Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

Synthesis and characterization of waterborne polyurethane dispersion from glycolyzed products of waste polyethylene terephthalate used as soft and hard segment

Waste polyethylene terephthalate (PET) bottles were collected, cleaned and then depolymerized by glycolysis with neopentyl glycol (NPG) and dipropylene glycol (DPG), in the presence of N-butyl titanate catalyst. The product, named glycolyzed oligoesters, obtained through the depolymerization, were employed respectively in hard segment and soft segment in the synthesis of novel waterborne polyurethane dispersions (PUDs) via a simple and environmentally benign process. In addition, a polyurethane dispersion without glycolyzed oligoesters was synthesized as a comparison. The bulk structure of PET glycolyzed oligoesters and PUDs films were characterized by Fourier transform infrared spectroscopy (FT-IR), H-nuclear magnetic resonance (¹H NMR) and Gel permeation chromatography (GPC). The results illustrated that glycolyzed oligoesters were successfully introduced into the hard and soft segment of the polyurethanes. Furthermore, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the PET glycolyzed oligoesters and PUDs films. The results showed that the thermal resistance of waterborne polyurethanes obtained with glycolyzed oligoesters increased due to lower degrees of phase separation. X-ray diffraction indicated that all synthesized polyurethanes exhibited reduced degrees of orientation. Due to the balance between hard-/soft-segment of the waterborne polyurethane dispersions, the formulations containing glycolyzed oligoesters within the hard segment sections of the polyurethanes provided the best performance.     

Preparation and characterization of waterborne polyurethane containing PET waste/PPG as soft segment

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis using a 1 : 3 molar ratio of PET repeating unit to glycols like neopentyl glycol (NPG) and dipropylene glycol (DPG). Further, a series of waterborne polyurethanes (WPUs) was synthesized using pure polypropylene glycol (PPG), and glycolyzed oligoesters/PPG blends in different molar ratios as soft segment. Thermal property of WPU was tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, viscosity and particle size of WPU were also investigated. The results show that introduction of a certain amount of glycolyzed oligoester to soft segment makes the degree of hard‐soft domain microphase separation smaller, and can also improve thermal stability of WPU. Furthermore, WPUs synthesised from glycolyzed oligoesters and PPG blends possess larger particle size, better particle size distribution, relative lower and more stable viscosity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42757.     

Recycling of off‐grade pet via partial alcoholysis to synthesize functionalized pet oligomer nanocomposites

Off‐grade poly(ethylene terephthalate) (PET) of industrial manufacturers was partially depolymerized using excess ethylene glycol in the presence of manganese acetate as a transesterification catalyst to synthesize PET oligomers. Influences of reaction time, Ethylene Glycol (EG)/PET molar ratio, catalyst concentrations, and particle size of off‐grade PET on yield of partial glycolysis reaction were investigated based on Box–Behnken's design of experiment. Thermal analyses of glycolyzed products are examined by differential scanning calorimetry. The optimum samples were also well‐characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR). The optimal conditions to synthesize PET oligomer (melting point of about 180°C) for a 120‐min glycolysis reaction time were EG/PET molar ratio of 2 with no catalyst using granule‐shaped PET. The same results were obtained for a 60‐min glycolysis reaction time, including EG/PET molar ratio of 1 with the weight ratio (catalyst to PET) of 0.5% using average particle size of PET. Then, maleated PET as a compatibilizer for preparing PET nanocomposites was produced via reaction between maleic anhydride/phthalic anhydride composition and optimized PET oligomers based on central composite design of experiment. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 gave the best results based on d‐spacing and peak shift of nanocomposite samples. Hence, melt mixing of maleated PET with organoclay produced a good intercalation of layered silicate and good dispersion of clay in maleated PET matrix. Analysis of variance (ANOVA) was studied for both glycolyzed products and functionalized PET oligomers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Unsaturated polyester resins from poly(ethylene terephthalate) waste for polymer concrete

Depolymerization of poly(ethylene terephthalate), PET, textile waste was performed with a manganese acetate catalyst. Different ratios of diethylene glycol (DG) to propylene glycol (PG) were used for glycolysis. The weight ratio of PET to the glycol mixture was 1:0.65. The glycolyzed products were analyzed for hydroxyl value and the amount of free glycol. These glycolyzed products were reacted with mixtures of sebacic acid (SE) and maleic anhydride (MA) to prepare a series of unsaturated polyesters having different molecular weights. The molecular weights of the unsaturated polyesters produced were determined by the end group analysis. The obtained polyesters were dissolved in styrene (Sty) monomer and their curing behavior was investigated. Polymer concretes (PC) made with these resins were investigated for their compressive strength. The data revealed that the properties of the PC based on recycled PET are comparable to PC made from virgin materials. We concluded that recycling of PET waste may provide a potentially lower cost source of resin, and its recycling in PC will also help reduce an environmental problem.     

