Biodegradable Plastics from Renewable Sources可再生生物降解塑料能源ABSTRACT. Plastic waste disposal is a huge ecotechnological problem and one of the approaches to solving this problem is the development of biodegradable plastics. This review summarizes data on their use,biodegradability, commercial reliability and production from renewable resources. 塑料廢物處理是一個(gè)巨大的經(jīng)濟(jì)技術(shù)問題，一個(gè)解決問題的方法是發(fā)展可降解生物塑料。本文綜述的數(shù)據(jù)是從它們的使用，生物可降解性，商業(yè)的可靠性和從可再生資源中生產(chǎn)得來的。Some commercially successful biodegradable plastics are based on chemical synthesis (i.e. polyglycolic acid, polylactic acid,polycaprolactone, and polyvinyl alcohol). Others are products of microbial fermentations (i.e. polyesters and neutral polysaccharides) or are prepared from chemically modified natural products (e.g., starch, cellulose,chitin or soy protein).一些商業(yè)上的可降解生物塑料是在化學(xué)合成法的基礎(chǔ)上取得成功的（如聚乙醇酸，聚乳酸，聚己內(nèi)酯，和聚乙烯醇）。其他的，是通過微生物發(fā)酵產(chǎn)生（如聚酯和中性多糖）或通過化學(xué)改性天然產(chǎn)品所產(chǎn)生（例如，淀粉，纖維素，甲殼素或大豆蛋白）。1 INTRODUCTIONBiopolymers are polymers that are generated from renewable natural sources, are often biodegradable and nontoxic. They can be produced by biological systems (i.e. microorganisms, plants and animals),or chemically synthesized from biological materials (e.g., sugars, starch, natural fats or oils, etc.). 生物大分子是從可再生的天然資源中產(chǎn)生的聚合物，往往是可生物降解、無毒的。它們可以通過生物系統(tǒng)（例如，微生物，植物和動(dòng)物），或化學(xué)合成的生物材料（例如，糖，淀粉，天然脂肪或油，等）中生產(chǎn)出來。Two strategies are applied in converting these raw materials into biodegradable polymers: extraction of the native polymer from a plant or animal tissue, and a chemical or biotechnological route of monomer polymerization.Biodegradable biopolymers (BDP) are an alternative to petroleum-based polymers (traditional plastics).Some BDP degrade in only a few weeks, while the degradation of others takes several months. In principle the properties relevant for application as well as biodegradability are determined by the molecular structure. 兩種策略都適用于這些原料轉(zhuǎn)化成可生物降解的聚合物：從植物或動(dòng)物組織和化學(xué)或生物技術(shù)路線的單體聚合的聚合物中提取出來的高分子?？缮锝到獾纳锞酆衔铮˙DP）是可替代以石油為基礎(chǔ)的聚合物（傳統(tǒng)塑料）的一種聚合物。一些BDP降解僅需幾個(gè)星期，而別的降解需要幾個(gè)月的時(shí)間。原則上性能相關(guān)的應(yīng)用，以及生物可降解性是由分子結(jié)構(gòu)所決定。According to the American Society for Testing and Materials, biopolymers are degradable polymers in which degradation results from the action of naturally occurring microorganisms such as bacteria,fungi and algae (Shimao 2001). This means that BDP can be produced from natural raw materials such as starch, sugar and cellulose as well as fossil oils. In Europe, EC and DIN (e.g., 54 900) are proposing standards for the evaluation of biodegradability based on the composting technique. 根據(jù)美國測試和材料協(xié)會，生物聚合物是可降解聚合物是從天然存在的微生物中得到的，如細(xì)菌、真菌和藻類（世茂，2001年）。這意味著，可以從天然原料如淀粉，糖，纖維素和礦物油中生產(chǎn)BDP。在歐洲，歐盟和DIN（例如，54 900）所建議的標(biāo)準(zhǔn)是在堆肥技術(shù)生物降解性的評價(jià)基礎(chǔ)上的。