B - 一种不可逆热致变色功能塑料及其制备方法 - Google Patents
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Abstract
本发明提供一种不可逆热致变色功能塑料及其制备方法,不可逆热致变色功能塑料,按照质量百分比计,其包含如下组分:塑料70.0‑99.9%,纳米级非晶丁二炔类材料0.1‑30%,稳定剂0‑10%。制备方法,包括:1)将塑料、纳米级非晶丁二炔类材料在添加或不添加稳定剂的条件下混合均匀;2)按照工程塑料或者塑料薄膜的制备工艺进行制作得到。本发明的功能塑料具有无毒副作用、成本低廉、温度适用范围广、热致变色灵敏且不可逆的特点。
Description
技术领域
本发明属于功能高分子领域,涉及一种含纳米级非晶丁二炔类化合物的不可逆热致变色功能塑料及其制备方法。
背景技术
随着科技社会的发展以及人们生活水平的提高,食品、药品安全问题已经成为社会关注的一个焦点。需冷链储存的食品或药品因温度变化造成的各类人员中毒事件在世界各地已多次发生,严重危害人类身体健康并造成了极大的经济损失。食品、药物,尤其是医用疫苗需在低温下(2~8℃)进行冷链运输和保存,若超出这个温度,各种不同程度的失效(如最敏感的口服脊髓灰质炎疫苗,在37℃下暴露2天就完全失效)。食品失效虽然不会像药品失效那样造成严重的后果,但是与药品相比,失效食品造成的危害范围更加广泛且出现频率更高。
鉴于以上所述现状,低成本的热致变色功能塑料的制备及推广能够有望为解决需冷链储存的食品、药品因温度失控造成的食品药品安全问题提供技术支持。
目前坦普泰姆公司在世界范围有三十余件核心专利,核心的变色材料是丁二炔化合物。进入中国的发明专利(申请号:201510353615.7)中公开了具有脲基的丁二炔化合物,对化合物结构、重结晶溶剂、晶体的晶型、晶胞参数等进行了保护,然而晶形丁二炔材料对材料纯度及后处理要求极高,制备过程复杂,成本高。3M公司采用了一种名为Timestrip含有记忆芯片的冷链智能标签,能在启动后反映在不同温度情况下所处的时间。比利时DeltaTRAK公司开发的WarmMark温度标签也能通过标签的颜色变化,反映产品经受的热环境情况。目前尚未见纳米级非晶丁二炔类材料在不可逆热致变色功能塑料中应用的相关文献。
发明内容
针对现有技术中存在的问题,本发明提供一种不可逆热致变色功能塑料及其制备方法,成本低,制备方法简单。
本发明是通过以下技术方案来实现:
一种不可逆热致变色功能塑料,按照质量百分比计,其包含如下组分:
塑料 70.0-99.9%
纳米级非晶丁二炔类材料 0.1-30%
稳定剂 0-10%。
优选的,所述纳米级非晶丁二炔类材料的粒径为20~100nm。
优选的,所述纳米级非晶丁二炔类材料的制备方法为:将非晶丁二炔类材料通过研磨得到。
优选的,所述纳米级非晶丁二炔类材料为式I所示化合物中的一种或多种的混合物:
式I中,A1为O或S原子;R1为碳原子数为1~30的直链烷烃或支链烷烃,碳原子数为1~30的直链烷烃或支链烷烃的醚、硫醚或胺类衍生物,碳原子数为3~9的环烃,或者碳原子数为3~9的环烃的醚、硫醚或胺类衍生物。
进一步的,所述纳米级非晶丁二炔类材料为式A、式B和式C所示化合物中的一种或多种的混合物:
优选的,所述塑料为工程塑料或塑料薄膜。
优选的,所述稳定剂为二苯酮衍生物、水杨酸衍生物、1,3,5-三嗪衍生物、胺基镍盐衍生物或氨基镍盐衍生物。
所述的不可逆热致变色功能塑料的制备方法,包括:
1)将塑料、纳米级非晶丁二炔类材料在添加或不添加稳定剂的条件下混合均匀;
2)按照工程塑料或者塑料薄膜的制备工艺进行制作得到。
与现有技术相比,本发明具有以下有益的技术效果:
纳米级非晶丁二炔类材料具有稳定且重复性高的时间-温度双维度热致变色特性,本发明通过对不同粒度的纳米级非晶丁二炔类材料在多种塑料基底中分散后制备得到不可逆热致变色功能塑料,该功能塑料具有不可逆温度指示、制备工艺简单、柔性且便于切割等优点,制备成塑料薄膜或工程塑料时,可用于制作对温度变化有特殊要求、需冷链保存的的各类产品(如食品、药物等)的包装袋或标签;本发明的功能塑料具有无毒副作用、成本低廉、温度适用范围广、热致变色灵敏且不可逆的特点。
本发明将纳米级非晶丁二炔分散到无毒副作用的塑料中,制备得到的不可逆热致变色功能塑料,具有制备工艺简单、成本低、时间-温度响应度高、产品应用范围广等特点。
附图说明
图1中:a是实施例2在不同温度(4℃、室温、37℃)下的热聚合行为定量研究图;b是实施例4在不同温度(4℃、室温、37℃)下的热聚合行为定量研究图;c是实施例1、3、5、6在4℃下的热聚合行为定量研究图;d是实施例1、3、5、6在37℃下的热聚合行为定量研究图。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。
本发明所述的不可逆热致变色功能塑料,其各组分及质量百分比如下:
塑料 70.0-99.9%
纳米级非晶丁二炔类材料 0.1-30%
稳定剂 0-10%。
所述的纳米级非晶丁二炔类材料的制备方法为:将非晶丁二炔类化合物材料通过-低温机械研磨、离心分散等工艺控制丁二炔不可逆热致变色材料粒度为20~100nm。
所述的非晶丁二炔类材料为式I所示化合物中的一种或多种的混合物:
式I中,A1为O或S原子;R1为碳原子数为1~30的直链烷烃或支链烷烃,碳原子数为1~30的直链烷烃或支链烷烃的醚、硫醚或胺类衍生物,碳原子数为3~9的环烃,或者碳原子数为3~9的环烃的醚、硫醚或胺类衍生物。
具体结构举例如式A~C,所举例子并不限制本发明保护范围,只是为了更好地理解本发明。
所述塑料为无毒副作用的工程塑料或塑料薄膜,包括但不限于聚乙烯、聚丙烯、聚1-丁烯、聚丁二烯、聚苯乙烯、聚氯乙烯、聚丙烯酸酯、聚甲基丙烯酸酯、脂肪族聚酯类。所述稳定剂包括但不限于二苯酮衍生物、水杨酸衍生物、1,3,5-三嗪衍生物和胺(氨)基镍盐衍生物等。
所述不可逆热致变色功能塑料的制备步骤如下:
1)按照上述质量百分比备料,将塑料、纳米级非晶丁二炔类材料在添加或不添加稳定剂的条件下混合均匀;
2)按照本领域公知的工程塑料或者塑料薄膜的制备工艺进行制作即得。
实施例
含有纳米级非晶丁二炔类不可逆变色材料的功能塑料的制备步骤如下:
1)将塑料、纳米级非晶丁二炔类材料在添加或不添加稳定剂的条件下混合均匀;
2)按照本领域公知的工程塑料或者塑料薄膜的制备工艺进行制作即得。
实施例1~6的具体条件见下表1:
表1实施例1~6制备条件
含有纳米级非晶丁二炔类不可逆变色材料的功能塑料的性能评价方法如下:
(1)将表1所得的功能塑料通过溶液加工形式,低温下制备得到功能塑料薄膜;所用的溶剂包括但不限于甲苯、苯、三氯甲烷、四氢呋喃、环己酮等;
(2)将所得薄膜剪裁成5*5mm模块后,置于-80℃冰箱内保存;取出不同配方所得薄膜1~6置于4℃、25℃(室温)和37℃恒温箱中,每天采用光密度仪测定薄膜的透光密度,对其变色行为进行量化评价;
(3)以时间(单位:天)为横坐标、光密度作为纵坐标绘制变色曲线(图1);
图1a为实施例1所得不可逆热致变色功能塑料薄膜1的变色曲线,可见在4℃下60天内不可逆热致变色功能塑料薄膜1光密度增加低于0.05,室温下60天内不可逆热致变色功能塑料薄膜1光密度增加低于0.1,37℃下60天内不可逆热致变色功能塑料薄膜1光密度增加高达0.6,且在七天内达到最大变色光密度的85%,易于肉眼及设备识别;图1b为实施例3所得不可逆热致变色功能塑料薄膜3的变色曲线,可见在4℃下60天内不可逆热致变色功能塑料薄膜3光密度增加低于0.8,室温下60天内不可逆热致变色功能塑料薄膜3光密度增加0.8,37℃下60天内不可逆热致变色功能塑料薄膜3光密度增加高达1.3,且在七天内:4℃下光密度增加0.1;室温下光密度增加0.5;37℃下光密度增加1.2,表明该配方适用于需冷链储运的产品,可根据变色终点的颜色将保质期设置为1-30天;图1c-d评价了不同实施例配方在4℃和37℃两个温度下的变色行为,为后续不用应用场景的不可逆热致变色功能塑料设计提供依据。
