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Starch-based plastics are made by chemically modifying starch by chemical reactions, reducing the hydroxyl groups of starch and changing its original structure, thereby changing the corresponding properties of starch and turning the original starch into thermoplastic starch.
Starch is a natural polymer second only to cellulose in terms of production on Earth. It is abundant, renewable and inexpensive. It can be used to produce starch-based plastics through modification and plasticization. As an important category of bio-based materials, starch-based plastics have been successfully industrialized and applied. Starch-based plastics are a type of plastic product made from starch as the main raw material, which is modified and plasticized and then blended with other polymers. They are a type of bioplastics. Starch-based bioplastics can be divided into two categories: bio-based plastics and biodegradable plastics.
Starch-based biodegradable plastics are generally a blend of modified starch and biodegradable polyesters (such as PLA/PBAT/PBS/PHA/PPC, etc.). They are completely biodegradable, compostable, and environmentally friendly. The waste is suitable for treatment by composting, landfilling, and other methods. Starch-based bioplastics are generally a mixture of modified starch and polyolefins (such as PP/PE/PS, etc.). Its environmental significance lies in reducing the use of petrochemical resources, reducing carbon dioxide emissions, and waste is suitable for incineration. Both materials can replace traditional petroleum-based plastics and are widely used in plastic packaging materials, shockproof materials, plastic films and plastic bags, disposable tableware, food containers, toys, etc.
Starch is a natural high molecular polymer with a large number of hydroxyl groups in its molecules (molecular structure is вЄ and вє). Therefore, the interaction between starch macromolecules is very strong, which makes it difficult to melt process the original starch, and the compatibility with other polymers in the blending process is also poor. However, these hydroxyl groups can undergo chemical reactions such as esterification, etherification, grafting, and cross-linking. These chemical reactions are used to chemically modify starch, reduce the hydroxyl groups of starch, change its original structure, thereby changing the corresponding properties of starch and turning the original starch into thermoplastic starch.
1. Esterification, transesterification or etherification reaction
In order to change the hydrophilicity of starch to hydrophobicity, the hydroxyl groups on the starch molecules are esterified and transesterified with fatty acids, fatty acid esters, etc. to generate starch esters.
2. Cross-linking reaction
In order to improve the strength and heat resistance of starch materials, starch is cross-linked with compounds with two or more functional groups (such as polyacids, etc.) to make starch moderately cross-linked.
3. Independent innovation of blending and copolymerization
Most of the preparation technologies of starch plastics are to fill and blend starch with other polymer materials. The products obtained in this way have poor compatibility and low strength, and their scope of use is limited. In the starch modification process, starch-based plastics also copolymerize starch to obtain graft copolymers of starch and other polymers, thereby improving the compatibility of starch with other polymer materials. Through chemical modification, three modifications of starch are achieved: hydrophilicity is changed to hydrophobicity; heat sensitivity is changed to temperature resistance; hardness and brittleness are changed to plasticity. This modification solves the world's difficult problem of starch modification and lays a good foundation for subsequent processing.
Starch-based bioplastics have a 30-year research and development history. They are the biodegradable plastics with the longest research and development history, the most mature technology, the largest industrial scale and the highest market share. In the early 1980s, the research and development of modified starch and biodegradable plastic alloy masterbatch of completely biodegradable or soluble plastics was carried out, and the blending of starch and biodegradable resins received attention. Among them, the most successful is "MaterBi" of Novamont Company in Italy, which is an interpenetrating network structure polymer plastic alloy composed of modified starch and modified polyvinyl alcohol. It has good processing performance, secondary processing, mechanical properties and excellent biodegradability. In addition, "Vinex" developed by Air Product & Chemical Company in the United States is a resin based on polyvinyl alcohol with a low degree of polymerization. It has water solubility, thermoplastic processability and biodegradability, and has received great attention in recent years.
