Degradation of polyester film in alkali solution

In recent years there has been a remarkable growth in coatings technology, yet polymer‐coated metals still corrode when they are exposed to severe environments. If the effectiveness of polymer coatings is to be increased, it is essential to understand the microstructure of polymer coating film and the changes that occur to the film upon environmental exposure, and relate the changes to the protective performance of coatings. The degradation of a polyester immersed in alkali solution has been investigated using a number of analytical techniques including atomic force microscopy (AFM), liquid chromatography/mass spectrometry (LC/MS), and Fourier transform infrared spectroscopy (FTIR). AFM was used to characterize the heterogeneous phase in the unexposed films and films exposed to alkali solution. Film roughness was found to increase with aging of the film in alkali medium. Total organic carbon analysis of the leached aqueous medium showed the presence of organic compounds, suggesting a chemical degradation of the film in alkali medium. FTIR analysis of the leached medium showed evidence for the formation of carboxylate species upon degradation of polyester film in alkali solution, while LC/MS analysis of the leached medium confirmed the presence of isophthalic acid and sodium isophthalate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2454–2463, 2000     

Enzymatic hydrolysis of polyester based coatings

The potential of two hydrolytic enzymes, namely a lipase from Thermomyces lanuginosus (TlL) and a cutinase from Humicola insolens (HiC) for hydrolysis of the phthalic acid backbone based polyester coatings was assessed. Two phthalic acid/trimethylolpropane based model substrates resembling the structure of the polyester backbone of coatings were synthesized. Out of both enzymes, only the cutinase was able to hydrolyze both model substrates while the larger substrate was hydrolyzed at a lower rate. The cutinase was also able to hydrolyze a coating (alkyd resin) both in suspension and as dried film. LC–MS analysis of the hydrolysis products released from the coating revealed the presence of oleic acid, its monoglyceride, phthalic acid and 2-((3-((2-((2,3-dihydroxypropoxy)carbonyl)benzoyl)oxy)-2-hydroxypropoxy)carbonyl)benzoic acid. These results indicate that the enzyme was able to hydrolyze the polyester backbone as well as to release fatty acid side chains. Consequently, enzymatic hydrolysis has a potential for the removal of coatings, their recycling or their functionalization.     

A chemical means to study the in vitro hydrolytic degradation of poly(glycolic acid)

A chemical means was developed to examine the in vitro hydrolytic degradation of both γ-irradiated and nonirradiated poly(glycolic acid) (PGA)-absorbable polymers for the purpose of obtaining information how irradiation affected PGA degradation and how the results related to the previously observed mechanical and morphological data. The method was based on the chemical reaction between the degradation product of the polymer, glycolic acid, and chromotropic acid, and the subsequent measurement of the absorbance of the reaction products by a UV/visible spectrophotometer. It was found that the unirradiated PGA specimens exhibited a two-stage hydrolytic degradation mechanism. This observation supported the previously hypothesized hydrolytic degradation mechanism on the basis of the level of crystallinity data. As the dosage of irradiation increases, the characteristic two-stage degradation mechanism becomes less profound and eventually disappears at 20 Mrads. A monotonic degradation profile was then observed at this dosage level. As reported in the literature, the widespread use of mechanical properties to evaluate the degradation phenomena of this class of polymer does not, however, provide the details of the degradation mechanism as revealed by the present study. The interrelationship between tensile strength, level of crystallinity, glycolic acid concentration, and pH levels of the medium, and their changes as hydrolytic degradation proceeds, are discussed for the purpose of elucidating the mechanism in more detail.     

Synthesis and characterization of novel citric acid-based polyester elastomers

In this paper we report successful simple synthesis of unique elastic polyesters by carrying out catalyst-free polyesterification of multifunctional non-toxic monomers: 1,8-octanediol (OD), citric acid (CA) and sebacic acid (SA). The chemical, physical, and surface chemical properties of the resulting copolyester polyoctanediol citrate/sebacate [p(OCS)] have been investigated. This new material was characterized by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), thermal analysis (TA), mechanical tests, photo-acoustic Fourier-transform infrared spectroscopy (PA-FTIR), X-ray photoelectron spectroscopy (XPS) and swelling experiments. We demonstrate that the chemical structure, morphology, physical integrity and surface chemistry of the synthesized co-polymer can be controlled by simply varying the initial acid concentration (CA/SA) in the pre-polymer. This novel p(OCS) polymer exhibits versatility in mechanical properties, hydration and hydrolytic degradation as determined by the chemical structure of the polyester elastomer.     