Polyester polyols for polyurethanes from pet waste: Kinetics of polycondensation

The kinetics of polyesterification of the glycolyzed PET waste with adipic acid is reported. Glycolysis of PET waste was carried out with ethylene glycol at three different ratios of PET waste to glycol. The glycolyzed products could be readily polyesterified by reacting with adipic acid, to give polyester polyols with low acid number. Kinetics of polyesterification of the glycolyzed product made from 62.5% ethylene glycol (EG) and 37.5% waste were investigated further at different hydroxyl to carboxyl ratios. Reaction conditions were nonisothermal, comparable to the industrial process scheme consisting of two isothermal regions at 170° and 200°C. The kinetic results of the polyesterification of glycolyzed PET waste are compared to the polyesterification of pure diols, namely ethylene glycol and bis(hydroxyethyl) terephthalate (BHET) with adipic acid. The reactions follow second-order kinetics at 170°C and the rate of polyesterification of the mixed diol system from PET waste lies intermediate between those of the pure diols, namely, EG and BHET. Ethylene glycol exhibited the highest reactivity. At 200°C the kinetic plots of the mixed diols from PET waste were nonlinear, and thus the reaction may not follow second-order kinetics. The nonlinearity is explained in terms of the different reactivities of the different diol species in the reaction mixture. The polyester polyols, when cured with polymeric 4,4′ diphenyl methane diisocyanates, gave polyurethane rigid foams and elastomers.     

Physical properties of unsaturated polyester resin from glycolyzed pet fabrics

Physical properties of unsaturated polyester resins (UPE resins) prepared from glycolyzed poly (ethylene terephthalate) (PET) and PET/cotton blended fabrics were investigated. Initially, PET and PET/cotton blended fabrics were chemically recycled by glycolysis. The depolymerizations were carried out in propylene glycol with the presence of zinc acetate as a catalyst. The reaction time was varied at 4, 6, and 8 h. The glycolyzed products were then esterified using maleic anhydride to obtain UPE resins. The prepared resins were cured using styrene monomer, methyl ethyl ketone peroxide, and cobalt octoate as a crosslinking agent, an initiator and an accelerator, respectively. The cured resin products were tested for their mechanical properties and thermal stability. The results indicated that, among the fabric based resins, one prepared from the 8‐h glycolyzed product possessed the highest mechanical properties those are tensile strength, tensile modulus, flexural strength, impact strength, and hardness. The highest thermal stability was also found in the cured resin prepared from the 8‐h glycolyzed product. The mechanical properties of fabric based resins were slightly lower than those of the bottle based resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2536–2541, 2007     

废PET醇解产物及在聚氨酯弹性体合成中的应用

以醋酸锌或3A分子筛为催化荆、一缩二乙二醇(DEG)为醇解剂,降解废聚对苯二甲酸乙二醇酯(PET),得到PET醇解产物;再用此废PET醇解产物合成聚氨酯弹性体(PUEs).讨论了醇解催化剂种类、nDEG:nPET重复单元、醇解产物添加量对PUEs性能的影响,同时采用TIG、DSC、X-射线衍射等分析手段对PUEs进行表...     

Glycolyzed poly(ethylene terephthalate) waste and castor oil-based polyols for waterborne polyurethane adhesives containing hexamethoxymethyl melamine

Glycolysis of poly(ethylene terephthalate) (PET) waste using different molar ratio of poly(ethylene glycol) (PEG400), was used to produce saturated hydroxyl-functional polyester polyols with castor oil (CO) by transesterification process. The waterborne polyurethane (WBPU) adhesives were synthesized from these saturated polyester polyols, isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), and hexamethoxymethyl melamine (HMMM) as cross-linking agent by a conventional prepolymer process. The glycolyzed polyols and polyester polyos formations were characterized using Fourier transform infrared spectroscopy (FTIR) and the molecular weights were determined using gel permeation chromatography (GPC). The cross-linking reaction between WBPU and HMMM was verified using FTIR and ¹H NMR analysis. Thermal properties were investigated by thermogravimetric analysis (TG). Thermal stability of cross-linked WBPU significantly increased with decreasing castor oil content in the process of transesterification to obtain polyester polyol as a soft segment. The T_15% and T_50% (the temperature where 15 and 50% weight loss occurred) of WBPU increased with the decreasing of castor oil content in the obtained polyester polyols, caused by the steric hindrance of polyester polyol with higher castor oil content, in the process of cross-linking reactions with HMMM. The physico-mechanical properties of WBPU, such as hardness, adhesion test, and gloss of the dried films were also determined considering the effect of participation of HMMM in cross-linking reactions with polyurethane, on coating properties.     

