CN109422983A - 一种淀粉/pva复合抗菌保鲜膜及其制备方法 - Google Patents
一种淀粉/pva复合抗菌保鲜膜及其制备方法 Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract
本发明公开了一种淀粉/PVA复合抗菌保鲜膜及其制备方法。本发明的保鲜膜是以淀粉、阳离子淀粉、聚乙烯醇构成骨架结构,加入交联剂、增塑剂、消泡剂、成膜助剂组成。制备方法:将淀粉、阳离子淀粉配成一定浓度的水溶液加热糊化,加入聚乙烯醇加热搅拌至完全溶解;加入交联剂加热搅拌反应一定时间;加入增塑剂、消泡剂、成膜助剂,配制成固含量为15‑25%的均匀水溶液(胶);将混合均匀的水溶液(胶)倒入模具中成型,干燥成膜。该抗菌保鲜膜在保持对氧气、氮气、二氧化碳高阻隔性能,适中的水汽透过能力,同时拥有一定的杀菌能力;抗菌基团连接在高分子骨架上,其性能更稳定,不易挥发,使用寿命长。
Description
技术领域
本发明属于食品材料领域,具体涉及一种淀粉/PVA复合抗菌保鲜膜及其制备方法。
背景技术
新鲜果蔬、肉类食品含有充足的水分及营养成分,因此是微生物理想的繁殖基地;现有的新鲜果蔬、肉类食品大多使用抗菌剂抑制微生物的大量繁殖,但容易吸附残留在果蔬、肉类食品表面,影响食品安全。
聚乙烯醇是一种可生物降解的合成型高分子材料,具有很多优异的性能,如水溶性、成膜性、对氧、二氧化碳和乙烯等气体的阻隔性以及较高的水汽透过能力。淀粉是一种可再生可生物降解的天然高分子材料,来源广泛,可再生,价格低廉。淀粉/PVA膜用于果蔬保鲜,安全无毒、完全生物降解、完全水溶,对氧气、二氧化碳、乙烯等有强阻隔性能,还能保持适当的水气穿透量等特点;但存在下列问题:1、无抗菌性能,主要依靠调节保鲜对象环境气氛达到保鲜效果,仅对强呼吸果蔬保鲜效果明显,应用范围受限制;2、亲水受潮,膜表面容易滋生微生物,影响果蔬保鲜效果。
发明内容
为解决现有技术的缺点和不足之处,本发明的首要目的在于提供一种淀粉/PVA复合抗菌保鲜膜。本发明采用来自于柑橘、山楂、苹果和葡萄等天然植物的有机酸作为淀粉、阳离子淀粉、PVA共交联的试剂,在淀粉/PVA膜上植入抗菌基团(季铵盐),拓宽保鲜膜应用空间;抗菌基团通过化学键固定在淀粉/PVA膜上,避免了抗菌基团的流失,能够保持较长久的抗菌活性,另一方面不会对食品造成污染,使用更加安全;未反应的有机酸是淀粉、PVA的良增塑剂,交联反应后无需处理,可加入增塑剂、消泡剂、成膜助剂直接成膜,生产效率高;耐水性提高,减少膜表面微生物滋生,提高果蔬保鲜效果。
本发明的另一目的在于提供上述淀粉/PVA复合抗菌保鲜膜的制备方法。
为实现上述发明目的,本发明采用如下技术方案:
一种淀粉/PVA复合抗菌保鲜膜,以淀粉、聚乙烯醇和淀粉、聚乙烯醇与交联剂的共交联产物为基本骨架,加入增塑剂、消泡剂和成膜助剂制成;按重量份数计,其主要制备原料配比包括:
所述聚乙烯醇为醇解度小于或等于88%的聚乙烯醇,具体可优选为聚乙烯醇1788、聚乙烯醇0588或聚乙烯醇0580。
所述淀粉为玉米淀粉、番薯淀粉和木瓜淀粉等中的至少一种。
所述阳离子淀粉为淀粉叔氨基烷基醚、季铵烷基淀粉醚中的至少一种。
所述交联剂来自于柑橘、山楂、苹果和葡萄等天然植物的有机酸,具体为2-羟基丁二酸(苹果酸)、2,3-二羟基丁二酸(酒石酸)和蝶酰谷氨酸(叶酸)等中的至少一种。
所述增塑剂为多羟基增塑剂,优选为乙二醇、丙三醇、聚乙二醇-400、聚乙二醇-1000、聚乙二醇-2000、聚乙二醇-6000和山梨醇中的至少一种。
所述消泡剂为单硬脂酸甘油酯或磷酸酯类。
所述成膜助剂为增粘剂、流平剂和脱模剂等中的至少一种。所述增粘剂为歧化松香、氢化松香、萜烯树脂、汉生胶和阳离子瓜尔胶中的至少一种;所述流平剂为改性聚硅氧烷、丙烯酸酯中的至少一种;所述脱模剂二甲基硅油、乳化硅油中的至少一种。
上述淀粉/PVA复合抗菌保鲜膜的制备方法,包括以下步骤:
(1)将淀粉、阳离子淀粉配成一定浓度的水溶液加热糊化,加入聚乙烯醇加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液中加入交联剂搅拌反应一定时间,得到均匀的混合溶液或溶胶(交联度小为溶液,较大时为溶胶);
(3)往步骤(2)得到的混合溶液或溶胶中加入增塑剂、消泡剂、成膜助剂,高速搅拌,冷却,配制成固含量为15-25%的均匀水溶液或溶胶;
(4)将步骤(3)制得的水溶液或溶胶倒入模具中成型,干燥成膜。
