Photopolymerization and the related properties of dendritic methacrylated polyesters

Three kinds of photopolymerizable dendritic polyesters have been synthesized based on 1,1,1‐trishydroxymethyl‐propanol, pentaerythritol, and dipentaerythritol as polyols and polycarboxylic acid anhydride, modified with glycidyl methacrylate and then esterified by acetic anhydride, which contain a maximum of 6, 8, and 12 methacrylic groups at the molecular chains, respectively. Their dynamic viscosity and UV‐cure speed have been measured by a spinning viscometer and the tack‐free time of the product, and the mechanical properties have been investigated by pendulum hardness and tensile strength of the UV‐cured films. It is found by comparison with traditional linear epoxy (meth)acrylate oligomers with lower molecular weights that the dynamic viscosity of the dendritic methacrylated polyesters is only half of that for the linear oligomers. However, the UV‐cure speed is about five times of that for the latter. The tensile strength of the cured films increases with the functionality of the polyester and a small amount of comonomer addition. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 499–504, 2001     

Effect of catalyst on the reactive processing of polyesters with epoxy-functional polymers

The objective this work was to determine the effects of selected polyester catalysts on the reaction of a polyester with epoxy functional polymers. Polyesters containing various catalyst metals were melt blended with either an ethylene-co-glycidyl methacrylate or a styrene-co-glycidyl methacrylate copolymer. The viscosities of the blends were monitored as a function of mixing time using torque rheometry. In addition, the molecular weight distributions of selected samples were analyzed using gel permeation chromatography. Both the torque rheometry and the gel permeation chromatography results indicate that the polyester reacts with epoxy functional polymers. This reaction occurs under conditions and at processing times which are readily obtainable in conventional melt processing equipment. Furthermore, the reaction kinetics of polyesters with glycidyl methacrylate copolymers are dramatically affected by the nature of the catalyst system used to prepare the polyester. Under the conditions used, antimony catalysts are particularly effective at promoting the reaction between polyesters and the epoxy functionality and the activity of the catalysts studied appears to decrease in the following order: antimony > gallium > tin ? titanium > germanium. Manipulation of the polyester catalyst system may offer a method to control the extent of reaction obtained in reactive processing of polyesters with epoxy functional compounds.     

UV固化水性高支化聚酯

以偏苯三酸酐(TMA)、环氧氯丙烷(ECH)、甲基丙烯酸缩水甘油酯(GMA)、三乙胺(TEA)合成了末端羧基与氨基不同比例的一系列可UV固化的高支化聚酯,研究了末端官能团对合成产物水溶性、粘度以及凝胶转化率的影响。结果表明:高支化聚酯的水溶性随着末端的羧基增多而变大,光固化速度与末端的丙烯酰基官能度有关。水作为溶剂引入10%后,可以将树脂的粘度从6500mPa·s降低到3200mPa·s。     

Studies on hexolic anhydride based polyesters,II. Thermogravimetric analysis

Unsaturated polyesters based on hexolic anhydride (5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methanonaphthalene-2,3-dicarboxylic anhydride), maleic anhydride, phthalic anhydride, cis-2-butene-1,4-diol, 2,3-dichloro-2-butene-1,4-diol and 2,3-dibromo-2-butene-1,4-diol were synthesized. The thermal behaviour of the polyesters was studied using thermogravimetric technique. The results were compared with those available for other hexolic anhydride and HET-acid (1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid) based polyesters. The direct study and comparative study of the polyesters revealed that the bromodiol is prominent in increasing the flame retardant character of the polyesters in which it is incorporated; alkenic diols are inferior compared to saturated diols regarding the thermal stability of the polyesters; as the number of carbon atoms in the saturated diol increases, the stability and flame retardancy of the polyesters decrease; branching in the diol part decreases the stability of the polyesters, with hexolic anhydride based polyesters being thermally more stable than HET-acid based polyesters.     