Modified unsaturated polyester resins synthesized from poly(ethylene terephthalate) waste, 1. Synthesis and curing characteristics

The depolymerization of poly(ethylene terephthalate) (PET) by alcoholysis reaction is an easy operation and gives prospects for the valorization of wastes. PET waste was first depolymerized by glycolysis reaction at different molar ratios of diethylene glycol (DEG), in the presence of Mn acetate as a transesterification catalyst. The glycolyzed products obtained were reacted with p‐hydroxybenzoic acid (PHBA) and maleic anhydride (MA) to prepare modified unsaturated polyesters. The molar ratio of added PHBA was varied in order to investigate its effect on the curing characteristics of these modified unsaturated polyesters. The data obtained revealed that an increasing molar ratio of PHBA, within the studied range of concentrations, leads to a reduction in the peak exothermic temperature (T_max) accompanied with the required delay in the curing time. The curing characteristics of these modified polyesters are not so fast anymore, which is not manageable and considered as disadvantageous from the practical point of view, showing instead a moderate speed.     

Synthesis and applications of unsaturated polyester resins based on PET waste

Three types of unsaturated polyester resins were synthesized from the glycolysis of polyethylene terephthalate (PET) plastic waste, considering environment, cost and properties for their applications. These synthesized unsaturated polyester resins could be used for various construction processes and materials such as no dig pipelining (NDR-1), pultrusion (PLR-1) and polymer concrete (PCR-1). PET was taken from common soft-drink bottles, and ethylene glycol (EG), diethylene glycol (DEG) and MPdiol glycol mixtures were used for the depolymerization at molar ratios. The glycolyzed PET 1 ^st products (oligomers) were reacted with maleic anhydride, phthalic anhydride and dicyclopentadiene (DCPD) (especially for polymer concrete) to form unsaturated polyester resins with mixed styrene. The lab scale (1–5 kg) and pilot plant scale-up tests (200 kg) were experimented to evaluate the processing characteristics, viscosity, acid number and curing behaviors. The main properties such as hardness, flexural strength, tensile strength, heat distortion temperature, elongation, and chemical resistance were determined based on the various uses of the three resins. Furthermore, the applicability and the properties of these developed resins were verified through many real application tests.     

New epoxy resins based on recycled poly(ethylene terephthalate) as organic coatings

Glycolysis of poly(ethylene terephthalate), PET, waste using trimethylol propane (TMP), triethanolamine (TEA), diethylene glycol (DEG) and diethanolamine (DEA) was used to produce suitable hydroxy-oligomers for epoxy. The glycolyzed products were reacted with epichlorohydrine to prepare a series of di- and tetraglycidyl epoxy resins with different molecular weights. The glycolysis was carried out in presence of manganese acetate as a catalyst at normal and high pressure in presence and absence of xylene at 210 °C. The produced resins were cured with different mole ratios of 1-(2-amino ethyl) piprazine as curing agent at room temperature. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins based on glycolyzed oligomer of PET and DEA have excellent chemical resistances as organic coatings among other cured resins.     

Moisture-cured polyurethane based on polyester and polycarbonate polyols

Moisture-cured polyurethanes were prepared by reacting toluene diisocyanate and sebacic acid-based hydroxy esters such as ethylene glycol sebacate, propylene glycol sebacate, diethylene glycol sebacate, and polyester polyols such as poly(ethylene glycol sebacate), poly(propylene glycol sebacate), poly(diethylene glycol sebacate), and poly(butane diol sebacate). The effect of molecular weight of the esters on film properties and the catalytic effect of 3–5% triethylamine, triethanolamine, and 2-diethylaminoethanol on curing of such films were investigated. Polyurethanes were also prepared using a blend of poly(butane diol carbonate) polyol with polyester polyols. Best polyurethane compositions were obtained when sebacic acid-based polyester polyols were blended with poly(butane diol carbonate) polyol in the ratio of 3:2. These polyurethanes show good tensile strength (120–215 kg/cm²) and elongation (340–460%) properties, having high melting points (247–268°C) and good resistance to solvents and chemicals. Moreover, they are colorless and transparent.     

