CN1318510C - 交联型谷类醇溶蛋白可食性膜及其制备方法 - Google Patents
交联型谷类醇溶蛋白可食性膜及其制备方法 Download PDFInfo
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- CN1318510C CN1318510C CNB2005100604799A CN200510060479A CN1318510C CN 1318510 C CN1318510 C CN 1318510C CN B2005100604799 A CNB2005100604799 A CN B2005100604799A CN 200510060479 A CN200510060479 A CN 200510060479A CN 1318510 C CN1318510 C CN 1318510C
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Abstract
本发明公开了一种交联型谷类醇溶蛋白可食性膜及其制备方法。交联型谷类醇溶蛋白可食性膜含谷类醇溶蛋白100重量份、增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份、防腐剂0~0.1重量份与交联剂1~7重量份,采用溶液流延法或可塑性加工方法制膜,经高温交联反应而成。本发明以为谷类醇溶蛋白为成膜基质,采用取代二甘醇醛为新型交联剂,配以多元醇增塑剂及作为食品添加剂使用的疏水改性剂、抗氧剂与防腐剂,以提高醇溶蛋白交联膜的力学强度、柔韧性、疏水性与抗老化性能。
Description
技术领域
本发明涉及一种交联型谷类醇溶蛋白可食性膜及其制备方法。
背景技术
大量使用塑料包装造成塑料垃圾泛滥,严重危害生态环境。20世纪90年代后,“环境与发展”成为世界关注的焦点问题。用可食性材料包装代替传统塑料包装,发展所谓的“绿色包装材料”,成为食品包装行业的发展趋势之一。在众多“绿色包装材料”的研究开发中,应用天然生物高分子制成可食性包装膜,是食品包装新技术发展的重要课题。可食性包装材料具有良好的机械性能及防潮、隔氧、保鲜、防紫外线等功能,能阻止食品吸潮、失水,延缓食品氧化、变质。可食性包装材料的主要原料包括多糖、蛋白质、脂类等,其中蛋白质包括小麦面筋蛋白、玉米醇溶蛋白、大豆分离蛋白和乳清蛋白等。Gennadios等评述了基于谷朊粉、大豆蛋白、玉米蛋白、牛奶蛋白、花生蛋白或胶原蛋白等的可食性薄膜或涂层材料的制备方法与性能(Gennadios A.,McHugh TH.,WellerCL.,Krochta JM.,Edible coatings and films based on proteins.In Edible coatingsand films to improve food quality;Krochta JM.,Baldwin EA.,Nisperos-CarriedoMO.,Eds.,Technomic Publishing Co.:Lancaster,PA,1994;201-277)。
蛋白质是由多种氨基酸组成的天然高分子,分子间存在较强的氢键相互作用以及分子内/分子间二硫键。通常以蛋白质、增塑剂及其它试剂的溶液或悬浮液为成膜介质,采用溶液流延法制备蛋白质薄膜(Anker A.,Foster GA.,LoaderMA..Method of preparing gluten containing films and coatings.美国专利3.653,925,1972;Aydt TP.,Weller CL.,Testin RF.,Mechanical and barrier properties of ediblecorn and wheat protein films.Trans.ASAE,1991,34,207-211),通过热或酸碱处理来提高蛋白质溶解度,改善膜材料性能(Gennadios A.,Brandenburg AH.,WellerCL.,Testin RF.,Effect of pH on properties of wheat gluten and soy protein isolatefilms.J.Agric.Food.Chem.,1993,41:1835-1839;Roy S.,Gennadios A.,WellerCL.,Zeece MG.,Testin RF.,Physical and molecular properties of wheat gluten filmscast from heated film-forming solutions.J.Food Sci.,1999,64:57-60)。