In this issue the wide use of BDP plays an important role.First,BDP can prevent or reduce any impact of industrial waste on the environment, thus providing a high level of environmental protection. Second, the use of BDP protects the soil and ensures that the application of biologically treated biowaste enhances soil carbon level. Third, the use of BDP ensures the functioning of the internal market and helps in avoiding obstacles to trade and distortion and restriction of competition within and outside the EU (Anonymous 2000b).BDP在這個(gè)問題上的廣泛使用起著重要的作用。首先，BDP可以防止或減少工業(yè)廢水對環(huán)境造成任何影響，從而提供了一個(gè)高層次的環(huán)保。第二，使用的BDP保護(hù)土壤，并確保該應(yīng)用程序的生物處理生物垃圾提高了土壤有機(jī)碳水平。第三，使用的BDP確保了內(nèi)部市場的運(yùn)作的，并有助于避免對歐盟以外的內(nèi)貿(mào)易的扭曲和限制競爭的障礙（匿名2000B）。3 BIODEGRADABLE POLYMERS PRODUCED THROUGH FERMENTATIONBY MICROORGANISMSMany microorganisms overproduce polyesters and neutral polysaccharides if they have access to a carbon source. Both groups of compounds are easy biodegradable and they can be produced from renewable resources. Polyesters, which are more important for the production of BDP, consist of simple carbon chain monomers. About 90 polyesters are identified as intracellular storage compounds performing different properties (Jendrossek et al. 1996).3由微生物通過發(fā)酵生產(chǎn)的生物可降解聚合物許多微生物如果它們有機(jī)會獲得碳源，它們就會過量生產(chǎn)聚酯和中性多糖。這兩種基團(tuán)的化合物是容易生物降解的，并且它們可以從可再生產(chǎn)資源中生產(chǎn)出來。聚酯對于生產(chǎn)BDP是很重要的，包括簡單的碳鏈單體。大約90種聚酯被確定作為細(xì)胞內(nèi)儲存化合物形成不同的性質(zhì)（Jendrossek等人，1996）。4 BIODEGRADABLE POLYMERS FROM CHEMICALLY MODIFIED NATURAL PRODUCTSFinding new uses for agricultural commodities is an important area of research. New uses and marketsfor agricultural materials are needed to address the current slump in commodity prices. One applicationarea being investigated is the replacement of petroleum-based materials with natural materials such ascellulose, chitin, agricultural products such as starch, proteins from wheat and soybeans, milk, etc. Thesuccessful replacement of petroleum-based materials will open new value-added markets for agricultural commodities and lessen the dependence of national economy on foreign crude oil and gas. As shown above, many agricultural products can be used as blends with one or more additional materials. The main components of this material are storage and structural polysaccharides. 4從化學(xué)修飾的天然產(chǎn)物中得到的生物可降解聚合物為農(nóng)產(chǎn)品尋找新的用途，是一個(gè)重要的研究領(lǐng)域。對于農(nóng)產(chǎn)品，新的用途和市場是對于解決目前大宗商品價(jià)格暴跌的情況所必要的。一個(gè)應(yīng)用區(qū)域被調(diào)查，此區(qū)域是把石油為基礎(chǔ)的材料用如纖維素，甲殼素，農(nóng)業(yè)產(chǎn)品如淀粉，小麥和大豆蛋白質(zhì)，牛奶等的天然材料進(jìn)行替代。成功替代石油為基礎(chǔ)的材料將為農(nóng)業(yè)商品打開新的增值市場，并且減少國民經(jīng)濟(jì)對外國原油和天然氣的依賴。如上圖所示，許多農(nóng)業(yè)產(chǎn)品可以與一個(gè)或多個(gè)額外材料形成共混物。這種材料的主要組成部分是儲存性和結(jié)構(gòu)性多糖。