CN116284930B - 一种可降解环保防伪包装材料及其制备方法 - Google Patents
一种可降解环保防伪包装材料及其制备方法 Download PDFInfo
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- CN116284930B CN116284930B CN202310314951.5A CN202310314951A CN116284930B CN 116284930 B CN116284930 B CN 116284930B CN 202310314951 A CN202310314951 A CN 202310314951A CN 116284930 B CN116284930 B CN 116284930B
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Abstract
本发明涉及可降解环保防伪包装材料技术领域,公开了一种可降解环保防伪包装材料及其制备方法;通过控制基材、第一涂层、第二涂层中各组分原料之间的配比,形成独特软硬结构(软硬程度依次为第二涂层>基材>第一涂层),使得包装材料即拥有优异的抗菌性能和刚性,又拥有优异的韧性和耐热性能。
Description
技术领域
本发明涉及可降解环保防伪包装材料技术领域,具体为一种可降解环保防伪包装材料及其制备方法。
背景技术
聚乳酸是一种生物基可降解聚合物,其来源于植物淀粉、蔗糖和玉米等天然资源。相比于传统的石油基聚合物,聚乳酸具有可降解性、可生物降解性、可再生性等优点,因此广泛应用于食品包装、医疗器械、生物材料等领域。
随着人们对环境保护和可持续发展的重视,聚乳酸作为一种可降解的材料,被越来越多的人所关注。在包装领域中,聚乳酸作为一种环保型的包装材料,可有效降低塑料污染问题。然而,由于聚乳酸的力学性能,热稳定性能和加工工艺等方面的限制,其在包装领域的应用还面临一些挑战。
因此,发明一种可降解环保防伪包装材料具有重要意义。
发明内容
本发明的目的在于提供一种可降解环保防伪包装材料及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种可降解环保防伪包装材料,其结构由内而外依次为基材、第一涂层、第二涂层;
进一步的,所述基材的原料包括以下组分,按质量份数计,聚乳酸复合单体80-100份、茶多酚1-2份、乙酰柠檬酸三丁酯5-15份、聚乙二醇20-30份、羟基乙酸80-100份;
进一步的,所述基材中聚乳酸复合单体为70-80wt%聚L-乳酸和20-30wt%聚D-L-乳酸;
进一步的,所述基材中聚乙二醇分子量为1000-2000;
进一步的,所述第一涂层的原料包含以下组分,按质量分数计,聚乳酸复合单体80-100份、羧甲基纤维素钠2-4份、钼酸铵4-6、木质素磺酸钠5-10份、辛酸亚锡1-1.5份、聚乙二醇20-30份、柠檬酸酯15-25份;
进一步的,所述第一涂层中聚乳酸复合单体为20-30wt%聚L-乳酸和70-80wt%聚D-L-乳酸;
进一步的,所述第一涂层中羧甲基纤维素钠浓度为1-2wt%;
进一步的,所述第一涂层中聚乙二醇分子量为400-500。
进一步的,所述第二涂层的原料包含以下组分,按质量份数计,聚乳酸复合单体80-100份、聚乙二醇20-30份、改性二氧化钛纳米颗粒15-30份、N,N’-亚甲基双丙烯酰胺0.5-1份、过硫酸钾1-1.5份;
进一步的,所述第二涂层中聚乳酸复合单体为70-80wt%聚L-乳酸和20-30wt%聚D-L-乳酸;
进一步的,所述第二涂层中聚乙二醇分子量为1000-2000;
一种可降解环保防伪包装材料制备方法,包含以下步骤:
S1:将聚乳酸复合单体、茶多酚和乙酰柠檬酸三丁酯加热至145-155℃熔融共混后,加入聚乙二醇和羟基乙酸继续熔融共混,165-180℃挤出造粒,吹塑,得到基材;
S2:将聚乳酸复合单体溶于四氢呋喃中预热至50-55℃,依次加入羧甲基纤维素钠、钼酸铵、木质素磺酸钠搅拌均匀,加入辛酸亚锡反应12-24h,加入聚乙二醇和柠檬酸酯,得到涂料B;
S3:将聚乙二醇、改性二氧化钛纳米颗粒、N,N’-亚甲基双丙烯酰胺和过硫酸钾加入到聚乳酸复合单体中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,热处理,得到可降解环保防伪包装材料;
进一步的,所述热处理温度为45-70℃,时间为4-6h。
进一步的,所述改性二氧化钛纳米颗粒制备方法,包含以下步骤:
将二氧化钛纳米颗粒加入体积比为1:1的乙醇水溶液中,加入硅烷偶联剂加热至45-50℃反应12-24h,旋蒸出去乙醇水溶液;在氮气氛围下,加入蒸馏水、丙烯酰胺和过硫酸铵加热至65-70℃反应12-24h,得到改性二氧化钛纳米颗粒。