溶液法制膜消耗大量有机溶剂。近年来人们开始探索采用高分子常规成型技术制备蛋白质膜,如中国专利00116036.2公开了“耐水热塑性大豆蛋白膜的制备方法”。分子间的强相互作用使得蛋白质材料的热成型加工不易实施,且高温加工容易导致蛋白质热分解。因而,蛋白质材料热成型时需添加大量增塑剂,以降低分子间相互作用,提高分子链柔韧性。可使用的增塑剂有水或多元醇如甘油、单糖、二糖或低聚糖等。Mangavel等发现,热成型的谷朊粉膜的力学性能优于溶液浇注膜(Mangavel C.,Rossignol N.,Perronnet A.,Barbot J.,Popineau Y.,Gueguen J.,Properties and microstructure of thermo-pressed wheatgluten films:a comparison with cast films.Biomacromolecules,2004,5,1596-1601)。
在制备增塑蛋白质组合物过程中,强剪切可使分子间二硫键断裂,降低蛋白质分子量。在较高温度下,蛋白质分子之间重新形成化学交联。这为采用常规塑料加工设备制备交联型谷类蛋白质材料提供了理论依据。Domenek等采用机械混合制备增塑谷朊粉,采用模压方法制备交联样品(Domenek S.,Morel MH.,Redl A.,Guilbert S.,Rheological investigation of swollen gluten polymer networks:effects of process parameters on cross-link density.Macrom.Symp.,2003,200:137-146),并考察增塑谷朊粉的挤出加工工艺(Pommet M.,Redl A.,MorelMH.,Domenek S.,Guilbert S.,Thermoplastic processing of protein-based bioplastics:chemical engineering aspects of mixing,extrusion and hot molding.Macrom.Symp.,2003,197:207-218)。
以谷类蛋白质为基础的材料的综合性能较差,需经紫外辐照、γ-射线辐照、酶处理或化学交联等来提高材料的刚性、阻隔性、耐热性与疏水性。一些能与蛋白质分子中的氨基、酰胺基、羟基、硫醇基发生化学反应的物质,如卤化乙酸酯、双亚胺酯、双-n-羟基-琥珀酰亚胺、二醛或二酮类试剂,均可用作蛋白质的化学交联剂,其中最常用的是醛类试剂如甲醛、乙二醛或戊二醛。
本发明以取代二甘醇醛为新型交联剂,采用溶液流延法或可塑性加工法制备交联型谷类醇溶蛋白膜。本发明使用无毒或毒性极低的多元醇增塑剂,改善谷类醇溶蛋白的可塑性加工性能;使用作为食品安全助剂的疏水改性剂、抗氧剂与防腐剂等,以提高交联型谷类醇溶蛋白膜的疏水性与抗老化等性能。基于本发明所制备的交联型谷类醇溶蛋白膜,可用于食品、糖制品、药品等的可食性包装膜。
发明内容
本发明的目的是提供一种交联型谷类醇溶蛋白可食性膜及其制备方法。
交联型谷类醇溶蛋白可食性膜,含谷类醇溶蛋白100重量份、增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份、防腐剂0~0.1重量份与交联剂1~7重量份。
谷类醇溶蛋白是小麦醇溶蛋白、大麦醇溶蛋白、燕麦醇溶蛋白、黑麦醇溶蛋白、大米醇溶蛋白、粟米醇溶蛋白、玉米醇溶蛋白或高粱醇溶蛋白;增塑剂是1,2-丙二醇、1,3-丙二醇、二甘醇、三甘醇、四甘醇、甘油、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2,3-己三醇、1,2,6-己三醇、甘油单乙酸酯或甘油二乙酸酯;疏水改性剂为硬脂酸、羟基硬脂酸、硬脂酸正丁酯、单硬脂酸甘油脂、羟基硬脂酸甲酯、大豆油、花生油、玉米油、米糠油、菜籽油、棉籽油、葵花籽油或油茶籽油;抗氧剂为叔丁基羟基茴香醚、茶多酚、生育酚、没食子酸乙酯、没食子酸丙酯、没食子酸辛酯、没食子酸十二酯、没食子酸十八酯、抗坏血酸、抗坏血酸棕榈酸酯、D-异抗坏血酸、山梨糖醇或麦芽糖醇;防腐剂为山梨酸乙酯、山梨酸对羟基苯甲酸丁酯、脱氢乙酸、尼泊金甲酯、对羟基苯甲酸丙酯或对羟基苯甲酸乙酯;交联剂为D′-甲氧基二甘醇醛、D′-甲氧基-D-羟甲基二甘醇醛、L′-甲氧基-L-甲基二甘醇醛或D′-甲氧基-D′,D-二羟甲基二甘醇醛。
