CN116903979B - 一种抗静电淀粉基生物降解材料及其制备工艺 - Google Patents
一种抗静电淀粉基生物降解材料及其制备工艺 Download PDFInfo
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- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 claims abstract description 11
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- 239000002253 acid Substances 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
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- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 8
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 8
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- 239000012043 crude product Substances 0.000 claims description 6
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- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 4
- UNSAJINGUOTTRA-UHFFFAOYSA-N 3-(3-bromophenyl)prop-2-yn-1-ol Chemical compound OCC#CC1=CC=CC(Br)=C1 UNSAJINGUOTTRA-UHFFFAOYSA-N 0.000 claims description 3
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及生物降解材料技术领域,具体涉及一种抗静电淀粉基生物降解材料及其制备工艺,本发明合成了2‑((2‑(二甲基氨基)乙基)二硫代)乙基烷基酸酯,通过2‑((2‑(二甲基氨基)乙基)二硫代)乙基烷基酸酯与淀粉的接枝将季铵盐和二硫键引入淀粉分子中,从而使合成的抗静电淀粉基生物降解材料具有良好的抗静电性能和自修复能力。同时,添加聚乙烯醇和乙撑双油酸酰胺等助剂改善材料的机械性能。所述抗静电淀粉基生物降解材料的制备方法包括氯化淀粉的合成、化学反应的进行和挤出造粒等步骤。该材料可应用于食品包装、医疗器械等领域,具有可再生、可降解等环保优势。
Description
技术领域
本发明涉及生物降解材料技术领域,尤其涉及一种抗静电淀粉基生物降解材料及其制备工艺。
背景技术
在日常生活和工业生产中,静电积聚是一种普遍存在的问题。静电带电会影响物品表面的清洁度和卫生性,对生物医用品和食品包装等领域产生不利影响。同时,静电也容易引发火灾、爆炸等安全隐患,影响人们的生命安全。因此,在生产和使用过程中,需要使用具有抗静电性能的或经过防静电处理的材料来避免静电的积聚。
生物降解材料具有可再生性、可降解性和环境友好等优点,已经广泛应用于食品包装、医疗器械等领域。但是,由于传统生物降解材料常常缺乏抗静电能力,容易积聚静电,从而影响其性能,例如易吸附灰尘和细菌,影响安全性和卫生性。淀粉基生物降解材料由于其化学结构中含有大量的羟基和氧原子,其表面容易吸附水分子并形成氢键,从而在一定程度上具有抗静电性。但是淀粉的加工性能较差,进而会导致淀粉基生物降解材料机械性能较差,往往需要对淀粉进行改性以提高其加工性能,这在一定程度上可能会降低淀粉基生物降解材料的抗静电性。
中国发明专利CN109912889B公开了一种提高淀粉基生物降解塑料热稳定性的方法,所述淀粉基生物降解塑料是由酯化剂、淀粉酶和淀粉制备疏水酯化淀粉浆,然后加入二氧化硅湿凝胶,通过淀粉浆置换湿凝胶空隙中的水,再鼓风干燥得到球形微粉,最后将微粉与润滑剂、偶联剂、聚合物混合挤出造粒而制得。虽然疏水酯化改性的淀粉具有优异的加工性能,但是疏水性改性会减弱淀粉与水分子之间的吸附作用,导致静电的积聚和集中。
发明内容
有鉴于此,本发明的目的在于提出一种抗静电淀粉基生物降解材料及其制备工艺,以同时提高淀粉基生物降解材料的机械和抗静电性能。
基于上述目的,本发明提供了一种抗静电淀粉基生物降解材料的制备工艺,具体制备步骤如下:
S1:将2-(2-吡啶基二硫代)乙醇和三乙胺溶于二氯甲烷中,于0-5℃下滴加烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应12-16h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=9:1)提纯,得到中间体;
S2:将中间体和2-二甲氨基乙硫醇盐酸盐加入到二氯甲烷中,在氮气气氛中,于室温下搅拌反应12-16h,反应结束后,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=3:7)提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