Study on film forming organo-copper polymer

Film forming organo-copper polymer was synthesized from diethanol amine. The organo-copper polymer (copper salt of polyester amide) contains long chain amide in the side group. The intermediates and the final products were characterized for chemical structure, molecular weight, copper content, curing and thermal properties of cured resin. Organo-copper polymer was used as soluble resin to formulate a coating. Mechanical strength and leaching behavior of the coating were studied. The coating was found to be self-polishing in nature.     

Study on film forming organo-copper polymer

Film forming organo-copper polymer was synthesized from diethanol amine. The organo-copper polymer (copper salt of polyester amide) contains long chain amide in the side group. The intermediates and the final products were characterized for chemical structure, molecular weight, copper content, curing and thermal properties of cured resin. Organo-copper polymer was used as soluble resin to formulate a coating. Mechanical strength and leaching behavior of the coating were studied. The coating was found to be self-polishing in nature.     

Seed oil based polyester polyols for coatings

The hydroformylation of seed oil based fatty acid methyl esters leads to aldehyde intermediates that can be hydrogenated to give novel seed oil based monomers. In this study, the seed oil based monomers were polymerized with low molecular weight diols to produce novel aliphatic polyester polyols with very low viscosities. The seed oil polyester polyols provide environmentally friendly (green) coating formulations with low volatile organic compound emissions which lead to coatings with superior physical properties, such as exceptional hydrolytic resistance and flexibility. From these polyester polyols, waterborne polyurethane dispersions were also developed with excellent stability resulting in coatings with superior physical properties (i.e., good toughness and abrasion resistance), and exceptional hydrolytic and acid resistance.     

Effect of the polyester chemical structure on the stability of polyester–melamine coatings when exposed to accelerated weathering

The effect of the polyester chemical structure on the degradation of polyester/melamine coatings was studied. Four different polyesters were synthesized using different diacid monomers: (i) isophthalic acid (IPA) and mixtures of hexahydrophthalic anhydride (HHPA) with (ii) terephthalic acid (TA), (iii) phthalic anhydride (PAN) and (iv) 1,4 cyclohexanedicarboxylic acid (1,4-CHDA). Varnishes were prepared using melamine resin and submitted to accelerated degradation cycles. The process was monitored in terms of photooxidation index (POI), based on FTIR analysis, and in terms of changes in films’ hardness, level of gloss and surface morphology. The monomers which contributed the most to polymer degradation were the couple HHPA and 1,4-CHDA. The most important factor to degradation was the high number of hydrogen atoms attached to tertiary and secondary carbons in the polymer structure, due to their high sensitivity to abstraction, which favors the photooxidation reactions. The monomer IPA presented the lowest POI and the highest gloss retention.     

核分子比例对超支化聚酯结构和涂膜性能的影响

以双季戊四醇为核,二羟甲基丙酸为单体合成了不同代数的超支化聚酯。采用了IR、GPC、13C NMR、DSC和化学滴定等方法对产物进行了表征和分析。试验结果表明聚合物具有较小的多分散性指数(拟两代超支化聚酯M—w/M—n=1.159,拟四代超支化聚酯M—w/M—n=1.028)。通过聚合物的13C NMR分析了超支化聚酯的支化度,表明在超支化聚酯中,端羟基的反应活性大于线性单元中羟基的活性。并用油酸对聚合物进行改性,研究了固含量与黏度的关系及其涂膜的性能;结果表明该树脂具有良好的成膜性和涂膜性能。     

Synthesis,crosslinking and degradation of some unsaturated polyester resins

Some unsaturated polyester resins were prepared by the ester interchange between p-carbethoxymaleananilic acid and p-carbethoxysuccinanilic acid with saturated and unsaturated diols. Moreover, copolymers were also synthesized by the polyesterification of the aforementioned acids and maleic anhydride with the above-mentioned glycols. The structure of both the unsaturated polyester resins and copolymer resins was established by IR, UV, and NMR spectroscopy. Also, viscosity measurements and molecular weight determinations were further tools for their structural elucidation. All the products were attempted to cure with styrene in the presence of benzoyl peroxide as initiator, and the produced network structures, in the form of films, were tested as surface coating materials for glass and metals. The structure of the cured products was established after their degradation, by physical and spectroscopical means.     

