技术领域technical field
本发明涉及材料与环保领域，特别涉及一种多糖-蛋白复合膜及其制备方法。The invention relates to the fields of materials and environmental protection, in particular to a polysaccharide-protein composite membrane and a preparation method thereof.
背景技术Background technique
近几年，随着食品保鲜膜技术更深入、更广泛的研究，所使用的材料由过去的一些非食用或营养性、口感均不理想的材料逐步发展为可食用、营养价值较高的材料，如多聚糖类、类脂、蛋白质等，它们既是包装，又是食品中的一种组分，使用后丢弃在自然环境中可完全降解，从而防止对环境的污染。然而单一多糖或蛋白质作为天然高分子食品保鲜膜的制备成膜时，其成膜性、膜的亲水性和透气性等存在一定缺陷，膜的机械性能也不能满足广泛的需求。In recent years, with the in-depth and extensive research on food preservation film technology, the materials used have gradually developed from some non-edible or nutritious and unsatisfactory materials in the past to edible materials with high nutritional value. , such as polysaccharides, lipids, proteins, etc., which are not only packaging, but also a component of food, which can be completely degraded when discarded in the natural environment after use, thereby preventing environmental pollution. However, when a single polysaccharide or protein is used as a natural polymer food preservation film, there are certain defects in its film formation, hydrophilicity and air permeability of the film, and the mechanical properties of the film cannot meet a wide range of needs.
据报道，美国的多个食品研究院所利用多糖、脂类、蛋白质、淀粉等为材料，研制出用于葡萄干、干酪和饼干的可食性保鲜薄膜及降解食品袋。此外，可降解性、可食性膜在医药、化妆品、香精香料等方面也得到广泛应用。我国对可食性膜的研究起步相对较晚，近些年才逐步开展，在多糖膜、蛋白质膜、复合膜的研制方面已初见成效，但真正能用于大规模工业生产的产品较少，缺乏系统的基础和应用研究。在成膜材料的选择、成膜机理研究与工艺改进、膜的性能和质量以及应用等方面，仍存在许多亟待解决的瓶颈问题，与欧美日等发达国家之问仍存在极大的差距。According to reports, many food research institutes in the United States have developed edible fresh-keeping films and degradable food bags for raisins, cheese and biscuits using polysaccharides, lipids, proteins, starches, etc. as materials. In addition, degradable and edible films are also widely used in medicine, cosmetics, flavors and fragrances, etc. Research on edible films in my country started relatively late, and has only been gradually carried out in recent years. Initial results have been achieved in the development of polysaccharide films, protein films, and composite films, but there are few products that can be used in large-scale industrial production. There is a lack of systematic basic and applied research. In the selection of film-forming materials, film-forming mechanism research and process improvement, film performance and quality, and application, there are still many bottlenecks to be solved, and there is still a huge gap with developed countries such as Europe, America and Japan.
发明内容Contents of the invention
本发明的目的是在于针对背景技术中存在的问题提供了一种多糖-蛋白复合膜及其制备方法，本发明制备的多糖-蛋白复合膜可生物降解，有较好的阻湿阻氧等特性。The purpose of the present invention is to provide a polysaccharide-protein composite film and its preparation method for the problems existing in the background technology. The polysaccharide-protein composite film prepared by the present invention is biodegradable and has good moisture and oxygen resistance properties. .
具体技术方案如下：The specific technical scheme is as follows:
一种多糖-蛋白复合膜，由下列质量百分比的原料组成：A kind of polysaccharide-protein composite membrane, is made up of the raw material of following mass percentage:
多糖 20-80 % 粉体蛋白 80-20%。Polysaccharide 20-80% Powder protein 80-20%.
作为优选项：As a preference:
所述多糖为魔芋葡甘聚糖、普鲁兰、可得然胶、海藻胶、羧甲基纤维素中的一种或几种的混合物。The polysaccharide is one or a mixture of konjac glucomannan, pullulan, curdlan, alginate and carboxymethyl cellulose.
