CN1285376A - Process for preparation of water-proof and heat-resistant plastic soybean protein film - Google Patents
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Abstract
本发明公开了一种大豆蛋白膜制备方法。它是市售大豆渣蛋白提取物经分级后,与甘油混合后热压而成。这种热塑性膜无毒、可食、透明、耐沸水、耐寒及耐真空抽取,其强度和伸长率达5.5MPa和140%。而且生产工艺简单,成本低廉,生产过程中无污染。它可用作食品包装及生物降解材料,在医药、日用、化工和环保领域有应用前景。The invention discloses a method for preparing a soybean protein film. It is produced by grading commercially available soybean dregs protein extracts, mixing them with glycerin and then hot pressing them. This thermoplastic film is non-toxic, edible, transparent, resistant to boiling water, cold and vacuum extraction, and its strength and elongation are up to 5.5MPa and 140%. Moreover, the production process is simple, the cost is low, and there is no pollution in the production process. It can be used as food packaging and biodegradable materials, and has application prospects in the fields of medicine, daily use, chemical industry and environmental protection.
Description
本发明涉及一种耐水热塑性大豆蛋白膜的制备方法,它是用大豆渣中的大豆蛋白制得的功能材料,属于高分子领域。The invention relates to a preparation method of a water-resistant thermoplastic soybean protein film, which is a functional material prepared from soybean protein in soybean dregs and belongs to the field of macromolecules.
由于不可再生资源的日益消耗和合成材料的非降解性而造成的严重环境污染,可再生的环境友好材料越来越引人注目。新兴的“工业蛋白质塑料”属此类,它对环境无毒无害,可望替代某些石油化学品。大豆分离蛋白是从大豆渣炼油后的副产物中分离出来的,约占大豆渣的50%(w/w),是由多种氨基酸组成的天然高分子(Whitaker,J.R.Food proteins.1977,p498.)。大豆渣一般作为动物饲料,而大豆分离蛋白则可用于食品和粘合剂行业(J.Japanese Soc.Food Sci.and Tech.1995,42(9),672;J.Amer.Oil Chem.Soc.2000,77,101.)。采用流延法制备的大豆蛋白膜成本高昂,能耗高,脆性大,耐寒性差,而且不可热塑,实用性受到限制(J.Amer.Oil Chem.Soc.1994,71(11),1281)。用热压法制热塑性蛋白膜或大豆蛋白片材在国内尚未见报道,国外也是近几年才见报道(Ind.Eng.Chem.Res.1994,33(7),1821;J.Polym.Eng.1999,19(6),383)。在这些报道中,热塑性大豆蛋白膜的耐水性,尤其耐热水性尚不够高。Due to the increasing consumption of non-renewable resources and the severe environmental pollution caused by the non-degradability of synthetic materials, renewable and environmentally friendly materials are attracting more and more attention. Emerging "industrial protein plastics" fall into this category, which are non-toxic and harmless to the environment and are expected to replace some petrochemicals. Soybean protein isolate is isolated from the by-products of soybean dregs after oil refining, accounting for about 50% (w/w) of soybean dregs, and is a natural polymer composed of various amino acids (Whitaker, J.R.Food proteins.1977, p498 .). Soybean dregs are generally used as animal feed, while soybean protein isolate can be used in food and adhesive industries (J.Japanese Soc.Food Sci.and Tech.1995, 42(9), 672; J.Amer.Oil Chem.Soc. 2000, 77, 101.). The soybean protein film prepared by cast method has high cost, high energy consumption, high brittleness, poor cold resistance, and is not thermoplastic, so its practicability is limited (J.Amer.Oil Chem.Soc.1994, 71(11), 1281) . Making thermoplastic protein films or soybean protein sheets by hot pressing has not been reported in China, and it has only been reported in recent years abroad (Ind.Eng.Chem.Res.1994, 33 (7), 1821; J.Polym.Eng. 1999, 19(6), 383). In these reports, the water resistance, especially the hot water resistance, of the thermoplastic soybean protein film is not high enough.
本发明的目的是提供一种耐水热塑性大豆蛋白膜材料的制备新方法。该方法充分利用大豆蛋白这种价廉的再生资源,用简单、快速的方法制得。此热塑材料具有无毒、可食、耐沸水、低成本、耐寒、耐真空抽提、透明。这种膜材料可降解,原料提取过程及生产过程中无污染,能耗低,有利于环保,尤其对于解决天然高分子材料制备过程中遇到的成型问题有重要意义。The purpose of the invention is to provide a new method for preparing a water-resistant thermoplastic soybean protein film material. The method makes full use of soybean protein, which is a cheap renewable resource, and is prepared in a simple and rapid method. The thermoplastic material is non-toxic, edible, resistant to boiling water, low cost, cold-resistant, resistant to vacuum extraction, and transparent. This kind of membrane material is degradable, has no pollution in the process of raw material extraction and production, has low energy consumption, and is beneficial to environmental protection. It is especially important for solving the forming problems encountered in the preparation process of natural polymer materials.
