2—乙烯基—2—恶唑啉的合成及聚合

通过亚氨酸酯合成了２－乙烯基－２恶唑啉（ＶＯＺＯ）单体。对合成过程中溶剂及分离问题进行了讨论,ＶＯＺＯ在苯溶液中自由基聚合生成聚乙烯基恶唑啉（ＰＶＯＺＯ）,用元素分析和红外光谱表征的方法,证实了所得单体和聚合物的分子结构;发现聚合物ＰＶＯＺＯ为分子中仍保有恶唑啉侧基的对水和有机溶剂都有着良好溶解性的线型大分子。     

2—乙烯基—2—恶唑啉的合成及聚合

通过亚氨酸酯合成制备了２－乙烯基－２－恶唑啉（ＶＯＺＯ）单体，对合成过程中的溶剂及分离等问题进行了讨论、进一步在苯溶液中自由基聚合ＶＯＺＯ得到聚乙烯基恶唑啉（ＰＶＯＺＯ）。用元素分析和红外光谱表征的方法，证实了所得单体和聚合物的分子结构；发现聚合物ＰＶＯＺＯ为分子中仍保留有恶唑啉环侧基，对水和有机溶剂都有着良好溶解性的线型大分子。     

2-乙烯基-2-噁唑啉的合成及聚合

通过亚氨酸酯合成制备了２－乙烯基－２－唑啉（ＶＯＺＯ）单体，对合成过程中的溶剂及分离等问题进行了讨论；进一步在苯溶液中自由基聚合ＶＯＺＯ得到聚乙烯基唑啉（ＰＶＯＺＯ）。用元素分析和红外光谱表征的方法，证实了所得单体和聚合物的分子结构；发现聚合物ＰＶＯＺＯ为分子中仍保留有唑啉环侧基，对水和有机溶剂都有着良好溶解性的线型大分子。     

双—2—恶唑啉化合物对PET的改性作用研究

用挤出机熔融共混物法，比较了２，２′－双（２－恶唑啉），１，４－双（２－恶啉唑）苯和１，３－双（２－恶唑啉）苯３种双恶唑啉化合物ＰＥＴ端羧基进行偶联反应和封端反应的程度和差别，并考查双恶唑啉助剂加入量，挤出温度与时间，后热对扩链效果的影响，以及研究扩莲后ＰＥＴ的热失重，水解稳定性，力学性能及＾１３Ｃ～ＮＭＲ分析。结果表明，经恶唑啉化合物扩链的ＰＥＴ增进了热稳定性和耐水解性，提高玻纤增强ＰＥＴ的力学     

2-乙基-2- 唑啉的阳离子开环聚合及聚合物的表征

以对甲苯磺酸甲酯为引发剂进行２乙基２唑啉阳离子开环聚合研究，主要考察了不同的单体／引发剂配比、聚合温度和聚合时间对聚合转化率和聚合物分子量的影响。聚合物通过ＩＲ、１Ｈ核磁共振、ＤＳＣ进行表征，并考察了聚（２乙基２唑啉）与部分聚合物和共聚物的共混性能。     

3-取代苯基-5-羟基-5-三氟甲基异噁唑啉的合成

3 取代苯基 5 羟基 5 三氟甲基异口恶唑啉是合成具有异口恶唑结构的原卟啉原氧化酶抑制剂类除草剂的重要中间体。通过以下途径制得4个具有不同取代基的异口恶唑啉中间体:首先,在回流状态,n(甲醇钠)∶n(取代苯乙酮)=2∶1的甲醇钠存在下,取代苯乙酮与三氟乙酸乙酯缩合得到取代苯基 4,4,4 三氟 1,3 丁二酮;后者可在室温下,于二氯甲烷溶剂中,用氯化硫酰氯化,在侧链上引入氯原子;最后,以乙酸作溶剂,回流下,具有不同取代基的苯基 1,3 丁二酮与盐酸羟胺闭环得到产物。反应总收率大于95%。产品结构经质谱、核磁共振氢谱、碳谱确认正确。     