步骤(1)所述加热糊化温度为60-75℃,加热搅拌指加热至80-90℃以1500~2500转/min速度搅拌至完全溶解;步骤(2)搅拌速度为500转/min,反应时间为30-90min,得到的均匀溶液或溶胶的固含量为15-25%;步骤(3)以1500~3500转/min速度搅拌均匀后冷却至40-50℃。
步骤(1)所述加热糊化温度为60-75℃淀粉使完全糊化,加热搅拌指加热至80-90℃以1500~2500转/min速度搅拌使聚乙烯醇完全溶解,保证步骤(2)交联反应和步骤(2)成膜工艺顺利高效实施。
步骤(2)交联反应温度控制在70-90℃为宜,低于70℃,最终导致交联度偏低;高于90℃,得到的溶液(胶)会因流动性差无法铺展成膜;所述搅拌30-90min为交联反应时间,低于30min,交联反应尚未完全,交联度较低;高于90min,交联度过高,形成的溶液(胶)可能因流动性差无法铺展成膜。
步骤(3)溶液或溶胶固含量须控制在15%-25%,太高溶液(胶)粘度大,难以铺展,固含量太低成膜效率低。
步骤(4)所述干燥成膜的温度为110-150℃。
上述过程中阳离子淀粉添加0.5-1重量份,过低抗菌效果不明显,过高增大成本,过量抗菌剂的引入也会对食品卫生安全性带来副作用;所述交联剂添加0.5-3重量份,低于0.5份,交联反应无法发生;高于3份,对交联度不再有明显影响,相反会增加成本。
与现有技术相比,本发明具有以下优点及有益效果:
(1)本发明涉及到的原料均可生物降解,所用交联剂为天然植物中提取出的天然酸,自然环境中将最终降解为二氧化碳及水,是一种绿色环保保鲜膜;
(2)相比复合、涂覆、配位固定,抗菌基团连接在高分子骨架上,其性能更稳定,不会因为抗菌剂的挥发迁移污染食品,危害食品卫生安全。
(3)保持良好的气调功能,同时拥有一定的杀菌能力,拓宽了淀粉/PVA膜的保鲜应用空间;
(4)抗菌基团的引入减缓因膜亲水引起的细菌滋生,进一步提高保鲜膜的安全卫生性;
(5)交联剂为来自于大自然的有机酸,同时也是聚乙烯醇及淀粉的增塑剂,无需后处理;引入抗菌基团的同时完成淀粉、PVA交联,改善淀粉、PVA间的相容性,提高膜的物理机械性能。制膜工业绿色环保,简单高效,容易产业化。
附图说明
图1为本发明淀粉/PVA复合抗菌保鲜膜保鲜鸡肉3天实例照片,其中a为保鲜前新鲜鸡肉块,b为储存3天后的鸡肉块;
图2为PE保鲜膜保鲜鸡肉3天实例照片,其中a为保鲜前新鲜鸡肉块,b为储存3天后的鸡肉块。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
具体配方:
制备过程如下:
(1)按照配方计量称好各组分,将30g玉米淀粉、1g阳离子淀粉配置成一定浓度水溶于75℃水浴加热糊化,再加入聚乙烯醇继续加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液加入1.5g叶酸反应30min;
(3)往步骤(2)加入成膜助剂与去离子水并加热至完全溶解,然后加入消泡剂高速搅拌分散,冷却至50℃,得到混合水溶液。
(4)将混合均匀的水溶液均匀地平铺在干燥、洁净的模具上,形成厚薄均匀,表面光洁平整的液层,在110℃下烘干12h。
用该实施例制备的抗菌保鲜膜1号密封包装鲜切苹果,于25℃/相对湿度RH75%条件下储存3天,鲜切苹果无明显氧化现象,无特别难闻气味,无明显腐败现象;PE保鲜膜在相同的条件下,鲜切苹果颜色变深,能闻到酒精气味。
实施例2
具体配方:
制备过程如下:
(1)按照配方计量称好各组分,将20g玉米淀粉、0.5g阳离子淀粉配置成一定浓度水溶于75℃水浴加热糊化,再加入聚乙烯醇继续加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液加入1.5g叶酸反应30min;
(3)往步骤(2)加入成膜助剂与去离子水并加热至完全溶解,然后加入消泡剂高速搅拌分散,冷却至50℃,得到混合水溶液。
(4)将混合均匀的水溶液均匀地平铺在干燥、洁净的模具上,形成厚薄均匀,表面光洁平整的液层,在120℃下烘干12h。
使用该实施例制备抗菌膜密封包装菜心,于5℃/相对湿度RH75%条件下储存二周,菜心外观无明显变化;PE保鲜膜在相同的条件下,菜心变黄,出现腐烂迹象。
实施例3
具体配方:
制备过程如下:
(1)按照配方计量称好各组分,将40g玉米淀粉、0.8g阳离子淀粉配置成一定浓度水溶于75℃水浴加热糊化,再加入聚乙烯醇继续加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液加入1.5g叶酸反应45min;