Unsaturated polyester resins modified with perfluoropolyethers

Telechelic macromers based on hydroxyterminated perfluoropolyethers (HO-R_H-PFPE-R_H-OH) with different molecular weights were used for the preparation of fluorine-containing unsaturated polyester resins (FUPR). The products resulting from the reaction of the monomers usually employed for the preparation of unsaturated polyesters with HO-R_H-PFPE-R_H-OH were in any case milky liquids. The degree of reaction of the hydroxyl terminal groups of HO-R_H-PFPE-R_H-OH was monitored by ¹H-NMR analysis on the fractions collected after sedimentation experiments; amount and composition of the sediment and sedimentation rate were found dependent on both the molecular weight of fluorinated macromer and the method used for polyesterification. The molecular weight of HO-R_H-PFPE-R_H-OH and the reaction conditions had also a strong influence on the final morphology of crosslinked polymers. A very poor interphase adhesion was observed when unreacted HO-R_H-PFPE-R_H-OH was blended with the unsaturated polyester. On the contrary, when the fluorinated macromer was allowed to react during polyesterification, the adhesion of the fluorine-rich dispersed phase to the unsaturated polyester matrix was good for low molecular weight HO-R_H-PFPE-R_H-OH and when the fluorinated prepolymer had been modified by a previous reaction with chlorendic anhydride, but it was poor, as for unreacted macromers, for high molecular weight HO-R_H-PFPE-R_H-OHs. FUPRs prepared using a low molecular weight HO-R_H-PFPE-R_H-OH exhibited a significant improvement of the flexural strength even at very low level of addition (3% by wt). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1679–1691, 1998     

Synthesis of new polyesters with methacrylate pendant groups

Summary A catalytic process for synthesis of new polyesters with methacrylate pendant groups is presented. Thus, zinc succinate catalyzed reaction of succinic anhydride with glycidyl methacrylate (GMA) in dimethoxyethane gives linear oligoesters with low molecular weights (1380-2400 Da). The polyester formation takes place via simultaneous ring opening of the cyclic anhydride and oxirane units. GMA component can be partially replaced with cyclohexeneoxide to obtain polyesters with methacrylate pendant groups in various percentages. Nearly colorless waxy polymers are obtained in excellent yields (69–97%) within 48–60 h. at 90 °C. In the study structure of the polymers have been elucidated by conventional spectroscopic techniques and photo-crosslinking of ability of their thin films have been tested by monitoring intensity of methacrylate double bonds, using IR-spectrometry methodology.     

Synthesis and characterization of sulfonated liquid crystalline polyesters

Liquid crystalline polyesters based on hexanediol, dimethyl 4,4′‐biphenyldicarboxylate, and various levels of dimethyl 5‐sodiosulfoisophthalate (0–20 mol%) were prepared using a conventional melt polymerization process. The presence and quantification of the ionic functionality was surveyed using ¹H NMR spectroscopy. Solution viscosities and corresponding molecular weights decreased when the ionic monomer concentration exceeded a critical value (higher than 3 mol%). Differential scanning calorimetry indicated a maximum in the isotropic transition temperature versus ionic modification at approximately 10 mol%. Dynamic mechanical analysis indicated that the glass transition temperature was suppressed due to ionic association at high concentrations (greater than 3 mol%) of ionic functionality. Polarized light microscopy and wide‐angle X‐ray diffraction were used to identify the smectic liquid crystalline and crystalline phases. © 2002 Society of Chemical Industry     

Rheology of concentrated solutions of hyperbranched polyesters

The solution rheology of different generations of hyperbranched polyesters in N‐methyl‐2‐pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amidoamine) (PAMAM) dendrimers in ethylenediamine were compared with those of the hyperbranched polyesters in NMP. Both types of dendritic polymers have relative viscosities that are exponential functions of their molar fraction in solution. The slopes of these relative viscosity curves show a linear relationship with respect to the generation number. PAMAM dendrimers have the greater slopes for each generation, reflecting their relatively larger intrinsic viscosity values.     

