Evaluation of biodegradability of poly(ε-caprolactone)/poly(ethylene terephthalate) blends

The results of an investigation aimed at evaluation of the biodegradability of blends of poly(-caprolactone) (PCL) with poly(ethylene terephthalate) (PET) as the major component are reported. Specimens of the blends, as melt extruded films and/or powders, were submitted to degradation tests under different environmental conditions including full-scale composting, soil burial, bench-scale accelerated aerobic degradation, and exposure to axenic cultures and esterolytic enzymes. Indications have been gained that blending in the melt gives rise to insertion of PCL segments in the PET chain. Copolymers thus attained acted as macromolecular compatibilizers, allowing for a complete miscibility of PCL and PET. The biodegradation detected on the blend samples was, however, well below the values expected from chemical composition and behavior of individual homopolymers under the same environmental conditions. The presence of PET as the major component in PET/PCL blends apparently reduces the propensity of PCL to be degraded, at least in the investigated composition range. The degradation data collected under different environmental conditions indicate that the full-scale composting system is the most efficient among the tested degradation procedures.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Synthesis of copolyesters containing poly(ethylene terephthalate) and poly(ε-caprolactone) units and their susceptibility toPseudomonas sp. lipase

Copolyesters containing poly(ethylene terephthalate) (PET) and poly(-caprolactone) (PCL) were synthesized from PET and PCL homopolymers by transesterification reaction at 270°C in the presence of catalyst. The copolyesters were characterized by¹³C-NMR and differential scanning calorimetry (DSC). The degradation behavior of PCL byPseudomonas sp. lipase in buffer solution (pH 7) and tetrahydrofuran (THF) was investigated by gel permeation chromatography (GPC) and¹H-NMR. From these experiments, it was found thatPseudomonas sp. lipase acted endoenzymatically on PCL. Using this lipase, degradation tests for PET/PCL copolyesters whose PCL content was below 50% by weight were also performed in buffer solution (pH 7). However, evenPseudomonas sp. lipase with high degradation activity on PCL did not easily degrade the PCL unit in PET/PCL copolyesters.     

Preparation conditions and swelling equilibria of biodegradable hydrogels prepared from microbial poly(γ-glutamic acid) and poly(ε-lysine)

Biodegradable hydrogels prepared by -irradiation from microbial poly(amino acid)s are reviewed. pH-sensitive hydrogels were prepared by means of -irradiation of poly(-glutamic acid) (PGA) produced byBacillus subtilis IFO3335 and poly(-lysine) (PL) produced byStreptomyces albulus in aqueous solutions. The preparation conditions, swelling equilibria, hydrolytic degradation, and enzymatic degradation of these hydrogels were studied. A hydrogel with a wide variety of swelling behaviors has been produced by -irradiation from a mixture solution of PGA and PL.Paper presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995, Durham, New Hampshire, USA.     

The degradation of gel-spun poly(β-hydroxybutyrate) “wool”

The apparent biodegradability and biocompatibility of the microbially produced polyester, poly(-hydroxybutyrate) (PHB), has been the focus of much research by a number of authors with regard to its potential for use in packaging and medical implantation devices. PHB has recently been produced by gel-spinning into a novel form, with one possible application being as a wound scaffolding device, designed to support and protect a wound against further damage while promoting healing by encouraging cellular growth on and within the device from the wound surface. This new nonwoven form combines a large volume with a low mass, has an appearance similar to that of cotton wool, and has been called wool because of this similarity. The hydrolytic degradation of this wool was investigated in an accelerated model of pH 10.6 and temperature 70°C. It was determined that the PHB wool gradually collapsed during degradation. The surface area-to-volume ratio was concluded to be a primary influencing factor. Degradation was characterized by a reduction in the glass transition temperatures and melting points and a fusion enthalpy peak of maximum crystallinity, (88%), which coincided with the point of matrix collapse.     