5 PERSPECTIVES AND CONCLUSIONSThe development of biodegradable plastics is best viewed in the context of diminishing of crude oilreserves. In future years, it will be largely driven to derive more carbon for chemical processes from renewable resources and to preserve the ecosystem. As shown above there are three technological approaches to the production of BDP. Industrial chemistry can use the know-how of petrochemistry to produce suitable replacement of conventional plastics. Fermentation industry supported by developments of genetic engineering can yield microbes that more efficiently convert inexpensive raw materials to polyesters and neutral polysaccharides. The construction of new overproducing microbial strains will be facilitated by using genetic methods. These powerful technologies will allow designing industrially feasible cost-effective biological routes to a wide range of chemicals, including monomers and polymers. Now the technical background of food industry permits to develop an environmentally friendly products based on starch and composite materials.On the basis of economic and environmental considerations, the commercialization of BDP continues and shows increasing markets of products that have a relatively short-use lifetime. The number of research papers concerning BDP is an endless belt of knowledge, implicating new projects that end in building up of new manufacturing capacities.5觀點(diǎn)和結(jié)論可生物降解塑料的發(fā)展是在原油儲量遞減的背景下最好的前景。在未來幾年，將在很大程度上帶動(dòng)發(fā)展，以獲得更多的碳化學(xué)過程的可再生資源和保護(hù)生態(tài)系統(tǒng)。如上圖所示，有三種技術(shù)方法生產(chǎn)的BDP?？梢允褂檬瘜Ｓ屑夹g(shù)生產(chǎn)出適合工業(yè)化學(xué)的產(chǎn)品來替代傳統(tǒng)的塑料。發(fā)酵工業(yè)是通過基因工程的發(fā)展所支持。發(fā)酵可以產(chǎn)生微生物，可以更有效地轉(zhuǎn)換成廉價(jià)原料成聚酯和中性多糖。采用遺傳方法將促進(jìn)建設(shè)新的高產(chǎn)微生物菌種。這些強(qiáng)大的技術(shù)將讓設(shè)計(jì)工業(yè)上可行的符合成本效益的生物拓寬到化學(xué)品，包括單體和聚合物。現(xiàn)在食品行業(yè)的技術(shù)背景是在許可淀粉和復(fù)合材料的基礎(chǔ)上，發(fā)展環(huán)境友好型的產(chǎn)品。在此基礎(chǔ)上的經(jīng)濟(jì)和環(huán)境因素，商業(yè)化的BDP繼續(xù)并顯示，一個(gè)相對短的使用壽命的產(chǎn)品的日益增加的市場。大量有關(guān)的研究論文顯示BDP是一個(gè)無窮無盡的知識帶，暗示有新的項(xiàng)目，建立新的制造能力。Research on Butyl MethacrylateLauryl Methacrylate Copolymeric Fibers for Oil Absorbency甲基丙烯酸丁酯-甲基丙烯酸十二酯共聚纖維吸油的研究ABSTRACT: By adding hydroethyl methacrylate as potential crosslinker, the butyl methacrylate-lauryl methacrylate copolymeric (CPMA) fibers with oil-absorptive functionwere prepared using heat crosslinking technology after spinning. The effect of monomer feed ratio showed that by controlling the monomer ratio, crosslinker concentration,and crosslinking conditions, the maximum absorbencies of prepared fibers to different oil were 8 g (kerosene)/g (fiber),15 g (toluene)/g (fiber), and 34.75 g (chloroform)/g (fiber).The structures of fibers were characterized by FTIR, DSC,and SEM.摘要：通過增加潛在交聯(lián)劑羥乙基甲基丙烯酸甲酯，讓甲基丙烯酸丁酯十二烷基甲基丙烯酸甲酯共聚物（CPMA）纖維具有吸油功能，準(zhǔn)備在紡絲后使用熱交聯(lián)技術(shù)。單體進(jìn)料比的效果表明，通過控制單體比，交聯(lián)劑濃度，和交聯(lián)條件下制備的纖維，不同油的最大吸光度分別為8克（煤油）/克（纖維），15克（甲苯）/克（纖維），34.75克（氯仿）/ G（光纖）。通過FTIR，DSC和SEM對纖維的結(jié)構(gòu)進(jìn)行了表征。