Effect of hyperbranched poly(citric polyethylene glycol) with different polyethylene glycol chain length on starch sizing and compatibility with blended yarns

Blend of starch and water-soluble polyester has been widely used in warp sizing because of its good film-forming, biodegradability, and adhesion to polyester/cotton blended yarns (T/C). In this study, a series of hyperbranched polyesters poly(citric polyethylene glycol) (PCPEG) with varied chain length of polyethylene glycol (PEG) were prepared with citric acid and PEG at molar ratio of 1:3 and 150 °C for 3 h in vacuum and characterized by Fourier transformed infrared, gel permeation chromatography, and ¹H nuclear magnetic resonance. PCPEG blended maize starch (PCPEG/MS) as sizing agent of T/C 80/20 and effects of PEG chain length of PCPEG on the property of the blending sizing agent were studied. Results indicated PCPEG could improve the compatibility between starch and T/C 80/20 and the optimum content of PCPEG as blended sizing agent was 8%. PCPEG not only decreased apparent viscosity of MS paste but also increased viscosity stability of the paste. In addition, with increase of PEG chain length of PCPEG, viscosity stability of PCPEG/MS paste increased, but the value of all adhesion performances of T/C 80/20 after sizing decreased. Long chain of PEG is not good for compatibility between PCPEG and starch. The starch blending PCPEG has potential applications in sizing blended yarns in textile industry. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48928.     

Monophosphorylation of cornstarch to improve its sizing properties for heat‐sensitive wool yarns at reduced temperature

Commercial cornstarch was mono‐phosphorylated to different levels of substitution in order to investigate the effect of phosphorylation on the properties of cornstarch for sizing heat‐sensitive wool yarns at reduced temperature. The influences of starch phosphorylation and sizing temperature upon apparent viscosity and viscosity stability of cooked starch paste, starch retrogradation, adhesion to wool fibers, performance of starch film, aerobic biodegradation, mechanical properties, and hairiness of sized wool yarns were evaluated. The phosphorylation level was varied from 0.021 to 0.082 in degree of substitution (DS), while the temperature considered was from 60 to 95°C. It was found that mono‐phosphorylation of starch resulted in enhanced paste stability, reduced retrogradation, strong adhesion to wool fibers, increased performances of starch film, improved mechanical properties of sized wool yarns, and decreased hairiness on surface of sized yarns even if paste temperature was lowered to 60°C. Initially increasing phosphorylation level enhanced positive effects, but excessively increasing the level was not applicable due to marked reduction in tensile strength of starch film. The phosphorylation with a DS value of 0.061 could improve the performances of cornstarch for sizing wool yarns at 60–80°C. Moreover, measurement on BOD₅/COD ratios demonstrated that the phosphorylation did not impede aerobic biodegradation of starch. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of hyperbranched polyester‐amides and their application as crosslinkers for polyurethane curing systems

A series of hyperbranched polyester‐amides (S1, S2, S3) with trimethylolpropane as a core molecule were synthesized using core‐dilution/slow monomer addition strategy. The products were characterized by FTIR, ¹³C NMR, GPC, TGA, hydroxyl value measurement, and viscosity measurement. The result showed that the hyperbranched polyester‐amides synthesized had narrow molecular weight distribution and high degree of branching (DB). The hyperbranched polyester‐amides synthesized were used as crosslinkers for polyurethane curing systems and the mechanical properties of the polyurethane curing systems were investigated. It was found that the best tensile property and tear strength were obtained when the S2 were used as crosslinkers and the molar ratio of  OH and  NCO was 1 : 1. It was also found that the polyurethane curing systems had the highest hardness and T_g when the S3 were used as crosslinkers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