为实现上述目的,本发明采用的技术方案如下:To achieve the above object, the technical scheme adopted in the present invention is as follows:
一种耐水热塑性大豆蛋白膜的制备方法:将大豆蛋白粉加0.4-0.7倍的甘油,共混合30分钟后,在100-180℃,5-20 Mpa下热压,20分钟后冷至60-80℃,即得金黄色透明的耐水热塑性大豆蛋白膜。A method for preparing a water-resistant thermoplastic soybean protein film: add 0.4-0.7 times of glycerin to soybean protein powder, mix together for 30 minutes, heat press at 100-180°C, 5-20 Mpa, and cool to 60-20 minutes after 20 minutes. At 80°C, a golden-yellow transparent water-resistant thermoplastic soybean protein film is obtained.
根据本发明的技术方案,所述的大豆蛋白粉是按如下方法制备:将市售大豆蛋白溶于碱水中,离心除去杂质,用酸调节PH=5.70~6.5,待蛋白粉预沉淀后,离心,取出沉淀,加水,调PH=4.5,使蛋白充分沉淀,经离心,洗涤、真空干燥即可。According to the technical solution of the present invention, the soybean protein powder is prepared as follows: dissolve the commercially available soybean protein in alkaline water, centrifuge to remove impurities, adjust the pH to 5.70-6.5 with acid, and centrifuge after the protein powder is pre-precipitated. , take out the precipitate, add water, adjust the pH to 4.5, make the protein fully precipitate, centrifuge, wash and vacuum dry.
本发明所用的市售大豆蛋白从湖北云梦县龙云蛋白食品有限公司购得,其标准为卾Q/YZW×01-96。甘油为市售,未经任何处理。The commercially available soybean protein used in the present invention is purchased from Hubei Yunmeng County Longyun Protein Food Co., Ltd., and its standard is 卾Q/YZW×01-96. Glycerin is commercially available without any treatment.
本发明耐水热塑性大豆蛋白膜可用于化工、食品、环境领域中的包装材料,也可用作医用材料,如药品酶的固定化,药物传递及释放。The water-resistant thermoplastic soybean protein film of the invention can be used as packaging materials in the fields of chemical industry, food and environment, and can also be used as medical materials, such as the immobilization of drug enzymes, drug delivery and release.
与已有技术相比较,采用本发明的技术方案所取得的有益效果如下:Compared with the prior art, the beneficial effects obtained by adopting the technical solution of the present invention are as follows:
1.采用热压工艺,工艺简单,成本低,能耗低。由本发明所得膜具热塑性,1. The hot pressing process is adopted, the process is simple, the cost is low, and the energy consumption is low. The resulting film of the present invention is thermoplastic,
可反复热压,这是因为所用增塑剂为高沸点甘油,无低沸点化合物存在。It can be hot-pressed repeatedly, because the plasticizer used is glycerin with high boiling point and no low-boiling point compounds exist.
2.首次得到耐水性的天然高分子膜。测试表明:它既可耐冷水,又可耐沸水。2. For the first time, a water-resistant natural polymer film was obtained. Tests have shown that it is resistant to both cold and boiling water.
而且通过本方法分级的大豆蛋白的耐水性可大大提高。Moreover, the water resistance of the soybean protein classified by the method can be greatly improved.
3.由本发明所得的膜耐寒性高,测试表明其玻璃化转变温度Tg在-70℃左3. The film obtained by the present invention has high cold resistance, and tests show that its glass transition temperature Tg is around -70°C
右。而一般淀粉、纤维素膜类的Tg仅在室温左右,耐寒性差。right. However, the Tg of general starch and cellulose films is only around room temperature, and their cold resistance is poor.
4.由本发明所得膜耐真空抽提,环境稳定性高,测试表明:在2mmHg的真4. The film obtained by the present invention is resistant to vacuum extraction and has high environmental stability. Tests show that: at 2mmHg
空下抽提7小时,膜仍能保持较好的弹性。After extraction under vacuum for 7 hours, the film still maintains good elasticity.
以下结合具体的实施例对本发明的技术方案作进一步说明:The technical scheme of the present invention is further described below in conjunction with specific embodiment:
实施例1大豆蛋白粉的制备:The preparation of embodiment 1 soybean protein powder:
400g市售大豆分离蛋白分散于6升去离子水中,滴加2M的NaOH,直到PH=13,搅拌30分钟后,于8000转离心10分钟。取上清液用2M HCL调PH=5.70,此时有白色絮状粘性蛋白质沉淀产生,经8000转离心10分钟。取沉淀加水2升水,调PH=4.5,使重沉淀。再经8000转10分钟离心,取沉淀并用水及丙酮各洗三次,真空干燥即得褐白色产物。将产物高速粉碎,过140目筛,干燥、贮存即可。Disperse 400g of commercially available soybean protein isolate in 6 liters of deionized water, add dropwise 2M NaOH until the pH=13, stir for 30 minutes, and then centrifuge at 8000 rpm for 10 minutes. Take the supernatant and adjust the pH to 5.70 with 2M HCL. At this time, a white flocculent viscous protein precipitate is produced, and it is centrifuged at 8000 rpm for 10 minutes. Take the precipitate and add 2 liters of water to adjust the pH to 4.5 to re-precipitate. After centrifugation at 8000 rpm for 10 minutes, the precipitate was taken, washed three times with water and acetone, and dried in vacuum to obtain a brown-white product. The product is crushed at high speed, passed through a 140-mesh sieve, dried and stored.
