An oxidative batchwise shrink-resist treatment for wool using monoperoxyphthalic acid

The effectiveness of three oxidising agents have been compared in a batchwise process for conferring wash fastness to wool in the form of tops, knitting yarn and knitted and woven cloth. The three were dichloroisocyanuric acid (DCCA), peroxymonosulphuric acid (PSA) and monoperoxyphthalic acid. DCCA, the commonly used agent for batch shrink-resist treatments, reacts so rapidly as to cause unevenness. It also tends to harden and yellow the fibres and so is usually used at low application rates, as a pretreatment before the application of a resin. It contributes to the presence of organic halides in effluent (AOX). Neither PSA nor monoperoxyphthalic acid suffered from these deficiencies, but PSA could only be used successfully for woven cloth, unless applied with resins. Monoperoxyphthalic acid was effective for wool in all its forms, without subsequent resin treatment. However, it is not available in commercial quantities, so a simple process for preparing it cheaply from phthalic anhydride and hydrogen peroxide has been developed. It can be applied after dyeing with Lanaset dyes without significant shade change.     

Graft copolymers with hydrophilic and hydrophobic polyether side chains

Poly(ethylene glycol)methyl ether methacrylate (PEOMA) and oligo(propylene glycol)-4-nonylphenyl ether acrylate (OPOPhNA) were copolymerized by atom transfer radical polymerization (ATRP). Grafting through method was employed in the presence of CuBr/HMTETA or CuBr/PMDETA catalyst/ligand complex in anisole at 70 °C. It yielded a heterografted copolymers containing hydrophilic PEO and hydrophobic OPOPhNA side chains with polymerization degree DP = 68-315 in the presence of PMDETA and DP = 48-195 in the presence HMTETA. Moreover, higher reactivity of PEOMA than OPOPhNA (r_methacrylate > r_acrylate), which was observed during copolymerization, suggested the formation of copolymers with a spontaneous gradient composition starting from the grafted segment of P(PEOMA). The molecular weight distribution (MWD) was increased with DP in the range 1.2-1.6. The X-ray diffraction analysis (WAXS) indicated that larger number of PEO segments generated crystalline properties in the copolymers with amorphous OPOPhNA.     

Highly conductive polyaniline copolymers with dual-functional hydrophilic dioxyethylene side chains

We investigated new highly conductive polyaniline copolymers bearing a small amount of dual-functional hydrophilic dioxyethylene side chains, which can act as a stabilizer in a heterogeneous dispersion medium in polymerization and a reactive dispersant in polar solvents. Compared to the unsubstituted polyaniline, new polyaniline copolymers maintained their high electrical conductivity of 485 S/cm with camphorsulfonic acid dopant in m-cresol. Moreover, in the alcoholic butoxyethanol solvent with a dodecylbenzenesulfonic acid dopant, new polyaniline copolymers showed enhanced dispersion abilities with very small particle sizes of <10 nm and exhibited a high electrical conductivity of 13 S/cm, which is significantly higher than polyanilines in an organic aliphatic alcoholic solvent (10⁻⁶∼1 S/cm). Therefore, new polyaniline copolymers are very interesting materials for electronic applications.     

Synthesis and characterization of N-phenylmaleimide-methylvinylisocyanate copolymers with polystyrene side chains

Summary N-Substitued maleimide-methylvinylisocyanate copolymers with high glass transition temperature (T_g) was prepared and reacted with 4-hydroxy TEMPO (4-hydroxy-2,2,6,6-tetramethyl piperidinoxy) to yield polymers possessing stable radical at the side chain. The resulting polymers behaved as polymeric counter radicals for the radical polymerization of styrene. Thus, stable free radical mediated polymerization at the side chain was achieved. The resulting graft copolymers were characterized by spectral and thermal analysis. Received: 6 October 1999/Revised version: 7 March 2000/Accepted: 7 March 2000     

Developing a zero-AOX shrink-resist process for wool. Part 1: Preliminary results

The efficiency of the proteolytic enzyme papain in conferring shrink-resistance to wool tops and woven fabrics has been enhanced by pretreatment of the wool with lipase/sodium monoperoxyphthalate/sodium sulphite. This process may be considered as a zero-AOX shrink-proofing treatment. The wool samples treated with this system show excellent shrink-proofed properties. Infrared spectroscopy and X-ray photoelectron spectroscopy showed that the Buntë salt together with low concentrations of cystine monoxide and cystine dioxide are formed in the course of the reaction. Studies of the surface of the treated wool using scanning electron microscopy have shown the complete absence of wool scales. A mechanism is proposed for shrink resistance in the lipase/sodium monoperoxyphthalate/papain treatment.     