新型超支化聚酯对PVC力学及流变性能影响的研究

研究了BOLTORNTM型超支化聚酯对硬质聚氯乙烯(PVC)力学及流变性能的影响,并初步与传统加工助剂ACR进行了比较。结果表明,在100份的PVC中加入10份的超支化聚酯BOLTORNTMH40,材料的拉伸强度和断裂伸长率分别达到最大值39.58MPa和30.25%,拉伸强度比加入相同量的BOLTORNTMH20、H30要分别高4.2%、27.93%,而断裂伸长率则分别高400.1%、97.1%;在100份PVC中加入8份的超支化聚酯BOLTORNTMH20,材料的冲击强度达到最大值20.53kJ/m2;BOLTORNTM超支化聚酯与传统的加工助剂ACR相比,超支化聚酯对PVC有着更好的流变与塑化效果;另外,超支化聚酯可以降低PVC的黏度,随着超支化聚酯用量的增加,PVC黏度降低幅度增加。     

Cassava starch‐graft‐polymethacrylamide copolymers as flocculants and textile sizing agents

Cassava starch‐graft‐polymethacrylamide (PMAM) copolymers were synthesized by a free‐radical‐initiated polymerization reaction, and the products were tested for their efficiency as flocculants and textile sizing agents. The highest percentages of grafting and monomer conversion were 79.9 and 78.0%, respectively. The grafted starches were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. The average molecular weight of PMAM chains in the grafted starches ranged from 15.9 to 30.8 × 10⁵ g/mol. The grafted starches exhibited a higher peak viscosity and paste stability in comparison to the native starch (NS). Dynamic mechanical analysis showed that grafting provided fairly shear‐stable hydrogels, and the highest storage modulus obtained was 17,900 Pa compared to 1879 Pa for NS. The flocculation studies demonstrated the superiority of starch‐g‐PMAM over cassava starch and PMAM as an efficient flocculant. The tensile strength of cotton yarns sized with the starch‐grafted copolymer was significantly higher (104 MPa) compared to that sized with NS (34 MPa). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39810.     

Modal/涤纶混纺纱上浆工艺研究

根据Modal/涤纶混纺纱性能,制定出4种浆料配方,并对浆液及浆膜性能进行了测试分析。分别采用这4种配方的浆料对Modal/涤纶混纺纱进行浆纱试验,测试了不同配方浆纱的各项性能,从而得出适合Modal/涤纶混纺纱的浆料配方。     

聚酯水性化技术及水性聚酯稳定性研究进展

综述了4种含有不同亲水单体的聚酯水性化技术,包括传统型的以偏苯三酸酐为亲水性单体的水性聚酯、二羟甲基丙酸为亲水性单体的水性聚酯、紫外固化超支化水性聚酯以及磺酸盐型单体的水性聚酯。在此基础上,叙述了提高水性聚酯耐水解稳定性的方法及原理,并指出了水性聚酯的发展趋势。     

竹炭改性涤纶纱线的上浆工艺

针对竹炭改性涤纶纱线毛羽较多、耐磨性较差的缺点,制备了3种浆料配方,对各配方浆液及浆膜性能进行了测试分析;分别采用3种浆料配方对竹炭改性涤纶纱线进行浆纱试验,并测试了不同配方下浆纱的各项性能;通过对比分析,得出了适合竹炭改性涤纶纱线的浆料配方及上浆工艺。     

含氟超支化聚酯的合成及其性能研究

利用十三氟辛酸对超支化聚酯进行端基改性,得到了含氟超支化聚酯。采用傅里叶变换红外光谱仪、差示扫描量热分析仪等对聚合物进行了表征和分析。结果表明:十三氟酸成功接枝到超支化聚酯上,含氟超支化聚酯的玻璃化转变温度为-20.5℃,含氟超支化聚酯溶液在固含量高达70%时仍具有较低的黏度,该聚合物成膜性好,涂膜的附着力为1级,柔韧性为1 mm,铅笔硬度2 H,抗冲击强度4.9 J/cm2,与水的接触角为105°,具有良好的表面疏水性。     

Amphiphilic starch with 3-(trimethylammonium chloride)-2-hydroxypropyl and octenylsuccinyl substituents for strong adhesion to fibers