(3)往步骤(2)加入成膜助剂与去离子水并加热至完全溶解,然后加入消泡剂高速搅拌分散,冷却至50℃,得到混合水溶液;
(4)将混合均匀的水溶液均匀地平铺在干燥、洁净的模具上,形成厚薄均匀,表面光洁平整的液层,在120℃下烘干12h。
使用该实施例制备的抗菌膜密封包装新鲜花生,于20℃/相对湿度RH60%条件下储存10天,花生表面干爽,与10天前无明显不同;PE保鲜膜在相同的条件下,花生表面均出现明显霉变。
实施例4
具体配方:
制备过程如下:
(1)按照配方计量称好各组分,将20g玉米淀粉、1g自制阳离子淀粉配置成一定浓度水溶于75℃水浴加热糊化,再加入聚乙烯醇继续加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液加入1.5g叶酸反应60min;
(3)往步骤(2)加入成膜助剂与去离子水并加热至完全溶解,然后加入消泡剂高速搅拌分散,冷却至50℃,得到混合水溶液;
(4)将混合均匀的水溶液均匀地平铺在干燥、洁净的模具上,形成厚薄均匀,表面光洁平整的液层,在120℃下烘干12h。
使用该实施例制备的抗菌膜密封包装新鲜鸡肉块,于5℃/相对湿度RH75%条件下储存3天,膜内无难闻气味,鸡肉块未腐败。相同环境下,使用PE膜密封包装鸡肉块,鸡肉块颜色变深,膜内有大量粘液,有难闻气味,腐败严重。
上述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上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种淀粉/PVA复合抗菌保鲜膜,其特征在于,其制备原料包括:
2.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述聚乙烯醇为醇解度小于或等于88%的聚乙烯醇。
3.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述淀粉为玉米淀粉、番薯淀粉和木瓜淀粉中的至少一种。
4.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述阳离子淀粉为淀粉叔氨基烷基醚、季铵烷基淀粉醚中的至少一种。
5.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述交联剂为2-羟基丁二酸、2,3-二羟基丁二酸和蝶酰谷氨酸中的至少一种。
6.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述增塑剂为多羟基增塑剂,所述成膜助剂为增粘剂、流平剂和脱模剂中的至少一种。
7.根据权利要求6所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述增塑剂为乙二醇、丙三醇、聚乙二醇-400、聚乙二醇-1000、聚乙二醇-2000、聚乙二醇-6000和山梨醇中的至少一种;所述增粘剂为歧化松香、氢化松香、萜烯树脂、汉生胶和阳离子瓜尔胶中的至少一种;所述流平剂为改性聚硅氧烷、丙烯酸酯中的至少一种;所述脱模剂二甲基硅油、乳化硅油中的至少一种。
8.根据权利要求1所述的淀粉/PVA复合抗菌保鲜膜,其特征在于,所述消泡剂为单硬脂酸甘油酯或磷酸酯类。
9.权利要求1至8任一项所述的淀粉/PVA复合抗菌保鲜膜的制备方法,其特征在于,包括以下步骤:
(1)将淀粉、阳离子淀粉配成一定浓度的水溶液加热糊化,加入聚乙烯醇加热搅拌至完全溶解;
(2)往步骤(1)得到的溶液中加入交联剂搅拌反应一定时间,得到溶液或溶胶;
(3)往步骤(2)得到的溶液或溶胶中加入增塑剂、消泡剂、成膜助剂,高速搅拌,冷却,配制成固含量为15-25%的均匀水溶液或溶胶;
(4)将步骤(3)制得的水溶液或溶胶倒入模具中成型,干燥成膜。
10.根据权利要求9所述的淀粉/PVA复合抗菌保鲜膜的制备方法,其特征在于,步骤(1)所述加热糊化温度为60-75℃,加热搅拌指加热至80-90℃以1500~2500转/min速度搅拌至完全溶解;步骤(2)搅拌速度为500转/min,反应时间为30-90min,得到的溶液或溶胶的固含量为15-25%;步骤(3)以1500~3500转/min速度搅拌均匀后冷却至40-50℃。
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