Synthesis of reactive soybean oils for use as a biobased thermoset resins in structural natural fiber composites

Biobased thermosets resins were synthesized by functionalizing the triglycerides of epoxidized soybean oil with methacrylic acid, acetyl anhydride, and methacrylic anhydride. The obtained resins were characterized with FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy to confirm the functionalization reactions and the extent of epoxy conversion. The viscosities of the methacrylated soybean oil resins were also measured for the purpose of being used as a matrix in composite applications. The cross‐linking capability was estimated by UV and thermally initiated curing experiments, and by DSC analysis regarding the degree of crosslinking. The modifications were successful because up to 97% conversion of epoxy group were achieved leaving only 2.2% of unreacted epoxy groups, which was confirmed by ¹H‐NMR. The ¹³C‐NMR confirms the ratio of acetate to methacrylate methyl group to be 1 : 1. The viscosities of the methacrylated soybean oil (MSO) and methacrylic anhydride modified soybean oil (MMSO) were 0.2 and 0.48 Pas, respectively, which indicates that they can be used in resin transfer molding process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

低密度交联硬质聚氯乙烯泡沫塑料的研究

以酸酐和异氰酸酯为交联组分,糊用聚氯乙烯为基体树脂,制备了低密度交联硬质聚氯乙烯(Crosslinked-PVC)泡沫塑料。考察了甲基六氢苯酐、偏苯三酸酐和对苯二甲酸与甲苯二异氰酸酯及多亚甲基多苯基多异氰酸酯的不同官能度配比对模压块和泡沫塑料交联度的影响,酸酐/异氰酸酯配比对泡沫塑料的性能影响,不同[K]值PVC树脂对泡沫塑料的性能影响。研究表明,异氰酸酯和酸酐的官能度对模压块和泡沫塑料的交联度影响十分显著,模压块中过早产生交联对后续发泡过程不利。随着酸酐/异氰酸酯摩尔比的增加,泡沫密度减小,压缩强度降低,且泡沫密度达到最低密度的时间缩短。当糊用PVC树脂[K]值过小时,发泡体系容易发生并泡和中间鼓泡;当[K]值过大时,压缩性能反而下降。制备的Crosslinked-PVC泡沫塑料具有半互穿聚合物网络结构。     

Characterization of hyperbranched polyol polyesters based on 2,2‐bis (methylol propionic acid) and pentaerythritol

Hyperbranched polyesters (HBPs) of fourth and fifth generation were synthesized by procedures involving one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both of them (HBP1‐4, HBP1‐5) using 2,2‐bis(methylol)propionic acid (DMPA), pentaerythritol (PE), and acid catalysis. The characterization of the polyesters was done by nuclear magnetic resonance (NMR), rheology on solution, Fourier transform infrared spectroscopy (FTIR), and acid and hydroxyl values. The degree of branching of polyesters (DB) and the average molecular mass and polymerization degree _NMR were calculated by Frey and Fréchet methods and (DP)_NMR, respectively, being higher for HBP4P sample. The molecular structure of polyesters depends mainly on of the synthesis method. The hydroxyl values were larger than 430 mg/g KOH for all HBPs, and the conversion was controlled between 90 and 93% to avoid excessive cyclization reactions. The steady shear viscosities at different temperatures and at 41.77 s^?1 shear rate were measured for all HBPs solutions in dimethyl formamide (DMF) showing a shear thickening behavior. The flow activation energies (E_a) were calculated by Arrhenius equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on chemical resistance of polyesters

Chlorendic anhydride based polyester ( I ,) tetrachlorophthalic anhydride based polyester ( II ), dibromoneopentyl glycol based polyester ( III ,) general purpose polyester ( IV ,) blend of dibromoneopentyl glycol based polyester with general purpose polyester ( V ,) chlorendic anhydride and dibromoneopentyl glycol based polyester ( VI ), and a blend of chlorendic anhydride based polyester and dibromoneopentyl glycol based polyester ( VII ) were prepared and their chemical resistance and moisture absorption studied in various reagents, acid, alkali, and water, at 25 and 65°C. It is found that the polyester ( III ) is the least affected in the presence of the acids. In 20% NaOH, there was a decrease in weight for all polyesters at both the temperatures compared to the control except the polyester ( VII ). Increase in weight of all the polyesters was observed during the absorption of moisture both at 25 and 65°C. The increase was higher at higher temperature. Polyester ( III ) thus shows the least absorption of moisture.     