所述蛋白为大豆分离蛋白。The protein is soybean protein isolate.
the
本发明还提供了上述多糖-蛋白复合膜的制备方法，包括以下步骤：The present invention also provides a preparation method for the polysaccharide-protein composite film, comprising the following steps:
A、称取多糖，将多糖加入蒸馏水中，配制成质量浓度为1% -2%的水溶胶，搅拌均匀，得到多糖水溶胶，备用； A. Weigh the polysaccharide, add the polysaccharide into distilled water, and prepare a hydrosol with a mass concentration of 1%-2%, stir evenly to obtain the polysaccharide hydrosol, and set aside;
B、称取蛋白，将蛋白加入蒸馏水中，配制成质量浓度为1.5-2%的分散液，搅拌均匀后用弱碱性溶液调pH至7.0~11.0后均质，得到蛋白质分散液，备用；B. Weigh the protein, add the protein into distilled water, and prepare a dispersion with a mass concentration of 1.5-2%, stir evenly, adjust the pH to 7.0-11.0 with a weak alkaline solution, and then homogenize to obtain a protein dispersion for later use;
C、将步骤A制备的多糖水溶胶与步骤B制备的蛋白分散液混合,在65℃~75℃条件下搅拌150-200分钟使其混合均匀，得到混合溶胶； C. Mix the polysaccharide hydrosol prepared in step A with the protein dispersion prepared in step B, stir at 65°C~75°C for 150-200 minutes to mix evenly, and obtain a mixed sol;
D、将上步所得混合溶胶流延成膜，40-80℃温度范围内干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight in the temperature range of 40-80°C to obtain a polysaccharide-protein composite film.
作为优选项：As a preference:
所述多糖为魔芋葡甘聚糖、普鲁兰、可得然胶、海藻胶、羧甲基纤维素中的一种或几种的混合物。The polysaccharide is one or a mixture of konjac glucomannan, pullulan, curdlan, alginate and carboxymethyl cellulose.
所述蛋白为大豆分离蛋白。The protein is soybean protein isolate.
所述步骤A中当多糖为多糖混合物时，将每种多糖分别加入蒸馏水中，分别配制成质量比为1-2%的多糖水溶胶。In the step A, when the polysaccharide is a mixture of polysaccharides, each polysaccharide is added into distilled water to prepare polysaccharide hydrosols with a mass ratio of 1-2%.
所述步骤C中多糖水溶胶与蛋白分散液的质量比为多糖水溶胶/蛋白分散液=（1～4）/（2～1）。The mass ratio of the polysaccharide hydrosol to the protein dispersion in the step C is polysaccharide hydrosol/protein dispersion=(1-4)/(2-1).
所述步骤B中弱碱性溶液为NaOH溶液或乙酸钠溶液。The weak alkaline solution in the step B is NaOH solution or sodium acetate solution.
the
本技术方案是区别于现有技术的主要是利用新型多糖与蛋白通过简单方便的复合方法得到具有可降解性、可食性的复合膜。本发明制得的多糖-蛋白膜的抗拉强度可达到36.9 MPa，在膜性能方面优于单一多糖或者蛋白膜。The technical solution is different from the prior art mainly in that a degradable and edible composite film is obtained through a simple and convenient composite method by using novel polysaccharides and proteins. The tensile strength of the polysaccharide-protein film prepared by the invention can reach 36.9 MPa, which is superior to single polysaccharide or protein film in terms of film performance.
本发明制备方法技术简单易操作，复合膜性能比单一多糖或者蛋白膜具有优势。The preparation method of the invention is simple and easy to operate, and the performance of the composite membrane is superior to that of a single polysaccharide or protein membrane.
本发明提出的多糖-蛋白膜的制备方法具有可操作性。原料来源广泛，属可再生资源。制备成本低，成产过程无三废。使用后废弃物可生物降解，可广泛用于食品包装、保鲜等领域，无毒害。The preparation method of the polysaccharide-protein film proposed by the invention is operable. The raw materials come from a wide range of sources and are renewable resources. The preparation cost is low, and there are no three wastes in the production process. The waste after use is biodegradable, and can be widely used in food packaging, fresh-keeping and other fields, and is non-toxic.
该产品可广泛应用于食品保鲜膜，包装膜等领域。The product can be widely used in food preservation film, packaging film and other fields.