Synthesis and environmental degradation of polyesters based on poly (ε-caprolactone)

Poly (-caprolactone) (PCL), poly (-valerolactone) (PVL), poly (-caprolactone-co--valerolactone) [P(CL-co-VL)], and poly (-caprolactone-co-ethylene oxide-co--caprolactone) (PCL-PEO-PCL) were synthesized by ring-opening and diol-initiated polymerization of -caprolactone and -valerolactone. The degradation of the samples by chemical hydrolysis and in a soil burial test was evaluated. It was found that PCL, PVL, and P(CL-co-VL) degrade mainly enzymatically. The rate of degradation depends on their molecular weight, chemical structure, composition, and morphology. PCL-PEO-PCL block copolymers exhibit a repelling effect to the microorganisms in the soil, which depends on the molecular weight and relative amount of PEO block in the copolymer.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

Degradation of poly(β-hydroxyalkanoates) and polyolefin blends in a municipal wastewater treatment facility

Six types of plastics and plastic blends, the latter composed at least partially of biodegradable material, were exposed to aerobically treated wastewater (activated sludge) to ascertain their biodegradability. In one study, duplicate samples of 6% starch in polypropylene, 12% starch in linear low-density polyethylene, 30% polycaprolactone in linear low-density polyethylene, and poly(-hydroxybutyrate-co-hydroxyvalerate) (PHB/V), a microbially produced polyester, were exposed to activated sludge for 5 months, and changes in mass, molecular weight average, and tensile properties were measured. None of the blended material showed any sign of degradation. PHB/V, however, showed a considerable loss of mass and a significant loss of tensile strength. In a second study, PHB/V degraded rapidly, but another type of microbial polymer which forms a thermoplastic elastomer, poly(-hydroxyoctanoate), did not degrade. These results illustrate the potential for disposal and degradation of PHB/V in municipal wastewater.     

A method for the isolation of microorganisms producing extracellular long-side-chain poly (β-hydroxyalkanoate) depolymerase

A simple method was developed for the preparation of an autoclavable, long-side-chain poly (-hydroxyalkanoate) (LSC-PHA) colloidal suspension, which was used as a substrate for enzymatic degradation and to prepare agar overlay plates for the isolation of microorganisms producing extracellular LSC-PHA depolymerase. Six cultures producing extracellular LSC-PHA depolymerase were isolated from a composted hydrocarbon-contaminated soil. All were pseudomonads or related bacteria. All (with the possible exception ofXanthomonas maltophilia) could produce LSC PHA. Except forX. maltophilia none could hydrolyze poly (-hydroxybutyrate). Screening of sevenPseudomonas strains known to accumulate LSC PHA showed that all were negative for extracellular LSC-PHA depolymerase production. It was concluded that extracellular LSC-PHA depolymerase producers are found mostly in the genusPseudomonas but that they are relatively uncommon.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.     

Hydrolytic and enzymatic degradation of poly(γ-glutamic acid) hydrogels and their application in slow-release systems for proteins

The hydrolytic and enzymatic degradation of newly developed hydrogels, produced by cross-linking purified poly(-glutamic acid) (PGA) with dihaloalkane compounds, was studied and is reported in this paper. Analysis of hydrolysis of the hydrogel as a function of pH indicated that the hydrolysis occurred slowly at neutral pH, but fast in both acidic and alkaline solutions, while the polymer could be hydrolyzed rapidly only in acidic solutions. The ester bonds were more sensitive to hydrolysis than peptide bonds. The biodegradability of the hydrogel and polymer was further confirmed when enzymatic degradation was studied by three enzymes (cathepsin B, pronase E, and trypsin), which were able to cleave both ester and peptide bonds gradually. A slow-release system for porcine somatotropin (pST) formed by using the hydrogel as matrix to entrap the hormone was evaluatedin vitro andin vivo. Results demonstrated that the hydrogel was able to release the hormone for a period of 20–30 days and indicated its potential application in slow-release systems for bioactive materials, especially macromolecules, such as peptides and proteins.     

增敏碘量法同时测定微量Mn(Ⅱ)、 Mn(Ⅶ)、 Cr(Ⅲ)、 Cr(Ⅵ)

介绍了用增敏碘量法同时测定微量的Ｍｎ（Ⅱ）、Ｍｎ（Ⅶ）、Ｃｒ（Ⅲ）和Ｃｒ（Ⅵ）。将样品中的Ｍｎ（Ⅶ）和Ｃｒ（Ⅵ）用Ｎａ２ＳＯ３预先还原,在ｐＨ为３．０的醋酸盐介质中对Ｍｎ（Ⅱ）和Ｃｒ（Ⅲ）用过量ＫＩＯ４氧化（当用Ｈ２Ｐ２Ｏ２－７掩蔽Ｃｒ（Ⅲ）时,只有Ｍｎ（Ⅱ）被氧化）,过剩的ＩＯ－４用钼酸盐掩蔽,加入ＫＩ后,以Ｎａ２Ｓ２Ｏ３滴定游离出的Ｉ２。此法对Ｍｎ的测定范围为２９～１４７０６μｇ／Ｌ,相对标准偏差为０．３１％～１．１８％;对Ｃｒ的测定范围为５９～１０２９４μｇ／Ｌ,相对标准偏差为０．３６％～１．１２％。此法与常规滴定法测定Ｍｎ和Ｃｒ相比,分别可增敏２０倍和１２倍     