INTRODUCTIONOil-absorptive particles were widely used in the fields of waste oil recovery and wastewater purification.Compared with traditional oil-absorptive materials, ithas a three-dimensional network structure like water superabsorbent polymers. It gained excellent development prospect with the characteristics of good heat and cold resistance, large oil absorption capacity and convenient reclamation technology.14 However, becauseof its shape limit, oil-absorptive particles have many disadvantages, such as smaller specific-areas,lower absorptive rate, and absorptive abilities, compared with fibrous material and this restricted its applications.Fiber has desirable properties, such as large absorptive area, outstanding mechanical anisotropies,etc. And it could be manufactured into various forms of products, such as nonwoven fabrics, so its usingfield was effectively widened. Then, it was important to research and develop oil-absorptive functional fibers no matter in learning or application field. Buthighly oil-absorptive resin now was synthesized with single chemical crosslinking agent such as divinylbenzene,and oil-absorptive resin prepared in this way had perfect crosslinked structure, which made it insoluble in proper organic solvent. So the resin was difficult to be span into fiber.5,6 Although there were a lot of reports about oil-absorptive materials, the oilabsorptive fibers were still not successfully prepared and reported. The purpose of this research was to prepare fibers with oil-absorptive function. Methacrylate was used as monomer and hydroethyl methacrylate as potential crosslinker was put in polymerization system in this study. Resin synthesized by this method still kept a linear structure, which made it soluble in a solvent to prepare solution. After spinning, the fiber was heat-treated at certain conditions to formcrosslinked structure in fiber molecule, which made the fiber have the properties of oil-absorption. And the effect of monomer ratio, concentration of potential crosslinking agent on properties, and structures of CPMA fibers was analyzed. A detailed study of the swelling properties of CPMA fibers was conducted and the structures were characterized through FTIR,DSC, and SEM.簡介油吸收顆粒被廣泛使用，在廢油回收和廢水凈化。與傳統(tǒng)的油吸收材料相比較，它具有類似水的超吸收性聚合物的三維網(wǎng)絡(luò)結(jié)構(gòu)。因?yàn)樗哂辛己玫哪蜔岷湍屠湫裕蟮奈湍芰头奖愕奶詈＜夹g(shù)的特點(diǎn)，使得它具有良好的發(fā)展前景。但是，由于它的形狀限制，油吸收顆粒有許多缺點(diǎn)，如更小的特定區(qū)域，較低的吸收速率，和吸收能力，與纖維材料相比，這種限制其應(yīng)用。纖維具有理想的性能，如大的吸收面積，優(yōu)秀機(jī)械各向異性等。并且它可以被制造成各種形式的產(chǎn)品，如非織造織物，所以它有效地?cái)U(kuò)大了使用領(lǐng)域。然后，吸油功能性纖維的研究和開發(fā)無論是在學(xué)習(xí)或應(yīng)用領(lǐng)域都很重要。但現(xiàn)在高吸油性樹脂的合成具有單一的化學(xué)交聯(lián)劑如二乙烯基苯，和吸油樹脂相結(jié)合，以這種方式制備的樹脂有完美的交聯(lián)結(jié)構(gòu)，這使得它在適當(dāng)?shù)挠袡C(jī)溶劑中的不溶性。樹脂是難以跨越到纖維上的，雖然有很多的報(bào)告關(guān)于吸油材料，吸油纖維仍然沒有成功地制備和報(bào)告。本研究的目的是，制備具有吸油功能的纖維。本研究中，在聚合物體系中，甲基丙烯酸作為單體、羥乙基甲基丙烯酸酯作為潛在交聯(lián)劑。通過該方法合成的樹脂仍保持線性的結(jié)構(gòu)，這使得它可溶于溶劑中以制備溶液。纖維紡絲后，進(jìn)行熱處理，在一定條件下形成在纖維分子中的交聯(lián)結(jié)構(gòu)，這使纖維具有吸油的屬性。對單體比率、潛在交聯(lián)劑的性質(zhì)和濃度，和CPMA纖維結(jié)構(gòu)的影響進(jìn)行了分析。對CPMA纖維的溶脹性能進(jìn)行了詳細(xì)研究，并通過FTIR，DSC和SEM的結(jié)構(gòu)進(jìn)行了表征。