Effect of polyester polyol chain length on the properties of transparent poly (ester-urethane-acrylate)/MMA copolymer for optical applications

A series of poly(ester-urethane acrylate)/methyl methacrylate (PEUMA) crosslinked copolymers were prepared using hydroxyl terminated aromatic polyesters (PEs) with varying chain lengths. Four kinds of PEs with terminal hydroxyl groups were synthesized by reacting phthalic anhydride (PA) with 1,2- propanediol (PDO), 1,4-butanediol (BDO), 1,6-hexanediol (HDO) and diethylene glycol (DEG) respectively. The resultant PEs were reacted with isophorone diisocyanate (IPDI) in the presence of dibutyltin dilaurate (DBTDL) catalyst and end capped with 2-hydroxyethyl methacrylate (HEMA) to obtain ester-urethane-acrylate (EUA) prepolymer. Thereafter, crosslinked PEUMA copolymer were synthesized by reacting the EUA prepolymer with 40% (w/w) methyl methacrylate (MMA) in the presence of 1% azobisisobutyronitrile (AIBN) chain initiator. The PEs and EUA prepolymer were characterized by Fourier transform infrared (FT-IR) spectroscopy, ¹H NMR, and gel permeation chromatography (GPC) techniques. The average molecular weights (Mc) between two crosslinks of the samples were determined by using the Flory Rehner equation. The tensile modulus, flexural strength, thermal properties and transparency of PEUMA copolymers were also determined and correlated with the average molecular weight and crosslinked density. The transparency of PEUMAs was found to be above 90% and hence it is an excellent alternative to glass for optical applications.     

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters

Cholesteric liquid crystalline polyesters were successfully synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride. Homo/copolyesters were synthesized by the solution polycondensation method, for which a mild organic base such as pyridine was employed. Inherent viscosities of polyesters P‐3–P‐5 were in the range of 0.31–0.39 dL/g at 25°C in chloroform, and polyesters P‐1 and P‐2 were insoluble in chloroform. Homo/copolyesters based on isosorbide, methyl hydroquinone, and isophthalic acid had thermal stability at more than 300°C on the basis of 10% weight loss. The thermotropic liquid crystalline properties were examined by differential scanning calorimetry and polarizing optical microscopy. Wide‐angle X‐ray diffraction study demonstrated that polyesters P‐1, P‐2, and P‐3 were semicrystalline, whereas the degree of crystallinity of polyesters P‐4 and P‐5 was less than 5%. Copolyester P‐4 showed formation of a yellow iridescent streak at 209°C on heating and development of a Grandjean texture at 270°C on heating. These are typical textures of the cholesteric liquid crystalline phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1232–1237, 2007     

环氧树脂改性超支化聚酯的合成及性能

以偏苯三酸酐、环氧氯丙烷及甲基丙烯酸缩水甘油酯为原料合成了超支化聚酯(HBP),再通过超支化聚合物的羧基与环氧树脂环氧基的反应得到环氧改性超支化聚合物;用GPC1、H-NMR、DSC、TGA表征了环氧改性超支化聚合物的结构和热性能;比较了不同环氧树脂用量改性前后树脂的光反应活性以及光固化涂层的耐擦洗性和硬度,测定了凝胶率-曝光时间曲线;以环氧改性超支化聚合物配制了光刻胶,在混合光源以及接触曝光的条件下,分辨率达到2~3μm,且图像十分清晰,断面整齐。环氧树脂用量为HBP羧基物质量的70%左右时,改性的超支化聚酯的光固化活性有明显提高,力学性能得到明显改进。     

Base-hydrolyzed starch-polyacrylonitrile (S-PAN) graft copolymer. S-PAN-1:1, PAN M.W. 794,000

Starch-polyacrylonitrile (S-PAN) graft copolymer consisting of one part starch and one part polyacrylonitrile (M. W. 794,000) was hydrolyzed with aqueous KOH at 80 and 100°C to polyelectrolytes containing carboxyl and amide functionality but void of infrared-detectable amounts of nitrile. Viscosities of potassium salts of the polyelectrolytes in water were pH dependent with peak viscosities at 8.5. These dispersions were characterized by unusually high viscosities, 15,000 to 26,500 cp at 1% concentration, and by the ability to retain significant viscosities, 300 to 950 cp, upon dilution to 0.03% concentrations. A 1% dispersion of hydrolyzed S-PAN had a viscosity of 5,000 cp in the presence of 8% KCl; however, the depressing effect of added salts on viscosity of aqueous dispersions of hydrolyzed S-PAN increases as the valence of the cation increases.     