进一步的,所述硅烷偶联剂为KH570;
进一步的,所述二氧化钛纳米颗粒:丙烯酰胺的质量比为1:(3-4)
进一步的,所述硅烷偶联剂加入量为二氧化钛纳米颗粒的7-8wt%。
与现有技术相比,本发明所达到的有益效果是:本发明在制备基材过程中通过在聚乳酸中加入茶多酚和乙酰柠檬酸三丁酯大大提高基材的力学性能和抑菌性能,加入羧基乙酸进一步提高基材的成膜性能;
通过聚乳酸复合单体和羧甲基纤维素钠的氢键交联作用,将钼酸铵、木质素磺酸钠光致变色结构成功引入聚乳酸中,加入柠檬酸酯提高了第二涂层的柔顺性、韧性和热稳定性能;通过3-氧代戊二酸二甲酯和乙二醛的Weiss-Cook缩合反应和碘甲烷的甲基化反应,制备得到羧酸酯中间体,接着通过在浓盐酸中回流脱羧,制备得到二酮单体,最后在四氢铝锂中还原得到二醇单体;将二醇单体与丁酸和柠檬酸的两步酯化反应合成柠檬酸酯。与传统生物基增塑剂如异山梨醇酯相比,柠檬酸酯中二醇单体通过甲基化将四个甲基引入环戊烷结构中阻碍了聚合物中高分子链段在高温下的运动,提高了材料的韧性和力学性能;同时其在热分解下生成的环内烯烃具有更高的热稳定性;而异山梨醇酯耐热性能较差原因在于异山梨醇酯分子结构中的四氢呋喃环耐热性能较差,在高温环境下也易出现交联现象,大大降低了材料的应用范围;
通过硅烷偶联剂和丙烯酰胺对二氧化钛进行改性,提高了二氧化钛纳米颗粒在聚乳酸中的分散性能,提高了第二涂层的抗菌性和耐磨损性能,同时,当包装材料废弃时二氧化钛能够作为聚乳酸降解催化剂,促进包装材料的降解和环保性能;通过对材料最后进行热处理,使得第一涂层中的羧甲基纤维素钠交联聚乳酸与第二涂层中的N,N’-亚甲基双丙烯酰胺,过硫酸钾和丙烯酰胺产生交联聚合作用产生类似凝胶效果使得基材与各涂层之间紧密结合,涂层不易脱落;
本发明通过控制基材、第一涂层、第二涂层中各组分原料之间的配比,形成独特软硬结构(软硬程度依次为第二涂层>基材>第一涂层),使得包装材料即拥有优异的抗菌性能和刚性,又拥有优异的韧性和耐热性能。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
以下实施例中,聚L-乳酸mw=60000、聚D-L-乳酸mw=10000、茶多酚、四氢呋喃、钼酸铵、丙烯酰胺、辛酸亚锡由上海麦克林生化科技股份有限公司提供,乙酰柠檬酸三丁酯由上海研恬生物科技有限公司提供,羧甲基纤维素钠、木质素磺酸钠、N,N’-亚甲基双丙烯酰胺、过硫酸钾由上海蓝季科技发展有限公司,二氧化钛纳米颗粒由南京先丰纳米材料科技有限公司提供,粒径20nm,3-氧代戊二酸二甲酯由3-氧代戊二酸二甲酯提供,聚乙二醇mw=400、聚乙二醇mw=1500由北京谨明生物科技有限公司提供,乙二醛由上海阿拉丁生化科技股份有限公司提供,碘甲烷由上海嵩爰化工科技有限公司提供;以下份数为质量单位;
柠檬酸酯制备方法,包含以下步骤:
将0.2mol氢氧化钠、0.2mol3-氧代戊二酸二甲酯依次加入200mL甲醇中,加热至60℃回流4h,加入0.1mol乙二醛常温反应12h,抽滤,用50mL甲醇洗涤,干燥,得到产物D;将0.03mol产物D溶于水中加入盐酸进行酸化处理,加入0.25mol碳酸钾和0.25mol碘甲烷搅拌12h,加热至45℃搅拌回流12h,抽滤,用50mL丙酮洗涤三次,旋蒸,再加入50mL二氯甲烷,过滤,旋蒸,甲醇重结晶,得到产物E;将50mL浓盐酸加入10g产物E中,加热至115℃回流5d,用125mL二氯甲烷萃取三次,洗涤,干燥,抽滤,旋蒸,得到产物F;在冰浴条件下,将100mL四氢呋喃、0.1mol四氢铝锂加入5g产物F中,常温反应8h,加热至65℃回流4h,加入80mL水,150mL浓度为2M的盐酸和200mL三氯甲烷萃取,干燥,抽滤,旋蒸,正己烷重结晶,得到二醇单体;
将1mol丁酸、1mol二醇单体、0.5wt%总量对甲苯磺酸和15wt%总量甲苯加入到反应容器中加热至115℃反应5h,减压蒸馏,将产物加入200mL饱和氯化钠水溶液中,在75℃水浴中静置30min,将有机相在95℃下减压蒸馏提纯,得到二醇单丁酯;将0.1mol柠檬酸、0.4mol二醇单丁酯、0.6wt%总量对甲苯磺酸和15wt%总量甲苯加入到反应容器中加热145℃反应5h,减压蒸馏,将产物加入200mL饱和碳酸钠水溶液中,将2g活性炭加入有机相中75℃搅拌30min,过滤,再在95℃下减压蒸馏提纯,得到柠檬酸酯。
改性二氧化钛纳米颗粒制备方法,包含以下步骤:
将10g二氧化钛纳米颗粒加入体积比为150mL1:1的乙醇水溶液中,加入0.7g硅烷偶联剂加热至45℃反应12h,旋蒸出去乙醇水溶液;在氮气氛围下,加入30g丙烯酰、500mL蒸馏水中和2g过硫酸铵加热至65℃反应12h,得到改性二氧化钛纳米颗粒。