CONCLUSIONSThe following conclusions could be drawn from this study:1. The butyl methacrylate-lauryl methacrylate copolymeric(CPMA)fibers with oil-absorptive function were prepared using heat crosslinking technology,after spinning by adding hydroethyl methacrylate as potential crosslinker.2. Monomer ratio directly affected the absorbencies of fibers, especially the absorbencies to aliphatic oil. When LMA content was 25%, the kerosene absorbency could get 8.00 g/g.3. HEMA content was a main factor affecting absorptive properties of CPMA fibers, and the HEMA content was not less than 25% in this study;4. The highest absorbency of CPMA fiber to various oil was 15 g (toluene)/g (fiber), 34.75 g (chloroform)/g (fiber), and 8 g (kerosene)/g (fiber), respectively.結(jié)論從這項(xiàng)研究可以得出以下結(jié)論：1。甲基丙烯酸丁酯-甲基丙烯酸十二酯具有吸油性功能的共聚（CPMA）纖維是使用熱交聯(lián)技術(shù)制備的，紡絲后通過添加作為潛在交聯(lián)劑的羥乙基甲基丙烯酸酯。2。單體比直接影響的纖維的吸收能力，特別是脂肪族油的吸收能力。當(dāng)LMA含量為25，煤油吸收能力可以得到8.00克/克。3。 HEMA含量影響CPMA纖維的吸收性質(zhì)是一個(gè)主要因素，在本研究中，HEMA含量為不小于25;4。 CPMA纖維的各種油的最高吸光度分別為15克（甲苯）/克（纖維），34.75克（氯仿）/克（纖維），和8克（煤油）/克（纖維）。Surface characteristics and antistatic mechanism of plasma-treated acrylic fibers表面特性和抗靜電機(jī)制等離子體處理的丙烯酸類纖維AbstractAcrylic fibers are treated by nitrogen glow-discharge plasma to promote surface antistatic properties. The treated surfaces are characterized by scanning electron microscopy (SEM), specific surface area analysis (BET) and X-ray photoelectron spectroscopy (XPS). Plasma treatment is found to increase the surface roughness, to modify the nature and density of surface functionalities, and to drastically improve the wettability and antistatic ability of acrylic fibers.摘要腈綸纖維是通過氮輝光放電等離子體處理，來促進(jìn)表面的抗靜電性能。處理過的表面，其特征是通過掃描電子顯微鏡（SEM），比表面積分析（BET）和X-射線光電子能譜（XPS）來表征的。發(fā)現(xiàn)等離子體處理可增加表面粗糙度，修改表面功能的性質(zhì)和密度，并大幅度提高丙烯酸纖維的潤濕性和抗靜電能力。1. IntroductionAcrylic fiber is one of leading synthetic fibers due to its high strength, good elasticity and excellentdyeability. However, the inherent poor absorbency,accompanied by the high build-up of static chargeslimits its further development. These shortcomings might be alleviated by chemical and physical modification of the fibers14. Although chemical modification of the fibers has been somewhat successful in improving hydrophilic and antistatic properties, there are environmental concerns related to the disposal of chemicals after treatment 5. Plasma treatment, as a clean, dry and environmental friendly physical technique, opens up a new possibility in this field. Plasma treatment can usually induce the following processes: dehydrogenation and consequent unsaturated bond formation, trapped stable free radicals formation, generation of polar groups through post-plasma reaction, and generation of increased surface roughness through preferential amorphous structure ablation processes. The generation of increased surface roughness and polar groups resulting from plasma treatment has asignificant influence on the overall surface charges and water absorption. Therefore, it is expected that plasma treatment can be applied to improve the wettability and antistatic ability of acrylic fibers. Although there is an abundant of literature on the surface modification of materials by plasma action612, very little work has dealt with the modification of acrylic fibers by plasma treatment 1315. In this paper, we use nitrogen glow-discharge plasma technique to improve the wettability and antistatic ability of acrylic fibers. We investigate antistatic mechanism of the plasma-treated fibers.1。