Amphiphilic block copolymers with pendant thiol groups in side chains by RAFT polymerization

A new synthetic approach to thiol functional, well-defined amphiphilic block copolymers, which can be used to prepare multifunctional polymers and polymeric nanoparticles, is presented. Starting with a hydrophilic macroRAFT transfer agent and hydrophobic (meth)acrylate monomers that possess protected thiol groups, amphiphilic block copolymers are prepared in high yield. It is proven that the protected thiol groups in the monomer do not interfere with the RAFT polymerization process. Polymers with defined molecular weight, narrow polydispersities (PDI < 1.30) and varying length of the hydrophobic block are presented. Polymers with thiol groups in side chains and chain ends are obtained by aminolysis. With pyrene fluorescence spectroscopy and NMR measurements, it is shown that all synthesized polymers self-assemble into micelles. Furthermore, the possible application of these new polymers is exemplified by the preparation of polymer nanoparticles.     

PEGylated polylysine derived copolymers with reduction‐responsive side chains for anticancer drug delivery

Reduction‐responsive drug delivery systems have recently gained intense attention in intracellular delivery of anticancer drugs. In this study, we developed a PEGylated polypeptide, poly(ethylene glycol)‐block‐poly(?‐propargyloxycarbonyl‐l ‐lysine) (PEG₁₁₃‐b‐PPAL), as a novel clickable substrate for conjugation of reduction‐responsive side chains for antineoplastic drug delivery. PEG₁₁₃‐b‐PPAL was synthesized through ring‐opening polymerization of alkyne‐containing N‐carboxyanhydride monomers. A designed disulfide‐containing side chain was introduced onto the PEGylated polypeptide by click reaction. The obtained copolymer PEG₁₁₃‐b‐P(Lys‐DSA) formed micelles by self‐assembly, which exhibited reduction‐responsive behavior under the stimulus of 10 mmol L^–1 glutathione (GSH) in water. A small molecule intermediate, compound 2 , was used as a model to investigate the thiol reduction mechanism of PEG₁₁₃‐b‐P(Lys‐DSA) copolymers. The anticancer drug doxorubicin (DOX) was then loaded into the micelles with a drug loading content of 6.73 wt% and a loading efficiency of 40.3%. Both the blank and the drug‐loaded micelles (DOX‐loaded polylysine derived polymeric micelles (LMs/DOX)) adopted a spherical morphology, with average diameters of 48.0 ± 13.1 and 63.8 ± 20.0 nm, respectively. The in vitro drug release results indicated that DOX could be released faster from the micelles by the trigger of GSH in phosphate buffered saline. Confocal laser scanning microscopy and flow cytometer analysis further proved the intracellular delivery of DOX by LMs/DOX and their GSH‐sensitive release behavior. A 3‐(4,5‐dimethyl‐thiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide assay showed that the polymers exhibited negligible cytotoxicity towards normal L929 cells or cancer MCF‐7 cells with a treated concentration up to 1.0 mg mL^–1. In conclusion, our synthesized biocompatible and biodegradable PEGylated polypeptides hold great promise for intracellular antineoplastic drug delivery. © 2019 Society of Chemical Industry     

含聚氧乙烯支链的两亲性(丙烯酸丁酯-甲基丙烯酸甲酯)接枝共聚物的性能

由聚氧乙烯(PEO)大单体与丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)合成含PEO支链的两亲性(BA-MMA)三元接枝共聚物,对该共聚物的乳化性、吸水性和物理机械性能进行了研究.结果表明,合成的共聚物具有良好的乳化性及吸水性,并在一定组成下呈现热塑性弹性体的性质.     

Poly(p-phenylene) graft copolymers with polytetrahydrofuran/polystyrene side chains

1,4-Dibromo-2,5-bis(bromomethyl)benzene was used as a bifunctional initiator in cationic ring opening polymerization (CROP) of tetrahydrofuran. The resulting macromonomer, with a central 2,5-dibromobenzene ring, was reacted in combination with 2,5-dihexylbenzene-1,4-diboronic acid by a Suzuki coupling, in the presence of Pd(PPh₃)₄ as catalyst, leading to a poly(p-phenylene) (PPP) with alternating polytetrahydrofuran (PTHF) and hexyl side chains. A polystyrene (PSt) based macromonomer with a central benzene ring bearing cyclic boronic acid propanediol diester groups, synthesized by atom transfer radical polymerization (ATRP), was also used as partner for PTHF in the cross-coupling reaction. A PPP with alternating PSt and PTHF side chains was obtained. PTHF macromonomer was also homopolymerized by a Yamamoto reaction. The resulting PPPs have high solubility in common organic solvents at room temperature. The new polymers were characterized by GPC, ¹H NMR, ¹³C NMR, IR and UV analysis. Thermal behavior of the precursor PTHF macromonomer and the final polyphenylenes were investigated by TGA and DSC analyses and compared.     