Preparation and characterization of a hyperbranched polyethoxysiloxane based anti‐fouling coating

A hyperbranched polyethoxysiloxane was synthesized via hydrolytic polycondensation between methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS), with hydrochloride acid as catalyst. FTIR, ¹H NMR, ²⁹Si NMR, and GPC measurements confirmed that the polyethoxysiloxane synthesized was indeed a hyperbranched polymer with a degree of branching of 0.67. It was also found that there were no silanol groups in polymer matrix. This quality can effectively enhance its storage stability. Based on the hyperbranched polyethoxysiloxane, a novel antifouling coating with high curing speed at ambient temperature was developed. The recipe and other technique parameters of the coating were revealed and investigated. Experiments indicate that the coating performs well as an antifouling agent and can be applied to various ceramic products. By using scanning electron microscope (SEM) to inspect the surface of a polished tile applied with the coating, the antifouling mechanism was studied and the results were explained in accordance with the penetrating and crosslinking of the macromolecules of hyperbrached polyethoxysiloxane into the microdefects on the surface of tiles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5818–5824, 2006     

Synthesis, characterization and biodegradation studies of poly(ester urethane)s

Bis-isocyanoto polyester was synthesized by the polymerization of PPSe with MDI and reacted with 1,3-propanediol chain extender to obtain poly(ester urethane)s. The effect of chain extender and PPSe content in polyurethane was investigated. The polymers were characterized by ¹H NMR, FT-IR, viscosity measurement, TGA and XRD. Their biodegradability was investigated by the hydrolytic degradation in NaOH solution (3% and 10%); enzymatic degradation by Rhizopus delemar lipase and soil burial degradation using garden-composted soil. Furthermore, the degraded film was characterized by molecular weight, intrinsic viscosity, DSC, XRD, FT-IR and surface morphology by SEM. The biodegradation study revealed that hydrolysis and soil burial degradation affected morphology of the PEUs. Hydrophobicity and hard segment seem to resist the hydrolytic and enzymatic degradability of PEU. Hydrolytic degradation was very rapid in 3% and 10% NaOH solutions at 37 °C, within 2 days 20% weight loss was observed. PEUs showed a much slower degradation rate under the R. delemar lipase at 37 °C. Experimental data showed that as soft segment increases biodegradation rate decreased. A significant rate of degradation was occurred in all PEU samples under soil burial condition. Surface morphology, which interconnected to good adhesion of bacteria on polymer surface, is considered to be a factor sensible for the biodegradation rate under soil burial condition.     

Maleic Anhydride-Grafted PLA Preparation and Characteristics of Compatibilized PLA/PBSeT Blend Films

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3–6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry.     

Vegetable oil based highly branched polyester/clay silver nanocomposites as antimicrobial surface coating materials

The unison of nanotechnology and polymer science enables the development of novel silver-based polyester nanocomposite as an antimicrobial coating material. Highly branched polyester/clay silver nanocomposites based on vegetable oil with different loadings of silver were prepared via reduction of silver salt by employing dimethylformamide as solvent as well as reducing agent at room temperature. Organically modified montmorillonite clay of 2.5 wt% was used as the nanofiller for the property improvement of the pristine polymer. The highly branched polyester resin was synthesized by condensation of 2,2-bis(hydroxymethyl) propionic acid with Mesua ferrea L. seed oil based carboxyl terminated pre-polymer, as reported earlier. FTIR, UV–vis, XRD, SEM and TEM studies substantiate the formation of well-dispersed silver nanoparticles within the clay gallery with an average size of 15 nm. The thermostability of the silver nanocomposites obtained by thermogravimetric analysis was enhanced by 20 °C. The mechanical properties such as tensile strength and scratch hardness were improved 4.5 and 2.6 units respectively and impact resistance improved a little by nanocomposites formation. The antimicrobial efficacy of the as-prepared silver nanocomposites was also premeditated and highly antibacterial activity against Gram negative bacteria (Escherichia coli and Psuedomonas aeruginosa) was observed. Excellent chemical resistance in various chemical media except in alkali has also been noticed. The study reveals that the polyester/clay silver nanocomposites based on vegetable oil show the potential to be applicable as antibacterial surface coating materials.     