In recent years, countries have generally shifted their research focus to plastics with as high starch content as possible, and developed some fully degradable materials with excellent performance, and even obtained pure starch products without synthetic polymers, namely thermoplastic starch. The "Novon" biodegradable material produced by Warner-Lambert in the United States has a starch content of more than 90%; Japan Corn Company and Michigan Production Technology Research Institute jointly developed a high-starch content material, which has the advantage of strong water resistance; in addition, Japan Sumitomo Corporation and Italy Ferrizz Company also claimed to have successfully researched a full-starch plastic with a starch content of 90%. In terms of making starch into thermoplastic starch for the production of biodegradable plastics, research institutions such as the German Batekke Institute, the American Warner-Lambert Company and Swiss universities have made great progress. The Australian National Center for Food Processing and Packaging Science has launched a full-starch thermoplastic plastic with good fluidity, ductility and demoulding properties. The product is soft, transparent, high-strength, and has a controllable degradation rate. It can be used to make agricultural films, food packaging films and other products.
China's starch plastics were first successfully developed by the Institute of Applied Chemistry of Jiangxi Academy of Sciences in the late 1980s. According to incomplete statistics, there are more than 60 colleges and universities, research institutes and enterprises participating in the research. China is gradually narrowing the gap with developed countries in the research and development of starch-based plastics. At present, the main manufacturers and current status of starch-based materials and products in China are as follows: Wuhan Huali 40,000 tons/year, and is planning to build a production line with an annual output of 60,000 tons; Shenzhen Hongcai 15,000 tons/year; Suzhou Hanfeng 10,000 tons/year; Zhejiang Tianhe 10,000 tons/year; Zhejiang Huafa 10,000 tons/year; Shandong Bikecheng 10,000 tons/year; other manufacturers include Nanjing Bioge, Changzhou Longjun, etc.
The starch is modified and plasticized by chemical methods, and the modified starch has three characteristics: 1. Hydrophobicity. After chemical modification, the starch is completely hydrophobic, and the moisture content is less than 1%, which has good compatibility with other synthetic polymer materials. 2. Temperature resistance. The modified starch can withstand a high temperature of 230буC during the thermoplastic processing without yellowing or decomposition. 3. Thermoplasticity. Modified starch can be thermoplastically processed on plastic processing equipment. The starch-based plastics produced by the company are divided into two major series: bio-based and biodegradable. According to different processing techniques, they are divided into blown film materials, injection molding materials, sheet materials and foaming materials. They can replace ordinary petrochemical plastics and are widely used in the packaging of industrial, pharmaceutical, food, electrical products and other products, as well as tableware, kitchenware, toys and flower planting. This will save a lot of petroleum resources, reduce carbon dioxide emissions, achieve harmless treatment of garbage, and promote agricultural development and farmers' income, and promote the vigorous development of the circular economy.
It was reported on July 12, 2018 that Yu Long successfully developed and industrialized all-starch biodegradable materials for the first time in the world.
Compared with traditional plastic products, the advantages of starch-based materials and products are as follows:
в┼ Similar performance: It has the same and similar performance as similar traditional plastic products;
в╞ Environmental protection: Starch-based bio-based plastics and products have the advantages of saving petroleum resources and reducing carbon dioxide emissions; Starch-based biodegradable plastics and products have the advantages of being completely biodegradable and compostable, and achieving harmless treatment of garbage;
в╟ Safety: Starch-based materials and products do not contain plasticizers, bisphenol A, heavy metals and other toxic and harmful substances. Food-grade materials meet the relevant standards for food-grade plastics outside China;
в╚ Production process: There is no discharge of three wastes during the production process, and no new pollution will be caused to the environment;
в╔ Cost: Starch-based bio-based plastics and products are on par with ordinary petroleum plastics, and the cost of starch-based fully biodegradable materials and products is about twice that of ordinary petroleum plastics.