Toughening of cycloaliphatic epoxy resin improved by reactive copolymers with flexible alkyl side chains

Reactive copolymers with flexible alkyl side chains were used as modifiers to improve the toughness of a cycloaliphatic epoxy resin. In this study, we used three types of copolymers with different alkyl chain length (C₄H₉, C₆H₁₃, and C₁₀H₂₁). As a result, the system with an added copolymer having the longest alkyl chain length (C₁₀H₂₁) formed a phase separation structure. The addition of this copolymer (C₁₀H₂₁) led to a 50% increase in the fracture toughness (K_IC) of the cured resin at the slight expense of its glass transition temperature. Scanning electron microscope observations in the vicinity of a crack tip after a compact tension test showed that cavitation of the dispersed phase occurred. The crack growth was inhibited and thus the toughness was improved due to the plastic deformation of the epoxy matrix followed by cavitation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A new grafting monomer for synthesizing long chain branched polypropylene through melt radical reaction

A grafting monomer (p-(3-butenyl)styrene, BS)) containing two carbon–carbon double-bonds with different reactivity was used in melt radical reaction to prepare long chain branched polypropylene (LCB-PP). High-temperature size-exclusion (HT-SEC) coupled with triple detectors, rheometer and NMR were used to characterize the microstructure of the resultant LCB-PP. BS showed double functions in mediating radical reaction, i.e. stabilizing macroradicals and promoting branching reaction. Compared to styrene and divinylbenzene, using BS as a grafting monomer led to the formation of more uniformly distributed LCB structure on the PP backbone. Thus the resultant sample showed strain hardening in extensional flow and had high melt strength.     

DNA with branched internal side chains: synthesis of 5-tripropargylamine-dU and conjugation by an azide-alkyne double click reaction

5-Tripropargylamine-2'-deoxyuridine (1 a) containing two terminal triple bonds was synthesized by a Pd-assisted Sonogashira cross-coupling reaction and was subsequently converted into the corresponding phosphoramidite building block (9) and employed in solid-phase oligonucleotide synthesis. T(m) experiments demonstrate that the presence of covalently attached branched tripropargylamine residues has a positive effect on the base pair stability. The two terminal C[triple chemical bond]C bonds of modified DNA were functionalized by means of Cu(I)-mediated 1,3-dipolar cycloaddition reactions (click chemistry) with azides such as 3-azido-7-hydroxycoumarin or 3'-azido-3'-deoxythymidine (AZT) both in solution and on solid support. In particular, with the nonfluorescent 3-azido-7-hydroxycoumarin a strongly fluorescent oligonucleotide bis-dye conjugate was generated. For comparison, the N(3)-propargylated 2'-deoxyuridine 2 was prepared from 2'-deoxyuridine and propargyl bromide and incorporated into DNA. The two terminal triple bonds of 1 a allow the simultaneous post-modification of DNA by two reporter molecules and can be applied to almost any azido derivatives (oligonucleotides, proteins, polysaccharides etc.) including those forming dendrimeric side chains.     

pH responsive polymers with amino acids in the side chains and their potential applications

Design and synthesis of pH responsive polymeric materials has become an important subject in academia as well as in industrial field in recent years due to their applications in diverse field including controlled drug delivery, biomedical applications, membrane science, sensors and actuators, oil recovery, colloid stabilization, etc. Efforts have been made to incorporate stimuli‐responsive biomolecules in synthetic polymers to develop pH responsive “smart” non‐biological hybrid macromolecules with high water solubility, enhanced biocompatibility, bio‐mimetic structure and properties. This review is focused on the recent advances in side‐chain amino acid‐based pH responsive polymers synthesis and potential application aspects of these macromolecular architectures in drug and gene delivery, and other fields. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41084.     

Structure and gas sorption properties of an aromatic polyamide with long alkyl side chains

An aromatic polyamide with long alkyl side chain, A‐C12, was synthesized from the condensation of 1,4‐didodecylester of pyromellitic acid and p‐phenylenediamine to clarify the relationship between its higher order structure and gas sorption properties. A‐C12 formed a layered structure composed of alternating rigid aromatic main chain layers and flexible dodecyl side chain layers. This polyamide could be imidized by the usual imidization method. Imidized A‐C12 could not keep the layered structure of A‐C12. CO₂ sorption of A‐C12 occurred only in the side chain layer region, which is almost a liquid‐like environment, and the sorption isotherms obeyed Henry's law. This result also indicates that the main chain layer is very dense and cannot sorb CO₂. On the other hand, imidized A‐C12 showed a large sorption amount of CO₂ and dual mode sorption, despite high density, meaning imidized A‐C12 does not contain a layered order structure but an amorphous glassy state. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1771–1775, 2005     