聚氨酯用二聚酸聚酯二醇的合成

研究了以辛酸亚锡为催化剂、二聚酸（DA）与乙二醇（EG）为原料、制备聚氨酯用二聚酸聚酯二醇的方法,讨论了催化剂的类型和用量、反应温度、原料醇酸比、反应时间等对酯化率的影响,并用红外光谱对合成产物进行了表征。结果表明,DA与EG摩尔配比为1：2．4,催化剂辛酸亚锡用量为原料总质量的0．3％,反应温度在1h内缓慢升温到190℃,然后保温反应4h,并在130℃、2．66kPa下减压3h,酯化率可达99．7％,产品羟值为95mgKOH／g,酸值0．26mgKOH／g。     

Synthesis and characterization of novel polyurethanes based on aminolysis of poly(ethylene terephthalate) wastes,and evaluation of their thermal and mechanical properties

BACKGROUND: Much research is currently directed towards recycling post‐consumer poly(ethylene terephthalate) (PET) products for both environmental and economic reasons. Aminolysis of PET wastes using different amines, such as allylamine, morpholine, hydrazine and polyamines, leads to different reaction products as diamides of terephthalic acid, which do not possess any potential for further chemical reactions. In the past, the use of ethanolamine has been investigated for the aminolytic degradation of PET waste in the presence of different simple chemicals such as sodium acetate as catalysts. The product obtained, bis(2‐hydroxyethylene) terephthalamide (BHETA), has potential for further reactions to obtain useful products. Nevertheless, there has been no report on using recycled BHETA from PET to synthesize polyurethanes. RESULTS: In this research the product of aminolysis of PET waste, BHETA, was prepared. Then novel polyurethanes were synthesized based on the BHETA prepared, 1,4‐butanediol, ether‐type polyol and various molar ratios of hexamethylene diisocyanate. To evaluate the effect of BHETA, the properties of the polyurethanes without and with BHETA were compared. Fourier transform infrared spectra, thermal transitions, degradation, swelling ratio and chemical resistance of the synthesized polyurethanes were investigated. Also, the polyurethanes were applied as adhesives on various substrates. Comparison of the maximum bond strength of the synthesized polyurethane to that of commercial adhesives shows an about 2.2‐fold increase. CONCLUSION: It is possible to synthesize new polyurethanes with interesting properties using BHETA as an aminolysis product of PET waste. These kinds of materials have potential for many applications, such as adhesives and coatings. Copyright © 2008 Society of Chemical Industry     

Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl)triethoxysilane (APTES) content on properties

Waterborne castor oil-recycled polyol based polyurethane-silica nanocomposite adhesives (WPU) with polymer matrix and silica nanoparticles chemically bonded have been successfully prepared through a sol-gel process. A series of waterborne polyurethane adhesives with hard segment contents from 71.3 to 74.5 wt%, were synthesized using an isophorone diisocyanate, 2-bis(hydroxymethyl) propionic acid, recycled castor oil-based as soft segments and (3-aminopropyl)triethoxysilane (APTES) as chain extender. The depolymerized oligoester obtained from glycolysis of poly(ethylene terephthalate) (PET) waste using triethylene glycol (TEG), was transesterified with castor oil (CO) which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 414 mgKOH g⁻¹. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane-silica nanocomposite adhesives were estimated by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The structure and properties of the resulting films were investigated by FTIR, wide angle X-ray diffraction measurement (XRD), thermogravimetry (TG) and differential scanning calorimetry (DSC). TG analysis indicated that APTES can improve the thermal stability of WPU. XRD showed that the crystallinity of WPU decreased with the increase alkoxysilane content. The extent of crosslinking was investigated to show a dependence on silica concentration, which increased the glass transition temperature and particle size of polyurethane nanocomposites with increasing alkoxysilane content due to the condensation of the alkoxysilane groups. The hardness, adhesion and gloss quality of the polyurethane films were also determined considering the effect of APTES content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane-silica nanocomposites as new adhesive materials with high performance coatings materials. The experimental results reveal that the APTES and the hard segment content play a key role in controlling the structure and properties of the PU cast films based on castor oil-recycled polyols.     