实施例1:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入2份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、15份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
实施例2:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入3份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和20份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、20份改性二氧化钛纳米颗粒、0.7份N,N’-亚甲基双丙烯酰胺和1.2份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
实施例3:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入4份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和25份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、25份改性二氧化钛纳米颗粒、0.8份N,N’-亚甲基双丙烯酰胺和1.4份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例1:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入10份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、15份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例2:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入1份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、15份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例3:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入2份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、35份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例4:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入2份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、10份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例5:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入2份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份异山梨醇酯,得到涂料A;
S3:将20份聚乙二醇、15份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
对比例6:S1:将70份聚L-乳酸、30份聚D-L-乳酸、1份茶多酚和5份乙酰柠檬酸三丁酯加热至145℃熔融共混后,加入20份聚乙二醇和80份羟基乙酸继续熔融共混后,165℃、175℃、180℃三段加热挤出造粒,吹塑,得到基材;
S2:将20份聚L-乳酸、80份聚D-L-乳酸溶于四氢呋喃中预热至50℃,依次加入2份羧甲基纤维素钠、4份钼酸铵、5份木质素磺酸钠搅拌均匀,加入1份辛酸亚锡反应12h,加入20份聚乙二醇和15份柠檬酸酯,得到涂料A;
S3:将20份聚乙二醇、15份改性二氧化钛纳米颗粒、0.5份N,N’-亚甲基双丙烯酰胺和1份过硫酸钾加入到70份聚L-乳酸、30份聚D-L-乳酸中,得到涂料B;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,60℃热处理4h,得到可降解环保防伪包装材料。
试验:
取包装材料制备成边长为20mm的正方形样品;
抗撕裂强度检测:取样品放置在万能试验机上,以5mm/min的拉伸速度测试;