Amphiphilic starch derivatives with oleophilic octenylsuccinyl (OS) and hydrophilic 3-(trimethylammonium chloride)-2-hydroxypropyl (TMACHP) substituents were derived by the quaternization of acid-treated maize starch with N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride followed by the octenylsuccinylation with octenylsuccinic anhydride. Two series of amphiphilic starches with differential degrees of substitution (DS) and mole percentages of OS to the total substituents introduced onto the starch were characterized by elemental analysis, chemical titration, and FTIR spectroscopy. The effects of the DS and mole percentage on the adhesion of the starch to fibers were investigated using a legal method (FZ/T 15001-2008). The modification was able to significantly improve the adhesion of starch to cotton and polyester fibers due to the reduced surface tension of the cooked starch paste. The adhesion depended not only on the DS of OS and TMACHP substituents, but also on the mole percentage of the OS. The amphiphilic starch had superior adhesion to acid-treated and TMACHP-functionalized starches. The adhesion of the amphiphilic starch was found to reach its maximum at a mole percentage of 70.6% OS. An increase in the total DS reduced the surface tension and favored adhesion, but disfavored reaction efficiency. Based on the adhesion and reaction efficiencies, the amphiphilic starch with a total DS in the range of 0.029–0.051 and a mole percentage of 70.6% OS showed potential for use in warp sizing.     

Synthesis and Characterization of a Novel Low‐Viscosity Unsaturated Hyperbranched Polyester Resin

Hyperbranched thermosetting resin is the best additive for toughening and reinforcing linear thermosetting resin. A novel low‐viscosity unsaturated hyperbranched polyester resin (UHPR) is synthesized by the reaction between maleic anhydride monoisooctyl alcohol ester and a hydroxyl‐ended hyperbranched polyester resin (HPR) prepared from phthalic anhydride (PA) and trimethylolpropane (TMP). The structure of HPR is characterized by FT‐IR and ¹H NMR, and its degree of branching is deduced by comparing with the ¹H NMR spectrum of a model compound. The molecular weights of HPR and UHPR are determined by theoretical calculation and MALDI‐TOF MS measurements. This low‐viscosity (< 10 000 cP) novel UHPR can be applied in the field of environment‐friendly coatings and in toughening and reinforcing linear unsaturated polymers.     

Effect of Hyperbranched Poly (Trimellitic Anhydride Ethylene Glycol) Epoxy (HTME) on Thermal Degradation Activation Energies of HTME/Diglycidyl Ether of Bisphenol-A Epoxy Hybrid Resin by Kissinger and Flynn–Wall–Ozawa Method

The thermal degradation behavior and kinetics of hyperbranched poly (trimellitic anhydride ethylene glycol) epoxy (HTME)/diglycidyl ether of bisphenol-A epoxy (DGEBA) hybrid resin was investigated with thermogravimetric analysis (TGA) by using Kissinger method and Flynn–Wall–Ozawa method. The results show that the thermal degradation activation energies of DGEBA, 9 wt% HTME-1/91wt% DGEBA, 3 wt% HTME-2/97 wt% DGEBA, 9 wt% HTME-2/91 wt% DGEBA, 15 wt% HTME-2/85 wt% DGEBA, and 9 wt% HTME-3/91wt% DGEBA are 152.5, 144.4, 135.4, 133.2, 121.8 and 143.0 kJmol^?1, respectively, by Kissinger method. and the activation energies are 173.3, 165.0, 163.2, 151.7, 137.7 and 159.7 kJmol^?1, respectively by Flynn–Wall–Ozawa method. With the increase of HTME content, the activation energies of HTME/DGEBA hybrid resin decrease. Although molecular weight or generation of hyperbranched epoxy resins (HTME) has little effect on the thermal degradation activation energies and other kinetics data.     