有机硅改性聚酯的合成及其粉末涂料的性能

利用有机硅中间体合成了有机硅改性聚酯树脂。通过IR、GPC、SEM等分析了改性聚酯的结构与形态 ,用电子探针分析了改性聚酯的表面组成 ,考察了有机硅含量对改性树脂玻璃化温度、熔融黏度、对水的接触角及表面张力的影响。研究发现 ,改性聚酯中的含硅聚酯在表面富集 ,大大降低了聚酯树脂的表面张力 ,提高了其粉末涂料的涂膜耐候性。相对于纯聚酯树脂 ,有机硅质量分数为 1 %可使树脂的表面张力从 49.5降到 2 8.4mN/m ;经 2 1 6h中波紫外线照射后 ,涂膜的光泽保留率从 81 %上升到 91 .3 %。含有机硅质量分数超过 5 %后 ,涂膜的抗冲性能下降。     

一种新型聚丁二酸丁二醇酯类脂肪族生物可降解聚酯的性能

以丁二酸、L-乳酸、对苯二甲酸等二元酸和丁二醇、乙二醇等二元醇为原料,通过熔融缩聚法直接合成了一种聚（丁二烯-苯乙烯）类的脂肪族生物可降解聚合物。介绍了聚合物的聚合工艺,并对其进行力学性能测试和扫描电子显微镜分析。结果表明,这种聚合物具有一种独特的力学性能,在断裂伸长率为450 %典型的应力-应变橡胶平台曲线上,分别在断裂伸长率为10 %和300 %处出现典型的屈服应力,第二个屈服应力的存在使得该聚合物有极好的强度、柔韧性、记忆性和回弹性,它的高强高韧性能可用作脆性降解材料（如聚乳酸）的优良改性材料。     

水解剥离法制造超细纤维

在６ ｍ ３ 间歇式反应装置上合成了易水解聚酯（ＥＨＤＰＥＴ）,选择适宜条件,ＥＨＤＰＥＴ 的水解性能可以得到随意控制,将合成的ＥＨＤＰＥＴ 与ＰＥＴ（或ＰＡ）以 １５～２５／８５～７５ 质量比在 Ｈｉｌｌｓ 双组分复合纺丝机上进行复合纺丝,得到以ＥＨＤＰＥＴ为海组分,以ＰＥＴ（或ＰＡ６）为岛组分的海－ 岛型复合纤维;该复合纤维物理性能良好,用该复合纤维织造的机织物和针织物,其纺织加工性能均良好。织物经水解处理,复合纤维即被剥离成线密度为０．０４４ ｄｔｅｘ 的超细纤维。     

涂料用支化型饱和聚酯树脂的合成及表征

采用溶液缩聚的方法,以对苯二甲酸、间苯二甲酸、己二酸、新戊二醇、一缩二乙二醇和1,1,1-三羟甲基丙烷(TMP)为原料,合成了一类新型的涂料用支化型饱和聚酯树脂。介绍了合成工艺及原材料的选择。通过红外光谱分析、X-射线衍射、热重分析和差热分析等测试其结构、形态和热性能。结果表明,合成的涂料用支化型饱和聚酯树脂的热稳定性较高。     

易水解聚酯的热性能

用PTA法合成了一系列易水解聚酯(EHDPET)。采用DSC和TGA技术系统分析了SIPE、IPA、脂肪族化合物(A)等各组分含量对其热性能的影响。结果表明:tg、tcc(冷结晶温度)随SIPE含量的增加而升高,tm、tmc(热结晶温度)则下降;IPA的加入使tg、tm、tmc均下降,而tcc升高;随脂肪族化合物(A)含量的增加,tcc、tg下降。随SIPE、脂肪族化合物(A)含量的增加,EHDPET的热稳定性变差。     

Preliminary Studies on the Properties of Novel Polymeric Composite Materials Based on Polysuccinates

This study aimed to prepare novel biodegradable polymeric composites based on poly(3-allyloxy-1,2-propylene) succinate (PSAGE). These composite materials are composed of poly(ester-anhydride) (PEA) microspheres embedded in polyester matrix prepared by crosslinking PSAGE with oligo(1,2-propylene maleate) and methacrylic monomers. Methyl methacrylate and one of hydrophilic oligo(ethylene glycol) dimethacrytes with different length of oligooxyethylene chains were used as polymerizable solvents. Incorporation of microspheres that degrade faster than crosslinked polyester matrices enables formation of porous structure. The obtained materials are liquid before curing and harden in several minutes with moderate exothermic effect. The effect of the composition of polyester matrices and kind of PEA microspheres used on selected properties, such as water sorption, mechanical strength, porosity, and hydrolytic degradation behavior, was investigated. The morphology of the cured composite materials subjected to hydrolytic degradation was evaluated by SEM.