采用溶液流延法的交联型谷类醇溶蛋白可食性膜的制备方法为:以60~90%的乙醇/水混合物为溶剂,加入谷类醇溶蛋白100重量份,在30~50℃下强烈搅拌,配置成浓度为50~100mg/ml的溶液,加入增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份、防腐剂0~0.1重量份与交联剂1~7重量份,搅拌均匀得到成膜溶液,倾倒在光滑的塑料板上,待溶剂挥发完毕后,在50~120℃热处理0.5~1h,揭膜,得到交联型谷类醇溶蛋白可食性膜。
采用压延法的交联型谷类醇溶蛋白可食性膜的制备方法为:将谷类醇溶蛋白100重量份、增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份与防腐剂0~0.1重量份进行预混合,然后在10~40℃机械混炼5~15min,并在混炼过程中加入交联剂1~7重量份,获得醇溶蛋白组合物,送入压延机压延成膜,经150~180℃热处理2~10min,得到交联型谷类醇溶蛋白可食性膜。
本发明的优点是:
1)谷类醇溶蛋白不需经化学或物理改性,生产成本低;
2)利用取代二甘醇醛为新型交联剂,采用溶液流延法或常规塑料加工方法制备交联型谷类醇溶蛋白可食性膜,生产工艺简单;
3)交联型谷类醇溶蛋白可食性膜含有增塑剂、疏水改性剂、防腐剂与抗氧剂,容易加工成型,且具有较高的疏水性与抗老化性能;
4)交联型谷类醇溶蛋白可食性膜或其分解产物均无毒,可安全食用。
具体实施方式
本发明使用谷类醇溶蛋白是小麦、大麦、燕麦、黑麦、大米、粟米、玉米或高粱籽粒的醇溶蛋白。这些谷物籽粒蛋白质中含有40%以上由非极性氨基酸组成的醇溶蛋白。
从小麦谷朊粉(也称活性小麦面筋)中提取小麦醇溶蛋白的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“司学芝,李建伟,王金水,周长智,麦醇溶蛋白和麦谷蛋白提取条件的研究.郑州工程学院学报,2004,25(3):33-39”。
从大麦籽粒或籽粒粉中提取大麦醇溶蛋白的技术是公知的,如在如下文献中有述,这些文献引入本文作为参考:“颜启传,黄亚军,徐媛,试用ISTA推荐的种子醇溶蛋白电泳方法鉴定大麦和小麦品种.作物学报,1992,18(1):61-68;董牛,王丽蓉,兰兰,张德颐,大麦醇溶蛋白中高赖氨酸组分的溶解特性研究.植物学报,1989,31:689-695”。
从燕麦籽粒粉中提取燕麦醇溶蛋白的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“李连朝,雷建菊,汪沛洪,齐雅坤,反相高效液相色谱分析种子醇溶蛋白表征燕麦种质,色谱,1991,9(4):253-256”。
从黑麦籽粒粉中提取黑麦醇溶蛋白的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“Charbonnier L,Terce-Laforgue T.,Mosse J.,Ryeprolamins:extractability,separation,and characterization,J.Agric.Food Chem.,1981,29:968-973”。
从大米粉、米渣或米糟中提取大米蛋白质的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“王章存,姚惠源:大米蛋白质提取技术研究.粮食与饲料工业,2003,(8):37-38”。另外,中国专利03134973.0公开了“从大米中提取大米蛋白的方法”,中国专利03134972.2公开了“碱法提取大米蛋白的方法”,中国专利200410039303.0公开了“以大米为原料提取大米蛋白并制大米淀粉的工艺方法”。