In recent years, China and other countries have gradually recognized the environmental performance of bio-based products, which has greatly expanded the application field of bio-based materials. The biocarbon content of bio-based materials is an important feature that distinguishes them from ordinary plastics. The definition of biocarbon content is the percentage of biocarbon in the product to organic carbon (including biocarbon and fossil carbon). Since biocarbon is new carbon, it does not pollute the environment, so it has a good environmental protection effect. The biocarbon content detection standards include the United States ASTM D6866-08: Test method for determining the biocontent of solid, liquid and gas samples by radiocarbon analysis and China GB/T29649-2013 Liquid scintillation counter method for determining the biobased content in bio-based materials. Since contemporary organisms contain the same amount of radiocarbon elements, the principle of ASTM D6866 is to use this characteristic of organisms to measure the biobased content of samples in any state; this determination method can determine the exact percentage of biobased or renewable substances contained in any bio-based product and bio-based mixed products.
In 2009, the Belgian certification authority Vincotte issued the world's first batch of OK Biobased star-rated certification product certifications, authoritatively certifying the biocarbon content of bio-based materials, and providing a reliable third-party evaluation of product quality in the bio-based materials market. OK-Biobased is Belgium's environmental protection label for bio-based low-carbon products. After obtaining certification, bio-based plastic manufacturers can put its label on the outer packaging of products or on products to distinguish them from ordinary petrochemical products. It defines bio-based materials based on the content of biocarbon, and evaluates them by the percentage of biocarbon content and total carbon content. Its standard is ASTM D6866, which implements star-level distinction for materials. It is the authoritative bio-based material certification mark in the European Union. The OK Biobased mark uses asterisks to distinguish the environmental protection level of products. A certified product with a 1-star mark proves that its product contains 20%~40% biocarbon, 2 stars for 40%~60%, 3 stars for 60%~80%, and 4 stars for products with more than 80% biocarbon content. Vincotte's OK Biobased certification aims to help companies or distributors improve the market competitiveness of renewable products and guide consumers to better choose environmentally friendly products.
In order to encourage the development of bio-based materials and products, the U.S. Department of Agriculture has implemented the Bio-Preferred Program. The program has two programs, a government procurement priority program and a voluntary labeling program for consumers. The former was established in 2002 to encourage the development of bio-based products, and the latter was released in 2008. The purpose of the Bio-Preferred Program is to stimulate the consumption of biomass products in the United States. Federal government agencies and their contractors give priority to purchasing products with the highest biomass content. If the product meets the minimum bio-based content standard of the USDA Bio-Based Product List, any factory and distributor can participate in this program and can affix the certification logo issued by the agency on the product packaging.
International certifications for biodegradable plastics include the Belgian OK Compost certification, the German Compostable certification, and the American BPI certification.
OK Compost is a compostable certification named "OK Compost" issued by the Belgian certification body AIB-Vincotte Group after testing according to the testing standards for biodegradable materials EN13432 or ASTM D6400. The purpose of OK Compost certification is to help companies or dealers improve the market competitiveness of fully degradable products and guide consumers to better choose environmentally friendly products.
Compostable certification is a certification for biodegradable products launched by DIN CERTCO, a joint certification body of the German Rhine TUV Group and the German Standards Association (Deutsches Institut fr Normun, referred to as DIN). The certification mark is the "seeding" mark. Compostable certification can help buyers select products with strict quality, safety and environmental protection from many suppliers and manufacturers. At the same time, products with the Compostable mark indicate that they have successfully passed the testing and evaluation of authoritative third-party organizations, which helps to enhance customers' purchasing confidence and effectively promote product sales. In addition, the relevant information of the certificate holder can be queried on the official website of DIN CERTCO to prevent abuse or counterfeiting of the mark.
BPI is the abbreviation of Biodegradable Products Insitute. BPI educates manufacturers, legislators and consumers about the scientific standards of degradable materials through innovative compostable labeling programs. At the same time, a series of procedures are used to ensure that relevant products meet the requirements of degradable material standards.