Effect of amphiphilic phosphate/octenylsuccinate starch on enhancing adhesion to hydrophobic polyester fibers in sizing

Amphiphilic starch at different degree of substitution (DS) was prepared by phosphorylation and octenylsuccinylation of acid-thinned starch with sodium tripolyphosphate and 2-octenylsuccinic anhydride, respectively for improving the adhesion of starch to polyester fibers. Various assessment of starch such as ¹H NMR and FTIR analysis, apparent viscosity, starch clarity, adhesion to polyester fiber, desizing efficiency and biodegradability were conducted. The ¹H NMR and FTIR spectroscopy revealed that octenylsuccinate and phosphate substituents have been attached to the molecular chain of starch. Also, the apparent viscosity, paste clarity, desizing efficiency and biodegradability of the amphiphilic starch increased as the DS of phosphate increased. It was observed that the amphiphilic starch was an effective method for stronger adhesion unto polyester fibers but reduced at the highest DS of phosphate due to excessive hydrophilicity. As compared to acid-thinned starch, the stronger adhesion of the amphiphilic starch was attributed to the steric hindrance caused by the two substituents on starch and the good dispersibility impacted by the phosphate substituents on starch. Conclusively, the strongest adhesion on polyester fibers, good paste clarity, good desizing efficiency and enhanced biodegradability of starch were attained at phosphate and octenylsuccinate DS ratio of 0.031/0.014.     

Microwave irradiated synthesis of grafted cationic starch: Synthesis,characterization, application,and biodegradation

A biodegradable copolymer was synthesized by grafting copolymerization of acrylamide, β‐hydroxyethyl methacrylate, and n‐butyl acrylate onto corn cationic starch (CS) by microwave irradiation. The grafted cationic starch (GCS) was characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, and X‐ray diffraction. The optimum conditions on graft copolymerization with respect to reaction temperature, exposure time, and initiator concentration were investigated. Physicochemical properties of GCS, such as swelling power, solubility, intrinsic viscosity, and apparent viscosity, were studied, and its application performances as textile sizing agent were tested. Results showed that compared with CS, physicochemical properties of GCS were significantly improved, including decreased crystallinity, weakened granular, increased hydration capacity, and rheological property. Polyester/cotton blended yarns sized with GCS obtained more reinforced mechanical properties than samples sized with CS and exhibited higher tensile strength and abrasion resistance than polyvinyl alcohol (PVA) sized yarns. The mechanisms that the starch physicochemical properties affected on the sizing performances were discussed as well. Biodegradation analysis on these sizing agents showed that BOD₅/COD_cr of GCS was 0.263, which outclasses that of PVA (BOD₅/COD_cr = 0.009). This novel biomaterial could be expected to have promising applications especially in textile industry and be an ideal substitute for PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1645–1652, 2013     

氧化淀粉分子量分布对其性能的影响

淀粉氧化得到的产物是一种含有羧基的多糖,对金属离子有较强的络合能力。利用红外、扫描电镜和凝胶色谱对其结构、表面形貌和分子量分布进行了表征。研究了氧化时间对产物分子量分布及性能的影响。在配比为淀粉∶水=100∶500(g),温度85~90℃,时间160~180 m in,加碱量17 g,通氧量6~10 mL/m in时,相对去污力达到1.28。     

Modification of hyperbranched epoxy by vegetable oil-based highly branched polyester resin

Modification of existing polymers by physico-chemical technique is not only interesting and useful to the academic community but the resulted product is attractive to industrial application too. In this investigation, hyperbranched epoxy was modified by vegetable oil-based highly branched polyester resin at different weight percentages and properties of the cured systems were evaluated in order to justify them as advanced thin film materials with high adhesive strength. Modified systems were studied using FTIR, XRD, TGA and SEM analyses. Curing reaction was confirmed by FTIR study and swelling test. Performance characteristics like tensile strength, impact strength, adhesive strength, flexibility, scratch hardness, gloss and chemical resistance of cured films have also been studied. Modified systems showed improved properties over pristine epoxy. Comparison study of modified systems showed that hyperbranched epoxy with 30 wt% polyester content is the best composition w.r.t performance and might be utilized in advanced thin film application.     