S3:将氯化淀粉分散于三氯甲烷中,然后加入2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯,于室温下搅拌反应22 -25h,过滤,洗涤,干燥,得到改性淀粉;
S4:将聚乙烯醇、乙撑双油酸酰胺、改性淀粉加入到玉米淀粉中,搅拌均匀,得到混合料;
S5:将混合料在双螺杆挤出机中进行挤出造粒,得到抗静电淀粉基生物降解材料。
优选地,所述步骤S1中烷基酰氯为月桂酰氯,肉豆蔻酰氯和棕榈酰氯中的一种。
优选地,所述步骤S1中2-(2-吡啶基二硫代)乙醇、三乙胺、二氯甲烷和烷基酰氯的重量比为1-5:0.65-3.25:12-90:1.3-8.2。
优选地,所述步骤S2中中间体、2-二甲氨基乙硫醇盐酸盐和二氯甲烷的重量比为2-11:0.8-4:10-80。
优选地,所述步骤S3中氯化淀粉、三氯甲烷、2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯的重量比为2-10:20-100:1.6-8。
优选地,所述步骤S3中氯化淀粉的合成步骤如下:将玉米淀粉加入N,N-二甲基甲酰胺中,然后在氮气气氛中,缓慢滴加甲磺酰氯,滴加完毕后,于40-60℃下搅拌反应10-15h,过滤,洗涤,干燥,得到氯化淀粉。
优选地,所述玉米淀粉、N,N-二甲基甲酰胺和甲磺酰氯的重量比为2-10:20-100:0.8-4。
优选地,所述步骤S4中聚乙烯醇、乙撑双油酸酰胺、改性淀粉和玉米淀粉的重量比为20-40:0.5-1:10-20:80-160。
优选地,所述步骤S5中双螺杆挤出机的加工温度为160-180℃。
进一步地,本发明还提供了一种抗静电可生物降解包装膜,所述抗静电可生物降解包装膜根据上述抗静电可生物降解包装膜的制备工艺得到。
本发明的有益效果:
本发明提供了一种抗静电淀粉基生物降解材料,其中2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯中的叔胺和氯化淀粉中的氯反应会生成季铵盐,通过一步反应,在淀粉上引入了季铵盐、二硫键和柔性烷基长链,其中季铵盐是一种阴离子抗静电剂,可以大大提高淀粉基生物降解材料的抗静电能力,二硫键赋予了抗静电淀粉基生物降解材料一定的自修复能力,并且在熔融加工过程中,二硫键会断裂,柔性烷基长链从淀粉上脱落,穿插于淀粉分子之间,有助于提高淀粉的热塑性。
本发明还提供了2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯的制备方法,首先使用2-(2-吡啶基二硫代)乙醇和烷基酰氯(如月桂酰氯、肉豆蔻酰氯或棕榈酰氯等)反应,得到中间体,然后中间体和2-二甲氨基乙硫醇盐酸盐通过巯基-二巯基交换反应得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯。将其作为淀粉的接枝单体,可以显著提高抗静电淀粉基生物降解材料的机械性能和抗静电性。
附图说明
图1为本发明2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯的合成路线示意图;
图2为本发明实施例1中2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯、氯化淀粉和改性淀粉的红外光谱图。
注:图1中R为烷基链,链长为C11、C13或C15。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,对本发明进一步详细说明。
本发明具体实施方式中2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯的合成路线如图1所示。
实施例1
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将2g玉米淀粉加入20g N,N-二甲基甲酰胺中,然后在氮气气氛中,缓慢滴加0.8g甲磺酰氯,滴加完毕后,于40℃下搅拌反应10h,过滤,洗涤,干燥,得到氯化淀粉;
(2)将1g 2-(2-吡啶基二硫代)乙醇和0.65g三乙胺溶于12g二氯甲烷中,于0℃下滴加1.3g烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应12h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=9:1)提纯,得到中间体;
(3)将2g中间体和0.8g 2-二甲氨基乙硫醇盐酸盐加入到10g二氯甲烷中,在氮气气氛中,于室温下搅拌反应12h,反应结束后,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=3:7)提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
