A post curing strategy toward the feasible covalent adaptable networks in polyacrylate latex films

The implementation of covalent adaptable networks (CANs) in general resin system is becoming attractive. In this work, we propose a simple post-curing strategy based on the core-shell structured acrylate latex for the achievement on both the improved general performance and the CANs characteristics in latex films. The building to the CANs was relied on the introduction of 4,4′-diaminophenyl disulfide as the curing agent, which cured the acetoacetoxy decorated shell polymer through the ketoamine reaction. The metathesis reaction of aromatic disulfides in the crosslinking segments enabled the thermally induced dynamic behavior of the network as revealed in the stress relaxation tests by comparison with other diamine crosslinking agents without the incorporation of disulfide. The synergism of the dynamic crosslinking of the shell polymer and static crosslinking in the core polymer contributed to the improved mechanical strength (15 MPa, strain% = 250%) and the suppressed water adsorption (~1% in 24 h of soaking) of the latex film, which exhibited above 90% of recovery in both strength and strain from a cut-off film damage within 1 h at 80°C. Moreover, the cured latex film could be recycled, and 75% of the mechanical performance was regained after three fragmentation-hot-pressing cycles. These, in addition with the feasible and environmental friendly characteristics, suggest a sustainable paradigm toward the smart thermosetting latex polymers.     

Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base

A stable and efficient Pd(OAc)₂/PPh₃/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)₂ and PPh₃, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)₂/PPh₃/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.     

铁铝催化体系催化丙烯酸丁酯聚合

研究了Fe(acac)3-Al(i-Bu)3-8-羟基喹啉(acac=乙酰丙酮)催化体系催化丙烯酸丁酯(BA)聚合，考察了聚合规律，用凝胶渗透色谱研究了聚合物分子量和分子量分布．动力学研究表明聚合反应对单体浓度呈一级关系，表观活化能为13．9kJ／mol．     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Diffraction grating in noncrosslinked polymers

The diffraction efficiency and morphology of the transmission modes of holographic polymer dispersed liquid crystals were studied with respect to the molecular structure of poly(urethane acrylate) (PUA), the film (polymer/liquid crystal) and resin (oligomer/monomer) compositions, and the cell thickness. PUA, based on N‐vinylpyrrolidone and ethyl hexyl acrylate, with low‐molecular‐weight poly(propylene glycol) at a low oligomer content, showed high diffraction efficiency. The results were interpreted in terms of the monomer reactivity and polymer elasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 613–620, 2004     

Determination of residual monomers in acrylate dispersions by gas chromatography

The content of residual monomers is one of the most important characteristics of polymer dispersions. As a result of the similar physicochemical parameters of ethyl acrylate and methyl methacrylate, it is very difficult to determine the residual monomers in acrylate dispersions obtained by emulsion polymerization of both monomers. Gas chromatography with capillary columns, however, permits separation of these monomers and their quantitative determination in acrylate dispersions.     

聚丙烯酸长链酯的Huggins常数与其分子量的依赖性关系

聚丙烯酸高碳醇酯(PBA)及聚丙烯酸十八醇酯(POA)是具有长烷基侧链的梳状聚合物,在溶剂苯中的Huggins常数(k′)随其分子量(M)的变化而变化.在PBA-苯体系中发现,当M低于某一临界分子量(MLC)时,k′随分子量的降低显著增大;当M大于某临界分子量(MHC)时,k′随分子量的升高而增大;当M在MLC～MHC时,k′基本上保持不变.而在POA-苯体系中发现,当M低于某一临界分子量(MC)时,k′随分子量的降低显著增大;当M大于该临界分子量(MC)时,k′在0.33～0.43变化.文中同时给出了精确算法用来计算PBA-苯体系及POA-苯体系中PBA及POA的特性粘度.当k′＞0.758时,用稀释外推法计算;当0.758＞k′＞0.426时,用一点法公式[η]=ηsp/C(√)ηr计算;当0.426＞k′＞0.334时,用另一一点法公式[η]=(√)2(ηsp-lnηr)/C计算.     

修饰聚合物液-固亲和萃取体系纯化大豆中的组氨酸

聚乙二醇(PEG)6000经亚氨基二乙酸(IDA)修饰后和CuSO4反应,形成PEG修饰聚合物PEG-(IDA-Cu)2 ,与吐温80、磷酸盐混合,构成液-固亲和萃取体系,直接从大豆蛋白匀浆中提取氨基酸.选定萃取条件为磷酸盐摩尔比n(K2HPO4)∶n(NaH2PO4)为4.8∶1,体系pH值 7.70,总盐浓度为1.60 mol·L-1;吐温80的体积分数为10.5%.结果表明该体系对大豆蛋白匀浆中氨基酸的二次萃取率为66.5%,用离子交换技术后继处理,得纯度较高的组氨酸.     

Synthesis of side‐chain liquid‐crystalline homopolymers and triblock copolymers with p‐methoxyazobenzene moieties and poly(ethylene glycol) as coil segments by atom transfer radical polymerization and their thermotropic phase behavior

A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 10³ to 20.6 × 10³ with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 10³ to 1.7 × 10⁴ and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with ¹H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003     

Synthesis and characterization of 6‐ and 12‐arm star polymers by nitroxide‐mediated radical polymerization of St and MA from dendritic TIPNO‐based hexafunctional and dodecafunctional macroinitiators

Dendritic multifunctional macroinitiators having six and 12 TIPNO‐based alkoxyamines, TIPNO‐6 and TIPNO‐12 , were synthesized and used in the living radical polymerization of styrene (St), methyl acrylate (MA), N,N‐dimethylacrylamide (DMAAm), and isoprene (IP). The polymerizations of St initiated with TIPNO‐6 gave 6‐arm star polymers with narrow polydispersities of 1.14–1.18. In the polymerizations of MA initiated with TIPNO‐6 and TIPNO‐12 , the influences of added TIPNO on the polydispersity indexes (PDIs) of the resulting star polymers were first investigated, and this led to the successful formation of poly(MA) star polymers with narrow polydispersities (1.10–1.18). Moreover, the polymerizations of DMAAm and IP from TIPNO‐6 in the presence or absence of TIPNO were briefly investigated. The benzyl ether bonds of the poly(St) and poly(MA) star polymers were cleaved by treating with Me₃SiI or Pd/C, and the resulting arm's parts were analyzed with SEC. The PDIs of the resulting arm parts were low (1.19–1.23), and the M_ns agreed with the M_n,theor, indicating that the poly(St) and poly(MA) star polymers had well‐controlled arms. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4364–4376, 2007