双恶唑啉化合物偶联聚酯的研究：聚对苯二甲酸丁二酯的偶联反应

报告双恶唑啉化合物（ＢＯＺ）对聚对苯二甲酸丁二酯（ＰＢＴ）的偶联扩链的研究结果，表明与偶联聚对苯二甲酸乙二酯（ＰＥＴ）一样，特性粘数（［η］）在３￣６ｍｉｎ迅速达到极大值，随后缓慢下降，ＰＢＴ熔点较低，故此反应可在较低温度下进行，偶联效率与ＰＥＴ的结果相近，以丁二酸为模型化合物考察表明偶联作用是在羧基进行，同时反应的最低温度可至１６４℃左右。     

本体共聚法合成恶唑啉官能化聚苯乙烯的研究

本文以２－乙烯基－２－恶唑与苯乙烯自由基本体共聚合制得恶唑 啉官能化聚苯乙烯（ＲＰＳ）。考察了引发剂、单体比、反应条件对共聚合的影响。ＲＰＳ用ＩＲ、Ｈ－ＮＭＲ＾１３Ｃ－ＮＭＲ等方法进行表征并测定其拉伸性能和ＭＦＲ。     

抗抑郁药奈法唑酮中间体2-苯氧乙胺的合成工艺改进

以乙腈为原料与乙醇胺反应制得 2 甲基 2 口恶唑啉 ,再与苯酚反应 ,水解得到所需产物 2 苯氧乙胺 ,对工艺进行了改进 ,收率提高到 5 1 5 % ,成本低 ,有一定的工业应用前景。     

1-羟乙基-2-苯并咪唑氨基甲酸甲酯和1-乙基(2’一丙烯酸酯-1’-基)-2-苯并咪唑氨基甲酸甲酯的合成及用薄层一紫外分光光度法测定其含量

１－乙基（２’－丙烯酸酯－１’－基）－２－苯并咪唑氨基甲酸甲酯是合成多菌灵高 分子化学型缓释剂的重要单体。本文报道了１－乙基（２’－丙烯酸酯－１’－基）－２－苯并 咪唑氨基甲酸甲酯及其制备过程中的中间体－１－羟乙基－２－苯并咪唑氨基甲酸甲酯的 合成和分析方法。     

Thiol–ene addition enables tailored synthesis of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) copolymers for binder jetting 3D printing

The continued interest in graft copolymer architectures arises from their unique solution properties and potential for a myriad of applications ranging from drug delivery to adhesives. Poly(vinyl pyrrolidone) (PVP) represents a popular amorphous, water‐soluble polymer used as a polymeric binder in binder jetting additive manufacturing, as fillers in cosmetic products, and for subcutaneous drug delivery systems. This report describes the synthesis of poly(2‐oxazoline) and PVP graft copolymers using a ‘grafting to’ methodology with an efficient thiol–ene ‘click’ reaction. Copolymerization of 2‐methyl‐2‐oxazoline and 2‐(3‐butenyl)‐2‐oxazoline introduced pendent vinyl grafting sites with a predictable absolute number‐average molecular weight. In parallel, reversible addition‐fragmentation chain‐transfer polymerization and subsequent aminolysis yielded well‐defined, oligomeric, thiol‐terminated PVP. Thiol–ene click chemistry enabled the formation of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) (PMeOx‐g‐PVP) copolymers with varying mole percent grafting sites and PVP graft length. ¹H NMR spectroscopy, aqueous SEC with multiangle light scattering (SEC‐MALS), and bromine titrations confirmed chemical structure, and DSC with TGA elucidated thermal transitions. Aqueous SEC‐MALS and ¹H NMR spectroscopy also determined absolute number‐ and weight‐average molecular weights and average grafting levels, which revealed optimal reaction conditions. Zero‐shear viscosities of 5 and 10 wt% solutions in deionized water for each graft copolymer compared to their linear analogs demonstrated a significant (ca 31%) decrease in viscosity at the same number‐average molecular weight. This decrease in solution viscosity suggested PMeOx‐g‐PVP copolymers as exceptional alternatives to linear analogs for aqueous‐based, binder jetting additive manufacturing.     