介紹由于高強(qiáng)度，良好的彈性和優(yōu)良的可染性，腈綸纖維成為一種領(lǐng)先的合成纖維。但其固有的吸收能力差，伴隨著高積聚的靜電荷限制了其進(jìn)一步的發(fā)展。這些缺點(diǎn)，可以由化學(xué)或物理改性的纖維改善。雖然改性過的纖維已經(jīng)有些成功改善親水性和抗靜電性能，但有些化學(xué)品處理后仍有相關(guān)的環(huán)境問題。作為一種清潔，干燥，環(huán)境友好型物理技術(shù)，等離子體處理，在這一領(lǐng)域開辟了新的可能性。等離子處理通?？梢砸鹨韵逻^程：脫氫和由此產(chǎn)生的不飽和鍵的形成，被困穩(wěn)定的自由基形成，通過后等離子反應(yīng)生成極性基團(tuán)，通過優(yōu)先的無定形結(jié)構(gòu)的燒蝕過程，生成的表面粗糙度增加。增加表面粗糙度和極性基團(tuán)的等離子體處理產(chǎn)生的產(chǎn)品具有整體的表面電荷和水的吸收顯著的影響。因此，可以預(yù)期，等離子處理可以應(yīng)用于改善丙烯酸纖維的潤濕性和抗靜電能力。雖然有豐富的文獻(xiàn)材料用等離子處理的表面改性，但很少的工作對于用等離子處理來改性腈綸纖維。在本文中，我們使用氮?dú)廨x光放電等離子體技術(shù)，以改善腈綸纖維的潤濕性和抗靜電能力。我們研究的是等離子體處理過的纖維的抗靜電機(jī)制。4. DiscussionSurface wettability is directly related to surface energy, more energetically stable surface results inless wettable surface. It is now established that plasma modification of the fibers results in oxidation and degradation of the fiber surfaces. 表面的潤濕性直接關(guān)系到表面能，在很少的潤濕表面具有更大的穩(wěn)定性。它現(xiàn)在確立等離子體改性的纖維，使得纖維表面氧化和降解。 The oxidation creates oxidized functionalities, which lead to an increase in surface energy, while the degradation mainly changes surface morphology of the fibers. SEM photographs have shown that plasma treatment causes the increase of surface roughness. 氧化產(chǎn)生氧化的功能，從而導(dǎo)致表面能的增加，而降解主要是改變纖維的表面形態(tài)。SEM照片所示，等離子體處理導(dǎo)致表面粗糙度的增加。Eq. (1) indicates that for the surface having lower contact angle than 908, increasing surface roughness probably decrease the contact angle, which will contribute to the improved surface wettability. 方程（1）表明，對于具有較低的接觸角大于908的表面，表面粗糙度增加，可能減小接觸角，這將有助于改進(jìn)的表面的潤濕性。 Water is a conductor of electricity. Therefore, the improved surface wettability will decrease the accumulation of electrostatic charges. The increase of surface roughness also induces the increase in the specific surface area. The increased specific surface area will lead to a more moisturerich surface, which enhances the conductivity of the fibers. 水是導(dǎo)電體。因此，改進(jìn)的表面潤濕性會降低靜電荷的積累。 表面粗糙度的增加，還引起比表面積的增加。比表面積的增加，將導(dǎo)致更 親水“的表面，這提高了纖維的導(dǎo)電性。Plasma treatment not only causes the increase in surface roughness but also introduces the hydrophilic groups onto the fiber surface. XPS analyses have shown that amide and carboxyl groups have been created on the fiber surface after plasma treatment. 等離子體處理不僅使表面粗糙度增加，也把親水性基團(tuán)引入到纖維表面。XPS分析顯示，在等離子處理后，纖維表面附著上了酰胺基和羧基基團(tuán)。 There are two possibilities of generating the polar groups. The first one is that they are generated by reacting with the ambient gas during the processing. The second is that they are generated when the samples are exposed to air after plasma processing, that is, plasma treatment p