Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

异氰酸酯改性光敏水性环氧丙烯酸酯的合成

以双酚A型环氧树脂与丙烯酸反应合成了具有羟基侧基的环氧丙烯酸酯，再用甲苯二异氰酸酯与内烯酸-β-羟乙酯的半加成物对上述环氧丙烯酸酯树脂进行接枝改性，再用酸酐引入羧基，经胺中和后，水性化．可得较为稳定的自乳化光敏树脂水分散体系。通过化学测试和IR解析．确定了合成条件、合成终点及产物结构，并以此为基料配成紫外光固化涂料，所得涂层性能优异。     

聚硅氧烷-丙烯酸酯共聚物互改性产物的表面特性

通过测定参照液体在固体表面的接触角，计算固体的表面能及固体／液体接触体系的粘附功，考查了聚硅氧烷-丙烯酸酯共聚物互改性产物的表面特性及其对粘接性能影响。     

Different effects of tri(acryloyloxyethyl) phosphate on the thermal degradation of photopolymerized epoxy acrylate and polyurethane acrylate films

Tri(acryloyloxyethyl) phosphate (TAEP) was blended in different ratios with epoxy acrylate EB600 and polyurethane acrylate EB270 to obtain a series of UV curable flame retardant resins. The thermal degradation mechanisms of their cured films in air were studied by thermogravimetric analysis, in situ Fourier‐transform infrared spectroscopy, and direct pyrolysis/mass spectrometry measurements. The results showed that the phosphate group in TAEP first degraded to form poly(phosphoric acid) before the degradation of EB600. Then, the formed poly(phosphoric acid) effectively promoted the conversion of EB600 to form char, which prevented the sample from further burning. However, urethane group in EB270 degraded simultaneously with phosphate group in TAEP, leading to not effectively increase the conversion of EB270 to char during the thermal degradation. It was thus found that the addition of TAEP more effectively improved the thermal stability, flame retardance, and the char yield during combustion of EB600 than those of EB270. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3130–3137, 2006     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

Synthesis of polyethylene oxide end‐capped with perfluoroalkyl groups/polystyrene prototype brushes

Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free‐radical copolymerization of methacryloyl‐terminated PS and α‐vinylbenzyl‐ω‐hydroxy or α‐vinylbenzyl‐ω‐perfluoroalkyl (R_f) PEO macromonomers with the addition of Lewis acid (SnCl₄). It was found from their dilute‐solution properties that PS/PEO end‐capped with R_f (PBR_f), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N‐dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBR_f‐type brush by chemical modification, using corresponding acid chloride. The substitution of R_f groups was ～70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006     

High resolution solid state 13C n.m.r. of butadiene grafted polypropylene

¹H dipolar decoupled ¹³C n.m.r. experiments with the aid of the magic angle spinning technique have been used to determine the graft content and the isomer content of the polybutadiene grafts in a graft copolymer with isotactic polypropylene.     

氯化聚丙烯改性胶粘剂的合成及粘附性能研究

以甲苯为溶剂，过氧化二苯甲酰(BP0)为引发剂，通过自由基聚合，采用甲基丙烯酸羟乙酯(HEMA)和苯乙烯(St)接枝改性氯化聚丙烯(CPP)。研究了不同苯乙烯用量、不同反应温度、不同反应时间、不同引发剂用量对改性氯化聚丙烯胶粘剂粘附性能的影响，得出较佳的工艺条件为反应温度90℃，反应时问2h，原料配比m(CPP)：m(HEMA)：m(St)：m(BPO)=50：0．5：0．6：0．15。     

SIS-g-AN热降解性能的研究

采用热重分析法和差示热重分析法研究丙烯腈(AN)接枝热塑性弹性体SIS(SIS g AN)的热降解性能。结果得出,SIS g AN的平衡起始降解温度、平衡最大降解速率温度和平衡终止降解温度分别为659. 17, 713. 94 和740.05 K;热降解反应活化能为195.2 kJ·mol-1;热降解机理是Deceleration中的D3 降解机理;不同质量损失率下的热寿命与温度呈线性关系。     

A new core–shell type fluorinated acrylic and siliconated polyurethane hybrid emulsion

A novel core–shell type fluorinated acrylic and siliconated polyurethane (FSiPUA) hybrid emulsion was prepared by seeded emulsion polymerization using siliconated polyurethane (SiPU) as a seed and forming the structure with SiPU as a shell and the copolymer of butyl acrylate (BA) with 2,2,2-trifluoroethylmethacrylate (TFEMA) as a core. SiPU was synthesized using isophorone diisocyanate (IPDI), polytetramethylene ether glycol (PTMG), polypropylene glycol (PPG), dihydroxybutyl-terminated polydimethylsiloxane (PDMS), dimethylol propionic acid (DMPA), 1,6-hexanediol (HDO) and triethylamine (TEA). The contents of siloxane and fluorine were determined according to the feed ratio. Fourier transform infrared spectroscopy (FTIR) was used to identify the chain structure of SiPU and FSiPUA. Investigation of transmission electron microscopy (TEM) confirmed the core–shell structure of FSiPUA emulsion and gave the particle size at about 50 nm. The measurement results of water contact angles and the solvent absorptions in water and n-octane for cured films showed that the water and the oil repellency for FSiPUA had been improved significantly with a suitable content of fluorine and siloxane.