(4)将2g氯化淀粉分散于20g三氯甲烷中,然后加入1.6g 2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯,于室温下搅拌反应22h,过滤,洗涤,干燥,得到改性淀粉;所述2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯、改性淀粉和氯化淀粉的红外光谱图如图2所示,从图2可以看出,2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯被成功接枝到氯化淀粉上;
(5)将20g聚乙烯醇、0.5g乙撑双油酸酰胺、10g改性淀粉加入到80g玉米淀粉中,搅拌均匀,得到混合料;
(6)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为160℃,得到抗静电淀粉基生物降解材料。
实施例2
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将6g玉米淀粉加入60gN,N-二甲基甲酰胺中,然后在氮气气氛中,缓慢滴加2.4g甲磺酰氯,滴加完毕后,于50℃下搅拌反应12.5 h,过滤,洗涤,干燥,得到氯化淀粉;
(2)将3g 2-(2-吡啶基二硫代)乙醇和1.95g三乙胺溶于51g二氯甲烷中,于0℃下滴加4.75g烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应14h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=9:1)提纯,得到中间体;
(3)将6.5g中间体和2.4g 2-二甲氨基乙硫醇盐酸盐加入到45g二氯甲烷中,在氮气气氛中,于室温下搅拌反应14h,反应结束后,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=3:7)提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
(4)将6g氯化淀粉分散于60g三氯甲烷中,然后加入4.8g 2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯,于室温下搅拌反应24h,过滤,洗涤,干燥,得到改性淀粉;
(5)将30g聚乙烯醇、0.75g乙撑双油酸酰胺、15g改性淀粉加入到120g玉米淀粉中,搅拌均匀,得到混合料;
(6)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为170℃,得到抗静电淀粉基生物降解材料。
实施例3
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将10g玉米淀粉加入100gN,N-二甲基甲酰胺中,然后在氮气气氛中,缓慢滴加4g甲磺酰氯,滴加完毕后,于60℃下搅拌反应15 h,过滤,洗涤,干燥,得到氯化淀粉;
(2)将5g 2-(2-吡啶基二硫代)乙醇和3.25g三乙胺溶于90g二氯甲烷中,于5℃下滴加8.2g烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应16h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=9:1)提纯,得到中间体;
(3)将11g中间体和4g 2-二甲氨基乙硫醇盐酸盐加入到80g二氯甲烷中,在氮气气氛中,于室温下搅拌反应16h,反应结束后,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=3:7)提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
(4)将10g氯化淀粉分散于100g三氯甲烷中,然后加入8g 2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯,于室温下搅拌反应25h,过滤,洗涤,干燥,得到改性淀粉;
(5)将40g聚乙烯醇、1g乙撑双油酸酰胺、20g改性淀粉加入到160g玉米淀粉中,搅拌均匀,得到混合料;
(6)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为180℃,得到抗静电淀粉基生物降解材料。
对比例1
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将1g 2-(2-吡啶基二硫代)乙醇和0.65g三乙胺溶于12g二氯甲烷中,于0℃下滴加1.3g烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应12h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=9:1)提纯,得到中间体;
(2)将2g中间体和0.8g 2-二甲氨基乙硫醇盐酸盐加入到10g二氯甲烷中,在氮气气氛中,于室温下搅拌反应12h,反应结束后,蒸发溶剂,再通过柱层析法(乙酸乙酯:石油醚=3:7)提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
(3)将2g玉米淀粉和1.6g 2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯混合,得到淀粉混合物;