耐热性能检测:尺寸稳定性进行测试:取试样划制标线,于25℃室温下调节状态,测量标线间的距离,放入180℃预热后的烘箱内的支撑物上,从烘箱温度回升至规定温度开始计时,达到30min时间后取出试样冷却至室温25℃,再次测量标线间的距离,所得数据的变化率即为尺寸稳定性的指标,其单位为%
结论:实施例1-3制备得到的可降解环保防伪包装材料均具有优异的力学性能和热稳定性能;
对比例1,3中第一涂层中羧甲基纤维素钠加入量过多和第二涂层中改性二氧化钛纳米颗粒加入量过多,都会导致热处理后改性二氧化钛纳米颗粒在涂层中出现团聚现象,导致耐热性能和力学性能降低;
对比例2,4中第一涂层中羧甲基纤维素钠和第二涂层中改性二氧化钛纳米颗粒加入量过少,导致热处理后涂层之间交联不够紧密,导致耐热性能和力学性能降低;
对比例5中第一涂层中异山梨醇制备柠檬酸酯耐热性能和力学性能降低
对比例6中将涂料B用于第一涂层,涂料A用于第二涂层导致耐热性能和力学性能降低。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种可降解环保防伪包装材料的制备方法,其特征在于:
S1:将聚乳酸复合单体A、茶多酚和乙酰柠檬酸三丁酯熔融共混后,加入聚乙二醇和羟基乙酸继续熔融共混,挤出造粒,吹塑,得到基材;所述聚乳酸复合单体A为70-80wt%聚L-乳酸和20-30wt%聚D-L-乳酸;
S2:将聚乳酸复合单体B溶于四氢呋喃中预热,依次加入羧甲基纤维素钠、钼酸铵、木质素磺酸钠搅拌均匀,加入辛酸亚锡反应;加入聚乙二醇和柠檬酸酯,得到涂料A;所述聚乳酸复合单体B为20-30wt%聚L-乳酸和70-80wt%聚D-L-乳酸;
S3:将聚乙二醇、改性二氧化钛纳米颗粒、N,N’-亚甲基双丙烯酰胺和过硫酸钾加入到聚乳酸复合单体C中,得到涂料B;所述聚乳酸复合单体C为70-80wt%聚L-乳酸和20-30wt%聚D-L-乳酸;
S4:将涂料A涂布在基材上,干燥,得到第一涂层;将涂料B涂布在第一涂层上,干燥,得到第二涂层;将第二涂层进行激光全息模压,真空蒸镀,热处理,得到可降解环保防伪包装材料;
所述柠檬酸酯制备方法包含以下步骤:
将氢氧化钠、3-氧代戊二酸二甲酯依次加入甲醇中,加热至60-65℃回流4-5h,加入乙二醛常温反应12-24h,得到产物D;将产物D进行酸化处理,加入碳酸钾和碘甲烷搅拌12-24h,加热至45-50℃搅拌回流12-24h,得到产物E;将浓盐酸加入产物E中,加热至115-120℃回流5-6d,得到产物F;在冰浴条件下,将四氢呋喃、四氢铝锂加入产物F中,常温反应8-9h,加热至65-70℃回流4-5h,得到二醇单体;
将丁酸、二醇单体、对甲苯磺酸和甲苯加入到反应容器中加热至115-120℃反应5-6h,提纯,得到二醇单丁酯;将柠檬酸、二醇单丁酯、对甲苯磺酸和甲苯加入到反应容器中加热145-150℃反应5-6h,提纯,得到柠檬酸酯;
所述改性二氧化钛纳米颗粒制备方法包含以下步骤:
将二氧化钛纳米颗粒加入乙醇溶液中,加入硅烷偶联剂加热至45-50℃反应12-24h,旋蒸出去乙醇溶液;在氮气氛围下,将加入蒸馏水、丙烯酰胺和过硫酸铵加热至65-70℃反应12-24h,得到改性二氧化钛纳米颗粒。
2.根据权利要求1所述的一种可降解环保防伪包装材料的制备方法,其特征在于:所述基材的原料包含以下组分,按质量份数计,聚乳酸复合单体80-100份、茶多酚1-2份、乙酰柠檬酸三丁酯5-15份、聚乙二醇20-30份、羟基乙酸80-100份;所述聚乙二醇分子量为1000-2000。
3.根据权利要求1所述的一种可降解环保防伪包装材料的制备方法,其特征在于:所述第一涂层的原料包含以下组分,按质量分数计,聚乳酸复合单体80-100份、羧甲基纤维素钠2-4份、钼酸铵4-6份、木质素磺酸钠5-10份、辛酸亚锡1-1.5份、聚乙二醇20-30份、柠檬酸酯15-25份;所述羧甲基纤维素钠浓度为1-2wt%;所述聚乙二醇分子量为400-500。
4.根据权利要求1所述的一种可降解环保防伪包装材料的制备方法,其特征在于:所述第二涂层的原料包含以下组分,按质量份数计,聚乳酸复合单体80-100份、聚乙二醇20-30份、改性二氧化钛纳米颗粒15-30份、N,N’-亚甲基双丙烯酰胺0.5-1份、过硫酸钾1-1.5份;所述聚乙二醇分子量为1000-2000。
5.根据权利要求1所述的一种可降解环保防伪包装材料的制备方法,其特征在于:所述热处理温度为45-70℃,时间为4-6h。
6.根据权利要求1所述的一种可降解环保防伪包装材料的制备方法,其特征在于:所述硅烷偶联剂为KH570;二氧化钛纳米颗粒:丙烯酰胺的质量比为1:(3-4);所述硅烷偶联剂加入量为二氧化钛纳米颗粒的7-8wt%。
7.根据权利要求1-6任一项所述的一种可降解环保防伪包装材料的制备方法制备得到的包装材料。
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