实施例2Example 2
取上述实施例1中的大豆蛋白粉3g,加入甘油1.5g,用研钵碾30分钟,充分混合后平铺于两片铜镍合金的上光板之间,光板尺寸为18.5cm×10.5cm×1mm。然后进行热压,控温于150℃,压力为15Mpa。热压20秒,风吹20分钟冷至80℃,取模即得黄色透明膜。膜的性能见附表1。Take 3g of soybean protein powder in the above-mentioned Example 1, add 1.5g of glycerin, grind it with a mortar for 30 minutes, mix it well and spread it between two copper-nickel alloy glazing plates, the size of the glazing plate is 18.5cm×10.5cm× 1mm. Then hot pressing is carried out, the temperature is controlled at 150° C., and the pressure is 15 MPa. Hot press for 20 seconds, blow with wind for 20 minutes and cool to 80°C, take a mold to get a yellow transparent film. The performance of the membrane is shown in Table 1.
实施例3Example 3
取上述实施例1中的大豆蛋白粉3g,加入甘油2g,用研钵碾30分钟,充分混合后平铺于两片上述上光板之间。经热压,并控温于180℃,压力为10Mpa,热压20秒。用风吹20分钟冷至80℃,取出即得黄色透明膜。Get 3g of the soybean protein powder in the above-mentioned Example 1, add 2g of glycerin, grind it with a mortar for 30 minutes, mix well and spread it between two above-mentioned glazing boards. After hot pressing, the temperature is controlled at 180°C, the pressure is 10Mpa, and hot pressing is performed for 20 seconds. Cool to 80°C by blowing with wind for 20 minutes, and take it out to obtain a yellow transparent film.
表1.分级对大豆蛋白膜性能的影响Table 1. The effect of fractionation on the properties of soybean protein films
续表1:Continuation of Table 1:
a于25℃水浸泡15大。 a Soak in water at 25°C for 15°C.
b于沸水浸煮15分钟。 b Soak in boiling water for 15 minutes.
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| CN103146004A (en) * | 2013-02-27 | 2013-06-12 | 江阴摩尔化工新材料有限公司 | Method for improving soybean protein isolate film water resistance through photo-crosslinking |
| CN103183837A (en) * | 2012-12-14 | 2013-07-03 | 江南大学 | Preparation method of heat resistant soy protein/graphene oxide composite membrane |
| CN103283937A (en) * | 2013-04-26 | 2013-09-11 | 中国国旅贸易有限责任公司 | Casing film and preparation method thereof |
| CN104686782A (en) * | 2015-03-16 | 2015-06-10 | 常熟理工学院 | Method for improving water vapor isolation performance of soy protein isolate film |
| CN105886677A (en) * | 2016-04-22 | 2016-08-24 | 广州市惠景皮革有限公司 | Aniline calfskin leather coating composition and coating technology thereof |
| CN106012092A (en) * | 2016-08-05 | 2016-10-12 | 翁冰雄 | A kind of multifunctional protein fiber and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183837A (en) * | 2012-12-14 | 2013-07-03 | 江南大学 | Preparation method of heat resistant soy protein/graphene oxide composite membrane |
| CN103183837B (en) * | 2012-12-14 | 2016-08-03 | 江南大学 | A kind of preparation method of heat resistant soy protein/graphene oxide composite membrane |
| CN103146004A (en) * | 2013-02-27 | 2013-06-12 | 江阴摩尔化工新材料有限公司 | Method for improving soybean protein isolate film water resistance through photo-crosslinking |
| CN103283937A (en) * | 2013-04-26 | 2013-09-11 | 中国国旅贸易有限责任公司 | Casing film and preparation method thereof |
| CN104686782A (en) * | 2015-03-16 | 2015-06-10 | 常熟理工学院 | Method for improving water vapor isolation performance of soy protein isolate film |
| CN105886677A (en) * | 2016-04-22 | 2016-08-24 | 广州市惠景皮革有限公司 | Aniline calfskin leather coating composition and coating technology thereof |
| CN105886677B (en) * | 2016-04-22 | 2018-05-18 | 广州市惠景皮革有限公司 | A kind of aniline calf-skin applies decorative composition and its Coating technology |
| CN106012092A (en) * | 2016-08-05 | 2016-10-12 | 翁冰雄 | A kind of multifunctional protein fiber and preparation method thereof |
| CN106012092B (en) * | 2016-08-05 | 2018-02-16 | 广东安之伴实业有限公司 | A kind of multifunctional protein fiber and preparation method thereof |
| CN113350319A (en) * | 2021-07-08 | 2021-09-07 | 周文超 | Medical plaster |
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