the
具体实施方式Detailed ways
实例1：Example 1:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将魔芋葡甘聚糖加入蒸馏水中，60℃下搅拌混匀180分钟，配制成质量浓度为2%的魔芋葡甘聚糖水溶胶； A. Add konjac glucomannan to distilled water, stir and mix at 60°C for 180 minutes, and prepare konjac glucomannan hydrosol with a mass concentration of 2%;
B、将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为2%的大豆分离蛋白分散液；搅拌均匀后用NaOH溶液调pH至10.0后均质，得到蛋白质分散液；B. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes, and prepare a soybean protein isolate dispersion with a mass concentration of 2%; after stirring evenly, adjust the pH to 10.0 with NaOH solution and homogenize to obtain protein dispersion liquid;
C、将魔芋葡甘聚糖水溶胶和蛋白质分散液按照质量比为魔芋葡甘聚糖水溶胶/蛋白分散液=1：2的比例混合，75℃下搅拌使其混合均匀得到混合溶胶； C. Mix the konjac glucomannan hydrosol and the protein dispersion according to the mass ratio of konjac glucomannan hydrosol/protein dispersion = 1:2, stir at 75°C to make it evenly mixed to obtain a mixed sol;
D、将上步所得混合溶胶流延成膜，80℃下干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry to constant weight at 80°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为23.1 MPa。The tensile strength of the obtained film was 23.1 MPa.
the
实例2：Example 2:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将魔芋葡甘聚糖加入蒸馏水中，60℃下搅拌混匀180分钟，配制成质量浓度为2%的魔芋葡甘聚糖水溶胶；A. Add konjac glucomannan to distilled water, stir and mix at 60°C for 180 minutes, and prepare konjac glucomannan hydrosol with a mass concentration of 2%;
B、将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为1.5%的大豆分离蛋白分散液；搅拌均匀后用乙酸钠溶液调pH至10.0后均质，得到蛋白质分散液；B. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes, and prepare a soybean protein isolate dispersion with a mass concentration of 1.5%; after stirring evenly, adjust the pH to 10.0 with sodium acetate solution and homogenize to obtain protein Dispersions;
C、将魔芋葡甘聚糖水溶胶和蛋白质分散液按照质量比为魔芋葡甘聚糖水溶胶/蛋白分散液=3:1的比例混合， 65℃下搅拌使其混合均匀得到混合溶胶；C. Mix the konjac glucomannan hydrosol and the protein dispersion according to the mass ratio of konjac glucomannan hydrosol/protein dispersion=3:1, stir at 65°C to make it evenly mixed to obtain a mixed sol;
D、将上步所得混合溶胶流延成膜， 80℃下干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight at 80°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为26.3 MPa。The tensile strength of the obtained film was 26.3 MPa.
the
实例3： Example 3:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将魔芋葡甘聚糖加入蒸馏水中，60℃下搅拌混匀180分钟，配制成质量浓度为2%的魔芋葡甘聚糖水溶胶； A. Add konjac glucomannan to distilled water, stir and mix at 60°C for 180 minutes, and prepare konjac glucomannan hydrosol with a mass concentration of 2%;
B、 将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为2%的大豆分离蛋白分散液；搅拌均匀后用乙酸钠溶液调pH至11.0后均质，得到蛋白质分散液；B. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes, and prepare a soybean protein isolate dispersion with a mass concentration of 2%; after stirring evenly, adjust the pH to 11.0 with sodium acetate solution and homogenize to obtain protein Dispersions;
C、 将魔芋葡甘聚糖水溶胶和蛋白质分散液按照质量比为魔芋葡甘聚糖水溶胶/蛋白分散液=4:1的比例混合，70℃下搅拌使其混合均匀得到混合溶胶； C. Mix the konjac glucomannan hydrosol and protein dispersion according to the mass ratio of konjac glucomannan hydrosol/protein dispersion=4:1, stir at 70°C to make it evenly mixed to obtain a mixed sol;
D、 将上步所得混合溶胶流延成膜，60℃下干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight at 60°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为36.2 MPa。The tensile strength of the obtained membrane was 36.2 MPa.
the
实例4：Example 4:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将普鲁兰多糖加入蒸馏水中，60℃下搅拌混匀120分钟；配制成质量浓度为2%的普鲁兰多糖水溶胶， A. Add pullulan to distilled water, stir and mix at 60°C for 120 minutes; prepare a pullulan hydrosol with a mass concentration of 2%,
B、将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为2%的大豆分离蛋白分散液；搅拌均匀后用NaOH溶液调pH至7.0后均质，得到蛋白质分散液；B. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes, and prepare a soybean protein isolate dispersion with a mass concentration of 2%; after stirring evenly, adjust the pH to 7.0 with NaOH solution and homogenize to obtain protein dispersion liquid;
C、将普鲁兰多糖水溶胶与蛋白质分散液按照质量比普鲁兰多糖水溶胶/蛋白分散液=4:1的比例混合，75℃下搅拌使其混合均匀得到混合溶胶； C. Mix the pullulan polysaccharide hydrosol and the protein dispersion according to the ratio of mass ratio pullulan polysaccharide hydrosol/protein dispersion = 4:1, stir at 75°C to make it evenly mixed to obtain a mixed sol;
D、将上步所得混合溶胶流延成膜，40℃下干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight at 40°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为34.6 MPa。The tensile strength of the obtained film was 34.6 MPa.