从脱脂粟米籽粒或脱脂粟米籽粒粉中提取粟米醇溶蛋白的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“Okoh PN,Nwasike CC.,Ikediobi CO.,Studies on Seed Protein of Pearl Millets.1.Amino Acid Compositionof Protein Fractions of Early and Late Maturing Varieties.J.Agric.Food Chem.,1985,33,55-57”。
从玉米蛋白粉(也称玉米麸质粉)中提取玉米醇溶蛋白的技术是公知的,如在如下文献中有述,该文献引入本文作为参考:“张钟,齐爱云,玉米醇溶蛋白提取工艺及功能性质研究,粮食与饲料工业,2004(9):21-23.”中国专利00101222.3公开了“用玉米谷朊制备醇溶玉米蛋白膜”的技术,其中描述了从玉米蛋白粉中提取玉米醇溶蛋白的方法。高纯度的玉米醇溶蛋白可以从醇溶蛋白含量≥80%(干基)的商业产品中选择,可以从日本和光纯药公司、美国Freeman Industries公司购买玉米醇溶蛋白。
从高粱籽粒或高粱粉中提取高粱醇溶蛋白的技术是公知的,如在如下文献中有述,这些文献引入本文作为参考:“Emmambux MN.,Taylor JRN.,Sorghumkafirin interaction with various phenolic compounds.J.Sci.Food Agric.,2003,83:402-407;Gao C.,Taylor J.,Wellner N.,Byaruhanga YB.,Parker ML.,Mills ENC.,Belton PS.,Effect of preparation conditions on protein secondary structure andbiofilm formation of Kafirin.J.Agric.Food Chem.,2005,53:306-312;Huang CP.,Hejlsoe-Kohsel E.,Han XZ.,Protelytic activity in sorghum flour and its interferencein protein analysis.Cereal Chem.,2000,77:343-344”。
本发明建议采用60~90%的乙醇/水混合物为溶剂,在30~50℃、搅拌条件下从小麦谷朊粉、脱脂大麦籽粒粉、脱脂燕麦籽粒粉、脱脂黑麦籽粒粉、大米蛋白粉、脱脂粟米籽粒粉、玉米蛋白粉与脱脂高粱籽粒粉中提取谷类醇溶蛋白,经离心或过滤分离得到提取液,直接用于交联型谷类醇溶蛋白可食性膜的制备。采用这种方法时,可根据不同固液比控制提取液中醇溶蛋白的浓度。在测得醇溶蛋白浓度后,直接向提取液中加入本发明所规定量的增塑剂、疏水改性剂、抗氧剂、防腐剂与交联剂,得到成膜溶液,用于流延法制备交联型谷类醇溶蛋白可食性膜。当然,也可将提取液浓缩、干燥,得到醇溶蛋白固体,按本发明所规定浓度配成溶液,并加入规定量的增塑剂、疏水改性剂、抗氧剂、防腐剂与交联剂,得到成膜溶液。
干燥后的醇溶蛋白固体可用于如本发明权利要求9所述的热塑性加工成膜,即压延法成膜。第一步将谷类蛋白质、增塑剂、疏水改性剂、抗氧剂与防腐剂进行预混合。本发明对预混合的要求不是很严格,可以采用高速混合机或Haake混炼仪,在50~3000r/min转速下室温混合2~10min;也可以借助工具手工搅拌10~30min,使物料基本混合均匀即可。第二步采用机械混炼法进一步混炼上述预混合物料,可采用开炼机在10~40℃下机械混炼5~15min,并在混炼过程中加入交联剂,获得谷类醇溶蛋白组合物。第三步将谷类醇溶蛋白组合物送入压延机压延成膜,将膜在150~180℃进行2~10min热交联,得到交联型谷类醇溶蛋白可食性膜。
本发明的关键之一是采用取代二甘醇醛即D′-甲氧基二甘醇醛、D′-甲氧基-D-羟甲基二甘醇醛、L′-甲氧基-L-甲基二甘醇醛或D′-甲氧基-D′,D-二羟甲基二甘醇醛为新型交联剂,对蛋白质膜进行化学交联。取代二甘醇醛的分子结构为
式中R1=R2=H、R1=H及R2=CH2OH、R1=H及R2=CH3、或R1=R2=CH2OH。取代二甘醇醛可以D-赤藓糖、D-苏糖、D-***糖、D-木糖、D-阿洛糖、D-葡萄糖、D-甘洛糖、D-古洛糖、D-半乳糖、D-果糖、D-山梨糖、L-岩藻糖或L-鼠李糖为原料,经甲基甙化、高碘酸氧化两步反应而制得。