The measurement of melt flow and melt stability

The melt flow of a plastic as measured by the standard method (ASTM D-1238) is at a high enough stress so that the flow is non-Newtonian. If the die in the plastometer is replaced by a nonstandard, tapered die of large orifice, a lower stress can be used and the flows are shown to be comparable to Newtonian viscosities measured in a cone and plate rheometer. Under these conditions the plastometer can be used as a sensitive measure of the melt stability of a plastic.     

Synthesis and properties of multiarm star hydroxyl-terminated polyesters for two-component polyurethane coatings

A series of multiarm star hydroxyl-terminated polyesters (MHPs) were synthesized through a “one-pot” method with di-trimethylolpropane as the core molecule, 2,2-dimethylolpropionic acid as the AB₂-type monomer, ε-caprolactone, and monocarboxylic acids as modifiers. The influence of different monocarboxylic acids on the viscosities of polyesters and their 2K-PU films hardness was studied and it was found that MHPs prepared from lauric acid displayed the higher films hardness and lower viscosities. IR spectra of MHPs disclosed the ring-opening reaction between ε-caprolactone and hydroxyl groups occurred. ¹H NMR spectra demonstrated that the molecular structures of MHPs were irregular due to the multiplicity of reaction processes. The measured number-average molecular weights (M _n) of MHPs were around 715–1854 g/mol with the PDI of 1.45–2.05. MHPs exhibited lower viscosities in the range of 3304–9060 mPa s at 100% solid contents and possessed lower intrinsic viscosities compared with linear polymers of similar molecular weight. The cured films of MHPs exhibited excellent impact resistance, adhesion, flexibility, and high hardness and displayed good thermal stability with 5% weight loss at 280°C. The solution viscosities of MHPs were less than 450 mPa s at 80% solid contents, and the VOC contents of 2K-PU coatings obtained from MHPs were low to 300 g/L.     

Ionic polymers with tunable liquid‐crystalline properties

Side‐chain polyesters were synthesized from N‐octyl‐, N‐dodecyl‐ or N‐hexadecyl‐diethanolamine and succinic acid anhydride. These polyesters were then transformed into polyester hydrochlorides by protonation of the amino groups using different amounts of HCl (20–100 mol%). Above 60 mol% the reaction is not quantitative and a degree of protonation of up to 88% is obtained. The structures of the synthesized polyesters and their hydrochlorides were determined by ¹H nuclear magnetic resonance spectroscopy. The thermal properties of the synthesized polyesters and their hydrochlorides were also studied using differential scanning calorimetry in relation to the side‐chain length and the degree of polyester protonation. The polyester with octyl side chains and its hydrochlorides were amorphous liquids at room temperature, while the polyester and polyester hydrochlorides with hexadecyl side chains formed a smectic crystalline phase, S_mB, or its tilted analogues. The polyester with a dodecyl side chain was also an amorphous liquid at room temperature, while its hydrochlorides with various degrees of protonation were smectic liquid crystals, as determined by X‐ray diffraction. By simply varying the degree of protonation the liquid crystal isotropization temperature was increased from 32 °C to 82 °C. Copyright © 2011 Society of Chemical Industry     

Effect of glycol and filler types on some polymeric composite properties

Two unsaturated polyesters based on maleic anhydride, phthalic anhydride, and sebasic acid with each of linear 1,6‐hexanediol (PE_L) and cyclic 1,4‐cyclohexanediol (PE_C) were prepared. Their structures were characterized by IR and ¹H NMR spectra. Their composites were prepared by mixing different ratios (60, 70, and 80%) with talc and kaolin with polyester/styrene mixture. The effect of linear and cyclic glycols and the effect of filler type and concentration of these composites were studied in terms of their electrical properties and the hardness before and after aging. The thermal behavior of styrenated polyesters and their composites was studied using thermogravimetric analysis. It has been found that both fillers increase the thermal stability and decrease the weight loss. The permittivity ε′ and the dielectric loss ε″ were measured in the frequency range 100 Hz up to 100 kHz at room temperature 25°C ± 1. The polyester composite samples containing 70% filler lead to good electrical properties in addition to its resistance to thermal aging. The hardness value was increased by increasing the filler content before and after aging. The polyester composites based on cyclic glycol and loaded with 80% kaolin gave the highest hardness values. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008