Claims (7)
2.根据权利要求1所述的不可逆热致变色功能塑料,其特征在于,所述纳米级非晶丁二炔类材料的粒径为20~100nm。
3.根据权利要求1所述的不可逆热致变色功能塑料,其特征在于,所述纳米级非晶丁二炔类材料的制备方法为:将非晶丁二炔类材料通过研磨得到。
5.根据权利要求1所述的不可逆热致变色功能塑料,其特征在于,所述塑料为工程塑料或塑料薄膜。
6.根据权利要求1所述的不可逆热致变色功能塑料,其特征在于,所述稳定剂为二苯酮衍生物、水杨酸衍生物、1,3,5-三嗪衍生物、胺基镍盐衍生物或氨基镍盐衍生物。
7.权利要求1所述的不可逆热致变色功能塑料的制备方法,其特征在于,包括:
1)将塑料、纳米级非晶丁二炔类材料在添加或不添加稳定剂的条件下混合均匀;
2)按照工程塑料或者塑料薄膜的制备工艺进行制作得到。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4788151A (en) * | 1986-09-29 | 1988-11-29 | Lifelines Technology, Inc. | Metal complexed acetylenic compounds useful as environmental indicating materials |
US4789637A (en) * | 1986-09-29 | 1988-12-06 | Lifelines Technology, Inc. | Acid complexed acetylenic compounds useful as environmental indicating materials |
CN102066293A (zh) * | 2007-10-30 | 2011-05-18 | 坦普泰姆公司 | 晶化的二乙炔指示剂化合物及其制备方法 |
CN111269128A (zh) * | 2020-04-02 | 2020-06-12 | 苏州爱玛特生物科技有限公司 | 1,1′-(六-2,4-二炔-1,6-二基)双(3-烷基脲)类化合物的合成方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4788151A (en) * | 1986-09-29 | 1988-11-29 | Lifelines Technology, Inc. | Metal complexed acetylenic compounds useful as environmental indicating materials |
US4789637A (en) * | 1986-09-29 | 1988-12-06 | Lifelines Technology, Inc. | Acid complexed acetylenic compounds useful as environmental indicating materials |
CN102066293A (zh) * | 2007-10-30 | 2011-05-18 | 坦普泰姆公司 | 晶化的二乙炔指示剂化合物及其制备方法 |
CN105037213A (zh) * | 2007-10-30 | 2015-11-11 | 坦普泰姆公司 | 晶化的二乙炔指示剂化合物及其制备方法 |
CN111269128A (zh) * | 2020-04-02 | 2020-06-12 | 苏州爱玛特生物科技有限公司 | 1,1′-(六-2,4-二炔-1,6-二基)双(3-烷基脲)类化合物的合成方法 |
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