Fe(Ⅱ)、Fe(Ⅲ)和Fe(Ⅵ)活化过硫酸盐氧化降解水中的菲

分别采用Fe(Ⅱ)、Fe(Ⅲ)和Fe(Ⅵ)活化过硫酸盐(PS)氧化降解水中的菲,考察了反应pH、药剂投加量及氧化时间等因素的影响,并对比了不同价态铁活化PS对菲的氧化降解效果.在反应pH为8、n(菲):n(Fe):n(PS)为1:2:2的优化条件下,反应60 min后Fe(Ⅱ)-PS和Fe(Ⅲ)-PS体系对菲的去除率分...     

酸性Fe(Ⅲ)溶液催化氧化S(Ⅳ)机理研究进展

烟道气SO2是大气污染的主要污染物之一.酸性Fe(Ⅲ)溶液催化氧化SO2是研究最早、最多、应用最广的一项烟气脱硫技术,但对其机理一直以来都存在争议.通过综述国内外的酸性Fe(Ⅲ)溶液催化氧化S(Ⅳ)机理研究进展,总结得出其机理为配位催化氧化;指出了机理研究中存在的问题.为我国湿法烟气脱硫技术及其机理研究的发展提供了理论依据.     

定量吸附分离Cr(Ⅲ)与Cr(Ⅵ)的研究

铬是一种多价态元素,不同价态的铬在环境中的作用机理和效果不同,因此对铬的价态分析越来越引起人们的重视,而Cr(Ⅲ)与Cr(Ⅵ)的定量分离是分析中一项很重要的基础工作。 Cr(Ⅲ)与Cr(Ⅵ)的分离通常采用离子交换和沉淀吸附分离法,但对于含有大量还原性物质,水质较复杂的水样,用离子交换法分离是困难的;沉淀吸附分离法可在碱性     

钙钛矿型La_(0.8)Ce_(0.2)Fe_(1-x)Co_xO_3催化剂的制备及其三效催化活性

采用自燃烧法制备了一组钙钛矿型复合氧化物La_(0.8)Ce_(0.2)Fe_(1-x)Co_xO_3(x=0.9,0.7,0.5,0.3,0.1),并考察了其对CO、C_3H_6和NO的三效催化活性。XRD和SEM表征结果显示,La_(0.8)Ce_(0.2)Fe_(1-x)Co_xO_3具有良好的钙钛矿型晶体结构,晶粒大小为纳米级并自组装成片状结构。催化剂的比表面积为14.73~22.43 m~2/g,含有微孔和介孔结构。催化活性评价结果表明:La_(0.8)Ce_(0.2)Fe_(0.1)Co_(0.9)O_3具有很好的三效催化活性,在理论空燃比的条件下,CO、C_3H_6和NO的起燃温度分别为195℃、264℃和290℃,完全转化温度分别为239℃、418℃和415℃,低温三效催化活性良好;Fe和Co的掺杂量同时影响着La_(0.8)Ce_(0.2)Fe_(1-x)Co_xO_3的催化效果。     

活性炭对废水中Cr(Ⅵ)、As(Ⅲ)的吸附

考察了单组分和混合组分条件下温度和pH对活性炭吸附废水中Cr(Ⅵ)、As(Ⅲ)的影响,实验结果表明:在单组分条件时,活性炭对Cr(Ⅵ)的最佳吸附温度和pH为35℃和2.00,对As(Ⅲ)的最佳吸附温度和pH为30℃和6.00;在混合组分条件时,溶液中的As(Ⅲ)对Cr(Ⅵ)的吸附有一定的抑制作用,随着As(Ⅲ)质量浓度的增加,对Cr(Ⅵ)吸附的抑制作用增大;溶液中有Cr(Ⅵ)时,As(Ⅲ)的吸附量增大,但随着Cr(Ⅵ)质量浓度的增加As(Ⅲ)的吸附量减小。pH和温度对溶液中Cr(Ⅵ)或As(Ⅲ)的吸附量变化趋势影响不大。     

家电以旧换新实施办法(修订稿)

第一章 总则 第一条 为进一步促进扩大消费需求,提高资源能源利用效率,减少环境污染,促进节能减排和循环经济发展,根据<商务部财政部环境保护部关于印发家电以旧换新推广工作方案的函>(商商贸发[2010]190号),制定本办法.