乙二胺后扩链TDI型聚氨酯水分散体的过程

以甲苯二异氰酸酯（TDI）、聚氧化丙烯二醇和二羟甲基丙酸等为主要原料制备了聚氨酯水分散体,研究了水、扩链温度、原料的-NCO/-OH摩尔比及扩链比对乙二胺（EDA）后扩链TDI型聚氨酯水分散体过程的影响。FT-IR测试表明,分散体中的H₂O可通过与聚氨酯中残留异氰酸酯基团（-NCO）的竞争反应影响EDA的后扩链过程。分子量及粒径与zeta电位测试表明,H₂O扩链导致分散体失稳;低扩链比时,H₂O对EDA的后扩链过程影响明显,但高扩链比时,后扩链聚氨酯的分子量降低;扩链温度升高,经EDA后扩链聚氨酯的分子量降低,而分散体粒径增大。当原料的-NCO/-OH摩尔比为1.20、扩链温度为30℃、扩链比为60%时,可有效降低H₂O对EDA后扩链聚氨酯过程的影响。     

聚酯装置酯化生产过程动态模拟

动态模型是进行生产过程动态优化的基础。本文采用链段法建立了聚酯装置酯化生产过程反应器和工艺塔相互影响的动态模型,分析了基本控制系统作用下过程操作工况的动态阶跃响应特性。模拟结果表明,酯化反应器进料摩尔配比及反应器温度、压力、液位的调整显著影响了酯化过程气相流的变化,且对反应产物中端羧基含量和聚合度等指标的响应比较灵敏;控制系统对稳定酯化生产过程操作起着显著的作用。     

Unsaturated polyester resin via chemical recycling of off‐grade poly(ethylene terephthalate)

BACKGROUND: The chemical recycling of poly(ethylene terephthalate) (PET), e.g. bottles and fibre wastes, has been studied for many years. Among several methods proposed for chemical recycling of waste PET, glycolysis makes it possible to employ very low amounts of reactants and lower temperatures and pressures compared with critical methanol and thermal degradation. Furthermore, unlike hydrolysis under acidic or basic conditions, glycolysis does not cause any problems related to corrosion and pollution. RESULTS: PET from off‐grades of industrial manufacture was depolymerized using excess glycol. The effects of the reaction time, volume of glycol and catalyst concentrations on the yield of the glycolysis products were investigated. A reaction time of 3 h, weight ratio (catalyst to PET) of 0.25 wt% and PET to ethylene glycol molar ratio of 1:5 were determined as suitable conditions for depolymerization. Then, the reaction of polyesterification of maleic anhydride (MA) and glycolysed products of PET was successfully performed at 160 and 190 °C for 8 h. CONCLUSION: Differential scanning calorimetry and vapour pressure osmometry results for the product of the glycolysis reactions, under suitable condition, confirmed the structure of the desired product. This sample underwent reaction with MA to produce unsaturated polyester resin (UPR). The results of Fourier transform infrared and NMR spectroscopy confirmed that the UPR had been synthesized successfully. This is the first direct report on the glycolysis reaction of off‐grade products of petrochemical companies in order to regenerate raw materials or other secondary value‐added products. Copyright © 2009 Society of Chemical Industry     

Enhanced dynamic mechanical and shape‐memory properties of a poly(ethylene terephthalate)–poly(ethylene glycol) copolymer crosslinked by maleic anhydride

Dimethyl terephthalate (DMT) and ethylene glycol (EG) were used for the preparation of poly(ethylene terephthalate) (PET), and poly(ethylene glycol) (PEG) was added as a soft segment to prepare a PET–PEG copolymer with a shape‐memory function. MWs of the PEG used were 200, 400, 600, and 1000 g/mol, and various molar ratios of EG and PEG were tried. Their tensile and shape‐memory properties were compared at various points. The glass‐transition and melting temperatures of PET–PEG copolymers decreased with increasing PEG molecular weight and content. A tensile test showed that the most ideal mechanical properties were obtained when the molar ratio of EG and PEG was set to 80:20 with 200 g/mol of PEG. The shape memory of the copolymer with maleic anhydride (MAH) as a crosslinking agent was also tested in terms of shape retention and shape recovery rate. The amount of MAH added was between 0.5 and 2.5 mol % with respect to DMT, and tensile properties and shape retention and recovery rate generally improved with increasing MAH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 27–37, 2002