单糖甲基糖甙的方法是公知的,如在如下文献中有述,该文献引入本文作为参考:“Hockett RC.,Phelps FP.,Hudson CS,Relations between rotatory powerand structure in the sugar group.XXXIII.The alpha and beta methyl pyranos ides ofL-fucose(L-galactomethylose)and their triacetates.J.Am.Chem.Soc.,1939,61:1658-1660”。本发明建议按如下步骤制备甲基糖甙:
向容器中加入甲醇,通入干氯化氢气体,使氯化氢质量浓度为1%,然后加入干燥过的单糖,配成单糖质量含量为10%的悬浮液,在回流条件下反应8h,冷却后用饱和氢氧化钠溶液中和至pH=7.0~8.0,减压蒸馏除去甲醇,用乙酸乙酯溶解固体并进行重结晶,过滤得到甲基糖苷。
由甲基糖甙制备取代二甘醇醛的方法是公知的,如在如下文献中有述,该文献引入本文作为参考:“Maclay WD.,Hann RM.Hudson CS.,The cleavage of thecarbon chains of some methyl aldohexomethylo-pyranosides by oxidation withperiodic acid.J.Am.Chem.Soc.,1939,61:1660-1666”。本发明建议按如下步骤制备取代二甘醇醛:
将甲基糖甙配成质量浓度为3~10%的水溶液,加入摩尔数为甲基糖甙2.1倍的高碘酸,在室温、避光条件下反应12~24h,用10%热氢氧化锶溶液中和至中性,过滤除去沉淀,将滤液在50~60℃抽真空浓缩至干燥,用乙醇萃取固体4次,将滤液合并,浓缩至糖浆状,用***溶解,加入石油醚,室温放置16h,过滤得到二醛晶体。
取代二甘醇醛含两个活泼醛基,可在较宽温度范围内与醇溶蛋白分子上的胺基发生如下反应,
从而将两个或多个醇溶蛋白交联起来,形成网状交联结构。式中Gliadin代表醇溶蛋白分子。
赋予交联型谷类醇溶蛋白可食性膜优异的成膜性能、疏水性能与抗老化性能是本发明的关键之一。增塑剂与疏水改性剂的配合使用,使得谷类醇溶蛋白组合物除了可采用溶液流延法成膜外,还可采用高分子材料热塑性加工设备与方法成膜。疏水改性剂的使用以及醇溶蛋白分子间的交联作用,使交联型谷类醇溶蛋白膜的疏水性得以大幅度提高。同时,本发明采用作为食品添加剂使用的抗氧剂与防腐剂,提高交联型谷类醇溶蛋白膜的储存寿命与耐老化性能。
以下结合具体实施例进一步说明本发明。
实施例1:
以小麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:称取100g谷朊粉,加入500ml60%的乙醇/水混合溶剂中,在30℃电磁搅拌2h提取小麦醇溶蛋白,离心分离获得上清液,补充适当的60%的乙醇/水混合溶剂使醇溶蛋白浓度为50mg/ml,取醇溶蛋白溶液100ml,加入1g 1,2-丙二醇、25mg硬脂酸、2.5mg叔丁基羟基茴香醚与50mg D′-甲氧基二甘醇醛,搅拌均匀得到成膜溶液,倾倒在光滑的塑料板上,待溶剂挥发完毕后,在50℃热处理1h,揭膜,得到交联型谷类醇溶蛋白可食性膜。
实施例2:
以大麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:称取100g大麦籽粒粉,加入500ml90%的乙醇/水混合溶剂中,在50℃电磁搅拌2h提取小麦醇溶蛋白,离心分离获得上清液,补充适当的90%的乙醇/水混合溶剂使醇溶蛋白浓度为100mg/ml,取醇溶蛋白溶液100ml,加入10g 1,3-丙二醇、100mg羟基硬脂酸、10mg茶多酚、10mg山梨酸乙酯与700mg D′-甲氧基-D-羟甲基二甘醇醛,搅拌均匀得到成膜溶液,倾倒在光滑的塑料板上,待溶剂挥发完毕后,在120℃热处理30min,揭膜,得到交联型谷类醇溶蛋白可食性膜。
实施例3:
以燕麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:称取10g燕麦醇溶蛋白,加入70%的乙醇/水混合溶剂中,配成质量浓度为80mg/ml的溶液,加入5g二甘醇、80mg硬脂酸正丁酯、8mg生育酚、80mg山梨酸对羟基苯甲酸丁酯与300mgL′-甲氧基-L-甲基二甘醇醛,搅拌均匀得到成膜溶液,倾倒在光滑的塑料板上,待溶剂挥发完毕后,在100℃热处理45min,揭膜,得到交联型谷类醇溶蛋白可食性膜。
实施例4:
以黑麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:称取100g黑麦醇溶蛋白、40g三甘醇、1g单硬脂酸甘油脂、100mg没食子酸乙酯与80mg脱氢乙酸,置于Haake混炼仪内,在50r/min转速下室温混合5min,将混合物物料置于开炼机上,于10℃混炼15min,并在混炼过程中加入300mgD′-甲氧基-D′,D-二羟甲基二甘醇醛,获得谷类蛋白质组合物,经四辊压延机压延成膜,在150℃热空气交联10min,得到交联型谷类醇溶蛋白可食性膜。
实施例5:
以大米醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:称取100g大米醇溶蛋白、40g四甘醇、1g羟基硬脂酸甲酯、100mg没食子酸丙酯与80mg尼泊金甲酯,置于高速混合机内,在3000r/min转速下室温混合2min,将混合物物料置于开炼机上,于40℃混炼5min,并在混炼过程中加入300mg D′-甲氧基-D′,D-二羟甲基二甘醇醛,获得谷类蛋白质组合物,经三辊压延机压延成膜,在180℃热空气交联2min,得到交联型谷类醇溶蛋白可食性膜。
实施例6:
以粟米醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以粟米醇溶蛋白代替燕麦醇溶蛋白、以甘油代替二甘醇、以大豆油代替硬脂酸正丁酯、以没食子酸辛酯代替生育酚、以对羟基苯甲酸丙酯代替山梨酸对羟基苯甲酸丁酯,其余条件同实施例3。
实施例7:
以玉米醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以玉米醇溶蛋白代替黑麦醇溶蛋白、以1,2-丁二醇代替三甘醇、以花生油代替单硬脂酸甘油脂、以没食子酸十二酯代替没食子酸乙酯、以对羟基苯甲酸乙酯代替脱氢乙酸,其余条件同实施例4。
实施例8:
以高粱醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以高粱醇溶蛋白代替大米醇溶蛋白、以1,3-丁二醇代替四甘醇、以玉米油代替羟基硬脂酸甲酯、以没食子酸十八酯代替没食子酸丙酯,其余条件同实施例5。
实施例9~14:
以小麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以1,4-丁二醇、2,3-丁二醇、1,2,3-己三醇、1,2,6-己三醇、甘油单乙酸酯或甘油二乙酸酯代替1,2-丙二醇,其余条件同实施例1。
实施例15~19:
以大麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以米糠油、菜籽油、棉籽油、葵花籽油或油茶籽油代替硬脂酸,其余条件同实施例2。
实施例20~24:
以燕麦醇溶蛋白为原料制备交联型谷类醇溶蛋白可食性膜的制备方法为:分别以抗坏血酸、抗坏血酸棕榈酸酯、D-异抗坏血酸、山梨糖醇或麦芽糖醇代替生育酚,其余条件同实施例3。
本发明提供了一种交联型谷类醇溶蛋白可食性膜及其制备方法。本发明所涉及的主要原料谷类蛋白质属于可再生农业资源,来源广泛;本发明所涉及的谷类醇溶蛋白可食性膜的制备方法与工艺流程简单,易于推广实施。基于本发明制得的交联型谷类醇溶蛋白可食性膜具有优异的力学性能、疏水性与抗老化性能,不含对人体有害的添加剂,可用于食品、糖制品与药品等的可食性包装膜。
Claims (7)
1.一种交联型谷类醇溶蛋白可食性膜,其特征在于,它包含谷类醇溶蛋白100重量份、增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份、防腐剂0~0.1重量份与交联剂1~7重量份,疏水改性剂为硬脂酸、羟基硬脂酸、硬脂酸正丁酯、单硬脂酸甘油脂、羟基硬脂酸甲酯、大豆油、花生油、玉米油、米糠油、菜籽油、棉籽油、葵花籽油或油茶籽油,交联剂为D′-甲氧基二甘醇醛、D′-甲氧基-D-羟甲基二甘醇醛、L′-甲氧基-L-甲基二甘醇醛或D′-甲氧基-D′,D-二羟甲基二甘醇醛。
2.根据权利要求1所述的交联型谷类醇溶蛋白可食性膜,其特征在于,所述的谷类醇溶蛋白是小麦醇溶蛋白、大麦醇溶蛋白、燕麦醇溶蛋白、黑麦醇溶蛋白、大米醇溶蛋白、粟米醇溶蛋白、玉米醇溶蛋白或高粱醇溶蛋白。
3.根据权利要求1所述的交联型谷类醇溶蛋白可食性膜,其特征在于,所述的增塑剂是1,2-丙二醇、1,3-丙二醇、二甘醇、三甘醇、四甘醇、甘油、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2,3-己三醇、1,2,6-己三醇、甘油单乙酸酯或甘油二乙酸酯。