the
实例5：Example 5:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将可得然多糖加入蒸馏水中，90℃下搅拌混匀150分钟，配制成质量浓度为1%可得然多糖水溶胶； A. Add curdlan polysaccharide into distilled water, stir and mix at 90°C for 150 minutes, and prepare curdran polysaccharide hydrosol with a mass concentration of 1%;
B、将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为2%的大豆分离蛋白分散液；搅拌均匀后用NaOH溶液调pH至8.0后均质，得到蛋白质分散液；B. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes to prepare a soybean protein isolate dispersion with a mass concentration of 2%; after stirring evenly, adjust the pH to 8.0 with NaOH solution and homogenize to obtain protein dispersion liquid;
C、将可得然多糖水溶胶与蛋白质分散液按照质量比为可得然多糖水溶胶/蛋白质分散液=4:1的比例混合，70℃下搅拌使其混合均匀得到混合溶胶；C. Mix the curdlan polysaccharide hydrosol and the protein dispersion according to the mass ratio of curdlan polysaccharide hydrosol/protein dispersion = 4:1, stir at 70°C to mix evenly to obtain a mixed sol;
D、将上步所得混合溶胶流延成膜，45℃下干燥至恒重后即得多糖-蛋白复合膜。D. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight at 45°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为33.8 MPa。The tensile strength of the obtained film was 33.8 MPa.
the
实例6：Example 6:
一种多糖-蛋白复合膜，包括以下步骤：A polysaccharide-protein composite film, comprising the following steps:
A、将魔芋葡甘聚糖加入蒸馏水中，60℃下搅拌混匀180分钟，配制成质量浓度为2%的魔芋葡甘聚糖水溶胶；A. Add konjac glucomannan to distilled water, stir and mix at 60°C for 180 minutes, and prepare konjac glucomannan hydrosol with a mass concentration of 2%;
B、将普鲁兰多糖加入蒸馏水中，60℃下搅拌混匀120分钟；配制成质量浓度为2%的普鲁兰多糖水溶胶；B. Add pullulan to distilled water, stir and mix at 60°C for 120 minutes; prepare a pullulan hydrosol with a mass concentration of 2%;
C、将可得然多糖加入蒸馏水中，90℃下搅拌混匀150分钟，配制成质量浓度为1%可得然多糖水溶胶；C. Add curdlan polysaccharide into distilled water, stir and mix at 90°C for 150 minutes, and prepare curdan polysaccharide hydrosol with a mass concentration of 1%;
D、将大豆分离蛋白加入蒸馏水中，90℃下搅拌混匀180分钟，配制成质量浓度为2%的大豆分离蛋白分散液；搅拌均匀后用NaOH溶液调pH至10.0后均质，得到蛋白质分散液；D. Add soybean protein isolate to distilled water, stir and mix at 90°C for 180 minutes, and prepare a soybean protein isolate dispersion with a mass concentration of 2%; after stirring evenly, adjust the pH to 10.0 with NaOH solution and homogenize to obtain protein dispersion liquid;
E、将魔芋葡甘聚糖水溶胶、普鲁兰多糖水溶胶、可得然多糖水溶胶与蛋白质分散液按照质量比为魔芋葡甘聚糖水溶胶/普鲁兰多糖水溶胶/可得然多糖水溶胶/蛋白质分散液=2:1:1:1的比例混合，70℃下搅拌使其混合均匀得到混合溶胶；E, konjac glucomannan hydrosol, pullulan hydrosol, curdlan polysaccharide hydrosol and protein dispersion liquid are konjac glucomannan hydrosol/pullulan polysaccharide hydrosol/curdlan polysaccharide water according to mass ratio Sol/protein dispersion = 2:1:1:1 ratio mixing, stirring at 70°C to make it evenly mixed to obtain a mixed sol;
F、将上步所得混合溶胶流延成膜，60℃下干燥至恒重后即得多糖-蛋白复合膜。F. Cast the mixed sol obtained in the previous step to form a film, and dry it to a constant weight at 60°C to obtain a polysaccharide-protein composite film.
获得的膜抗拉强度为36.9 MPa。 The tensile strength of the obtained film was 36.9 MPa. the
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