Synthesis and Application of a Hyperbranched Polyester Quaternary Ammonium Surfactant

In the presence of the alkaline catalyst sodium hydroxide, the intermediate of hyperbranched polyester (H20Cl) was prepared by the modification of the hyperbranched polyester Boltorn H20 with epichlorohydrin. Then a new kind of quaternary ammonium functionalized hyperbranched polyester (H20C16 N) was synthesized by the reaction of H20Cl and hexadecyldimethylamine. The characteristics of H20C16 N were determined by FT‐IR, ¹H NMR and TGA. The molecular and molecular weight distribution of H20C16 N were determined by Gel Permeation Chromatography (GPC) and the surface activities of H20C16 N including surface tension (γ) and the critical micelle concentration (CMC) were measured at 25 °C. The H20C16 N reduced the surface tension of water to 30.81 mN/m at concentration levels of 7.94 × 10^?5 mol L^?1 and micellization free energies of the quaternary ammonium salt in its solution showed a good tendency towards adsorption at interfaces. The H20C16 N was applied to the silk fabric. An antimicrobial test of the treated fabrics against Escherichia coli and Staphylococcus aureus was carried out. SEM and XPS analysis were performed to study the dispersion of H20C16 N onto the fabric. All results exhibited excellent antibacterial properties of the hyperbranched polyester quaternary ammonium salt.     

Poly(citrate glyceride): a hyperbranched polyester for starch plasticization

Hyperbranched polyesters (HBPETs), terminated with either hydroxyl or carboxyl groups, were prepared from citric acid and glycerol in simple one‐step syntheses. The HBPET structure and degree of branching were investigated using Fourier transform infrared and ¹H NMR spectroscopies and gel permeation chromatography. The HBPET plasticizers were combined with a maize starch via cooking and film formation. The mechanical, thermal, paste and structural properties of the plasticized starch composites were studied in detail using differential scanning calorimetry, thermogravimetric analysis, rapid viscosity analysis and X‐ray diffraction. The HBPETs reduced the pasting viscosity but slightly increased the pasting temperature of the starch. The smaller breakdown and setback values of the plasticized starch pastes relative to those of native starch suggested weaker retrogradation. Compared with glycerol/starch plasticized films, HBPET/starch composite films had lower crystallinity, lower glass transition temperature and better mechanical and thermal properties. The properties of the plasticized starch samples strongly depended on the terminal groups and the molecular weight of the HBPET plasticizers. © 2017 Society of Chemical Industry     

Synthesis and characterization of glycerol-adipic acid hyperbranched polyesters

The structure and molecular weight of the hyperbranched polyesterification of adipic acid and glycerol were characterized by ¹³C NMR spectroscopy and size-exclusion chromatography as a function of reaction time and reaction stoichiometry. The glycerol substitution patterns and the extent of reaction of both glycerol and adipic acid were determined by NMR. The glycerol species concentrations determined by NMR were used with a Macosko–Miller conditional probability model to predict the hyperbranched polyester weight-average molecular weight. The model accommodated the difference in primary and secondary –OH reactivity and any substituent effects to glycerol –OH reactivity. In all cases, the predicted weight-average molecular weights were in excellent agreement with the absolute molecular weights determined by size-exclusion chromatography with light scattering detection.     

超支化聚酯型环氧树脂的合成及表征

用多元酸酐与环氧氯丙烷开环聚合制备了端羟基超支化聚酯,在碱作用下对羟基封端的超支化聚酯进行了闭环反应合成了超支化聚酯型环氧树增,研究了碱及碱的用量对闭环反应的影响,通过DSC考察了超支化聚酯型环氧树脂/邻苯二甲酸酐固化体系的固化行为,计算出固化过程的2个固化反应活化能Ea分别为64 35kJ/mol和91 12kJ/mol,频率因子lnA分别为21 8和26 8。