4.根据权利要求1所述的交联型谷类醇溶蛋白可食性膜,其特征在于,所述的抗氧剂为叔丁基羟基茴香醚、茶多酚、生育酚、没食子酸乙酯、没食子酸丙酯、没食子酸辛酯、没食子酸十二酯、没食子酸十八酯、抗坏血酸、抗坏血酸棕榈酸酯、D-异抗坏血酸、山梨糖醇或麦芽糖醇。
5.根据权利要求1所述的交联型谷类醇溶蛋白可食性膜,其特征在于,所述的防腐剂为山梨酸乙酯、山梨酸对羟基苯甲酸丁酯、脱氢乙酸、尼泊金甲酯、对羟基苯甲酸丙酯或对羟基苯甲酸乙酯。
6.一种如权利要求1所述的交联型谷类醇溶蛋白可食性膜的制备方法,其特征在于,以60~90%的乙醇/水混合物为溶剂,加入谷类醇溶蛋白100重量份,在30~50℃下强烈搅拌,配置成浓度为50~100mg/ml的溶液,加入增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份、防腐剂0~0.1重量份与交联剂1~7重量份,搅拌均匀得到成膜溶液,倾倒在光滑的塑料板上,待溶剂挥发完毕后,在50~120℃热处理0.5~1h,揭膜,得到交联型谷类醇溶蛋白可食性膜。
7.一种如权利要求1所述的交联型谷类醇溶蛋白可食性膜的制备方法,其特征在于,将谷类醇溶蛋白100重量份、增塑剂20~100重量份、疏水改性剂0.5~1重量份、抗氧剂0.05~0.1重量份与防腐剂0~0.1重量份进行预混合,然后在10~40℃机械混炼5~15min,并在混炼过程中加入交联剂1~7重量份,获得醇溶蛋白组合物,送入压延机压延成膜,经150~180℃热处理2~10min,得到交联型谷类醇溶蛋白可食性膜。
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CN101092511B (zh) * | 2007-06-12 | 2010-05-26 | 浙江大学 | 易于成型的交联型谷类蛋白质可降解塑料及其制备方法 |
ITMO20070323A1 (it) | 2007-10-22 | 2009-04-23 | Illycaffe Spa | Contenitore |
CN103013139A (zh) * | 2012-12-19 | 2013-04-03 | 青岛海尔软件有限公司 | 一种蛋白/普鲁兰多糖复合型可食用膜及其制备方法 |
CN102964847A (zh) * | 2012-12-20 | 2013-03-13 | 青岛海尔软件有限公司 | 一种蛋白/壳聚糖复合型可食用膜及其制备方法 |
CN103554536B (zh) * | 2013-11-01 | 2016-04-20 | 江南大学 | 一种花生分离蛋白-***胶复合膜的制备方法 |
CN103602076A (zh) * | 2013-11-13 | 2014-02-26 | 哈尔滨派特纳生物科技开发有限公司 | 番茄可食膜 |
CN104397828B (zh) * | 2014-11-19 | 2017-05-10 | 渤海大学 | 一种改性玉米醇溶蛋白复合缓释抗菌液态膜的制备方法 |
CN106589430A (zh) * | 2016-12-26 | 2017-04-26 | 福建农林大学 | 一种超声波辅助碱处理制备大米蛋白膜的方法 |
CN107141518A (zh) * | 2017-06-07 | 2017-09-08 | 安徽中盛食用油科技有限公司 | 一种包裹茶籽油的可食性抗菌薄膜及其制备方法 |
CN110448723B (zh) * | 2019-07-12 | 2022-04-05 | 四川大学 | 协同抗氧型高交联超高分子量聚乙烯人工关节材料及其制备方法 |
CN110754663A (zh) * | 2019-11-21 | 2020-02-07 | 华南理工大学 | 一种含β-胡萝卜素的交联型核壳结构微胶囊及其制备方法和应用 |
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CN1302550A (zh) * | 2000-01-01 | 2001-07-11 | 天津商学院 | 用玉米谷朊制备醇溶玉米蛋白膜 |
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