含均匀聚氧乙烯支链的两亲性(丙烯酸丁酯-甲基丙烯酸甲酯)共聚物的结构及结晶性

由聚氧乙烯(PFO)大单体、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)共聚合成的产物经水及乙醚/丙酮(体积比3/7)分别萃取得取了纯化的两亲性接枝共聚物,用凝胶渗透色谱仪、红外光谱仪、核磁共振仪对接枝共聚物进行了表征,用蒸气渗透压计、膜渗透压计、X射线衍射仪及偏光显微镜研究了接枝共聚物的结构参数平均相对分子质量(M-nb)为9.1×103～15.2×103;随着共聚时间的延长,Ng有所下降,M-nb有所增加,接枝共聚物的结晶度为0～49.5%,且随着PEO含量及其相对分子质量的增加而增大;接枝物呈现球晶结构,且随着PEO含量的减少,球晶变小且不规整.     

A new kinetic model for wool dyeing

Previous kinetic models of the dyeing process are reviewed in an attempt to describe the exhaustion profile of acid dyes on wool fibres. A new kinetic model is proposed that describes the dye uptake throughout the whole kinetic period, and that takes into account the amount of dye and acid supplied at the beginning of dyeing. The equation is used to achieve isoreactive dyeing by calculating the amount of dye to add during the dyeing process.     

Synthesis and characterization of amphiphilic graft copolymers with poly(ethylene glycol) and cholesterol side chains

Amphiphilic graft copolymers comprising monomeric units of methoxy poly(ethylene glycol) (mPEG)-acrylate, 2-hydroxyethyl methacrylate (HEMA)–cholesterol conjugates and HEMA were synthesized and their properties characterized. The value of the critical micelle concentration (CMC) for these copolymers is linearly proportional to the ratio of the number of mPEG–acrylates to that of the HEMA–cholesterol conjugates per macromolecule (N_PEG/N_c), which is the most important parameter which influences the formation of polymeric micelles. The latter show excellent colloidal stability and their sizes decrease with increasing CMC. Based on the quenching of pyrene fluorescence, the relatively high levels of the loading capacity of pyrene are attributed to the elevated hydrophobicity of the micelle core. The loading capacity of pyrene decreases with increasing CMC. The weight-average partition coefficient for pyrene in polymeric micelles increases with increasing polymer concentration because more micelles are available for accommodating pyrene. Copyright © 2004 Society of Chemical Industry     

Synthesis,photophysical properties and microphase separation of all‐conjugated diblock copolymers with hydrophilic side chains

A series of new all‐conjugated diblock copolymers, poly(2,5‐dioctyloxy‐p‐phenylene)‐block‐poly(3‐methoxyethoxyethoxy‐methylthiophene) (PPP‐b‐P3MEEMT), with hydrophilic side‐chains have been synthesized by quasi‐living Grignard metathesis polymerization. The narrow polydispersity indices of the block copolymers are in the range 1.32–1.40. The block ratios in the obtained diblock copolymers can be well defined by the feed ratios of the monomers. Photoluminescence results reveal that resonance energy transfer occurs from the PPP block to the P3MEEMT block in dilute solution. Differential scanning calorimetry shows that both PPP and P3MEEMT blocks in the copolymers produce crystalline regions and lead to microphase separation as indicated by two endothermal transitions, corresponding to the melting peaks of the PPP and P3MEEMT blocks, respectively. The formations of microphase‐separated nanostructures in annealed copolymer films are also observed using transmission electron microscopy. © 2012 Society of Chemical Industry     

侧链带脲基的β-氨基酸的设计合成

以廉价的L-天冬氨酸为原料,成功设计合成了3个侧链带脲基的Boc保护的新的β-氮基酸.在分别对L-天冬氨酸的β-位羧基和氨基保护后,将其α-位羧基转化为酰基叠氮,该酰基叠氮经Curtius重排,成功得到合成脲的重要中间体异氰酸酯.所选取的胺都能与异氰酸酯迅速作用,得到期望的目标化合物,这些目标化合物结构经核磁氢谱、质谱确证.     

New alternating copolymers of fluorene and triphenylamine bearing terthiophene and acceptor groups in the side chains: Synthesis and photovoltaic properties

A series of conjugated copolymers (P1 and P2-CN-P4-CN) were prepared, in which two kinds of side chains were designed: one was the repeating units similar to that of P3HT, with the aim to increase the compatible with PC₆₁BM and the hole mobility; another one was the acceptor groups connected with the electron-rich backbone through the conjugated 3,4-ethylenedioxythiophene bridge, in order to broaden the absorption and lower the LUMO level. By controlling the ratios of these two kinds of side chains, the absorption band of the resultant conjugated polymers could be fine-tuned, while their energy levels nearly remained unchanged. As the result, the performance of the corresponding devices increased first, then decreased, indicating that there would be a balance between the different function of these two side chains.