(4)将20g聚乙烯醇、0.5g乙撑双油酸酰胺、10g淀粉混合物加入到80g玉米淀粉中,搅拌均匀,得到混合料;
(5)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为160℃,得到抗静电淀粉基生物降解材料。
对比例2
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将10g玉米淀粉分散在100g吡啶中,在搅拌下加热至95°C,再加入4.46g月桂酰氯(与实施例1中甲磺酰氯等摩尔),反应运行3-5h,过滤,洗涤,干燥,得到酯化淀粉;
(2)将20g聚乙烯醇、0.5g乙撑双油酸酰胺、10g酯化淀粉加入到80g玉米淀粉中,搅拌均匀,得到混合料;
(3)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为160℃,得到抗静电淀粉基生物降解材料。
对比例3
一种抗静电淀粉基生物降解材料,具体制备方法如下:
(1)将20g聚乙烯醇、0.5g乙撑双油酸酰胺加入到90g玉米淀粉中,搅拌均匀,得到混合料;
(2)将混合料在双螺杆挤出机中进行挤出造粒,加工温度为160℃,得到抗静电淀粉基生物降解材料。
性能测试
机械性能:参照国家标准 GB/T 1040.3—2006,试样大小为50 mm×10 mm,设定初始夹距30 mm,以1 mm/s的速度测定试样断裂时的拉伸强度和断裂伸长率,每个样品测量5次并取平均值。
表面电阻率的测试:参照国家标准GB/T 1410-2006,用高阻仪测试样品的表面电阻率,每个样品测量5次并取平均值。
耐擦洗实验:在蒸馏水中使用脱脂棉将试样表面擦拭50次,晾干后放置在恒温恒湿环境(相对湿度50%,温度20℃)中2 h,测定样品的表面电阻率。
注:电阻率比值=表面电阻率(擦洗后)/表面电阻率(未擦洗)
数据分析:从实施例1--3和对比例3可以看出,本发明制备的抗静电淀粉基生物降解材料相对于传统的淀粉基生物降解材料具有优异的机械性能和抗静电性能,从实施例1和对比例1、2可以看出,2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯与淀粉之间的接枝对于抗静电淀粉基生物降解材料机械性能和抗静电性能的提升具有至关重要的作用。
所属领域的普通技术人员应当理解:以上任何实施例的讨论仅为示例性的,并非旨在暗示本发明的范围(包括权利要求)被限于这些例子;在本发明的思路下,以上实施例或者不同实施例中的技术特征之间也可以进行组合,步骤可以以任意顺序实现,并存在如上所述的本发明的不同方面的许多其它变化,为了简明它们没有在细节中提供。
本发明旨在涵盖落入所附权利要求的宽泛范围之内的所有这样的替换、修改和变型。因此,凡在本发明的精神和原则之内,所做的任何省略、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 (2)
1.一种抗静电淀粉基生物降解材料的制备工艺,其特征在于,具体制备步骤如下:
S1:将2-(2-吡啶基二硫代)乙醇和三乙胺溶于二氯甲烷中,于0-5℃下滴加烷基酰氯,滴加完毕后,在氮气气氛中,于室温下搅拌反应12-16h,反应结束后,洗涤,干燥,蒸发溶剂,再通过柱层析法提纯,得到中间体;
S2:将中间体和2-二甲氨基乙硫醇盐酸盐加入到二氯甲烷中,在氮气气氛中,于室温下搅拌反应12-16h,反应结束后,蒸发溶剂,再通过柱层析法提纯粗品,得到2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯;
S3:将氯化淀粉分散于三氯甲烷中,然后加入2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯,于室温下搅拌反应22 -25h,过滤,洗涤,干燥,得到改性淀粉;
S4:将聚乙烯醇、乙撑双油酸酰胺、改性淀粉加入到玉米淀粉中,搅拌均匀,得到混合料;
S5:将混合料在双螺杆挤出机中进行挤出造粒,得到抗静电淀粉基生物降解材料;
所述步骤S1中2-(2-吡啶基二硫代)乙醇、三乙胺、二氯甲烷和烷基酰氯的重量比为1-5:0.65-3.25:12-90:1.3-8.2,所述烷基酰氯为月桂酰氯,肉豆蔻酰氯和棕榈酰氯中的一种;
所述步骤S2中中间体、2-二甲氨基乙硫醇盐酸盐和二氯甲烷的重量比为2-11:0.8-4:10-80;
所述步骤S3中氯化淀粉、三氯甲烷、2-((2-(二甲基氨基)乙基)二硫代)乙基烷基酸酯的重量比为2-10:20-100:1.6-8;
所述步骤S3中氯化淀粉的合成步骤如下:将玉米淀粉加入N,N-二甲基甲酰胺中,然后在氮气气氛中,缓慢滴加甲磺酰氯,滴加完毕后,于40-60℃下搅拌反应10-15 h,过滤,洗涤,干燥,得到氯化淀粉,所述玉米淀粉、N,N-二甲基甲酰胺和甲磺酰氯的重量比为2-10:20-100:0.8-4;
所述步骤S4中聚乙烯醇、乙撑双油酸酰胺、改性淀粉和玉米淀粉的重量比为20-40:0.5-1:10-20:80-160。
2.根据权利要求1所述的抗静电淀粉基生物降解材料的制备工艺,其特征在于,所述步骤S5中双螺杆挤出机的加工温度为160-180℃。
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