China Wuhan Huali Environmental Protection is the first Chinese company to obtain OK Biobased certification, and has obtained four-star bio-based product certification. At the same time, the company's biodegradable materials have obtained OK Compost certification and Compostable certification.
As consumers gradually shift their preferences for plastic products, renewable and environmentally friendly materials are increasingly sought after by the market. Affected by this, the demand for bio-based plastics has increased. As governments around the world pay more attention to bioplastics, the total value of global demand for bioplastics is expected to increase to US$5.9 billion in 2020, equivalent to an average annual growth rate of 20%.
Recently, the French Parliament passed a law on energy transition and green growth. In addition to reducing the share of nuclear energy in France's energy mix, the new law also includes legislative proposals related to renewable energy and plastic packaging. For example, renewable energy will grow by 40% by 2030 and carbon dioxide emissions will be reduced by 40% by 2030; lightweight packaging bags used to package fruits and vegetables will have to be made of bio-based materials starting January 1, 2017; in addition, plastic packaging used for commercial mail will also be implemented at the same time and with the same standards. The latest legislation of the French government requires that disposable tableware such as bowls, plates, cups and forks must be made of bio-based raw materials instead of petroleum-based raw materials.
Market analysts at RnR Market Research recently predicted that the global demand for bio-based plastics will increase at an annual rate of 19% in the next four years, and its market demand will reach 950,000 tons in 2017. Europe is the world's largest consumer market for bio-based plastics. In 2012, the region's use of bio-based plastics accounted for more than half of the global total. Survey reports show that European consumers prefer new bio-based plastic products over traditional plastics. Therefore, the region is expected to continue to lead the list of bio-based plastics consumption. In terms of types, starch-based plastics and polylactic acid will still be the most in-demand bio-based plastics in the next few years, and their market consumption will account for more than 60% of the total. RnR Market Research said that in recent years, countries have successively issued plastic bans and continuously increased supervision on the use of traditional plastics, which is conducive to further boosting the demand trend of bio-based, especially starch-based plastics.
In 2013, the State Council of China issued the "Biological Industry Development Plan" (hereinafter referred to as the "Plan"), which pointed out that it will accelerate the industrialization and promotion of bio-based materials, bio-based chemicals, and new fermentation products. The certification mechanism for bio-based products will also be established, and market incentive policies for the consumption of bio-based products and the allocation system of agricultural raw materials to the industrial field will be studied and formulated.
In February 2014, Jilin Province issued the Provincial Government Order No. 244---"Regulations on the Prohibition of the Sale and Provision of Disposable Non-degradable Plastic Bags and Plastic Lunch Boxes in Jilin Province", namely the "Plastic Ban Order". The regulations will be officially implemented from January 1, 2015, and violations of the regulations may be fined up to 30,000 yuan. At the same time, this also marks that Jilin Province has become the first province in the country to fully implement the "plastic ban".
In December 2014, the National Development and Reform Commission and the Ministry of Finance issued the "Reply on the 2014 Bio-based Materials Special Implementation Plan", which approved the implementation plan for the development of the bio-based materials industry in Tianjin, Shenzhen, Wuhan and Changchun. In the next three years, the central government will adopt a rolling approach to support pilot construction. The "Demonstration Implementation Plan for the Application of Bio-based Materials Products" takes regional cluster construction and product application as development carriers, combines demand-side pull with supply-side promotion, promotes the industrial chain development of non-grain bio-based materials, builds high-density, high-level, organically combined production, education, research and application, and has a significant leading demonstration role. The demonstration of the application of renewable and degradable bio-based materials products.
In addition, local governments such as Guangzhou, Hangzhou, and Nanjing have promoted garbage classification and tendered for the use of degradable garbage bags to collect kitchen waste.
In order to build a resource-saving and environmentally friendly society, the country will introduce more favorable policies to support the bioplastics industry in the future, such as the plastic ban, to promote the healthy development of bio-based and biodegradable plastics. Starch-based bioplastics, as a bio-based material with the most price advantage, will surely develop rapidly.
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