Delocalized π‐electrons in 2‐oxazoline rings resulting in negatively charged nitrogen atoms: revealing the selectivity during the initiation of cationic ring‐opening polymerizations

The inventory of the single‐crystal X‐ray structures of aliphatic and aromatic 2‐oxazolines, namely 2‐nonyl‐2‐oxazoline, 2,2′‐tetramethylenebis(2‐oxazoline) and 2‐phenyl‐2‐oxazoline, reveals significant delocalization of π‐electrons along the N? C? O segment. The delocalization of π‐electrons is stabilized by inductive and resonance contributions of the side‐chains; in 2‐phenyl‐2‐oxazoline, also π‐arene interactions between the benzene ring and the C? N and the C? O bond stabilize the crystalline phase. This delocalization gives a partial negative charge to the nitrogen atom and a partial positive charge to the oxygen atom. The partial negative charge of the nitrogen atom makes this atom the exclusive reaction partner also for highly reactive non‐selective cations, which explains the regioselectivity of electrophilic attacks in cationic ring‐opening polymerizations. Copyright © 2011 Society of Chemical Industry     

Synthesis of polyvinyl acetate-graft-poly-2-oxazolines

Poly(vinyl acetate-co-vinyl chloroformate) ( 1 ) was synthesized via phosgenation of poly(vinyl acetate-co-vinyl alcohol). It was shown that ( 1 ) is capable of initiating the polymerization of 2-phenyl-2-oxazoline and 2-methyl-2-oxazoline, when the counter ion is exchanged using potassium iodide. Polyvinyl acetate-graft-poly-2-phenyl-2-oxazoline and polyvinyl acetate-graft-poly-2-methyl-2-oxazoline are obtained in the grafting reaction.     

Miscible chitosan/tertiary amide polymer blends

The miscibility of five chitosan/tertiary amide polymer blend systems was studied. Based on the optical transparency of the blend and the existence of a single glass transition temperature, chitosan was found to be miscible with poly(N‐vinyl‐2‐pyrrolidone), poly(N‐methyl‐N‐vinylacetamide), poly(N,N‐dimethylacrylamide), poly(2‐methyl‐2‐oxazoline), and poly(2‐ethyl‐2‐oxazoline). Fourier transform infrared spectroscopy showed the existence of hydrogen‐bonding interactions between chitosan and the tertiary amide polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1785–1790, 2000     

C2对称双噁唑啉的新合成方法

在脱水剂PCl3的存在下,噻吩-2,5-二甲酸与乙醇胺反应直接生成噻吩-2,5-双噁唑啉及未环化产物1和2。副产物1和2碱性关环生成噻吩-2,5-双噁唑啉,总收率达63%。此方法的优点是合成路线短,操作简单。     

Synthesis and characterization of 2‐oxazoline‐benzoxazine compound and its polymer

A novel 2‐oxazoline‐benzoxazine (POB) was synthesized with 2‐(hydroxylphenyl)‐2‐oxazoline, 1,3,5‐triphenylhexahydro‐1,3,5‐triazine and paraformaldehyde. The chemical structure of the monomer was confirmed by FTIR, ¹H‐NMR, ¹³C‐NMR, and MS. The curing behavior of the monomer was studied by DSC and FTIR, and the ring opening reaction of the monomer was found to occur from 187.5°C. The results of DMA and TGA demonstrated that the thermal properties of polymer for POB monomer (P‐m) are better than polymer for POB precursor (P‐p), because that the oligomer in benzoxazine precursor decreased the perfection of the polymer's network structure; it was also found that the thermal properties of P‐m and P‐p are much better than the common polybenzoxazine and the composite material of benzoxazine and 2‐oxazoline. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci , 2008.     

The Catalytic Diastereo‐ and Enantioselective Claisen Rearrangement of 2‐Alkoxycarbonyl‐Substituted Allyl Vinyl Ether

The catalytic asymmetric Claisen rearrangement of 2‐alkoxycarbonyl‐substituted allyl vinyl ethers that contain two stereogenic double bonds is described. A combination of the highly Lewis acidic [Cu{(S,S)‐tert‐Bu‐box}](H₂O)₂(SbF₆)₂ complex and molecular sieves served as catalyst and afforded the Claisen rearrangement products, substituted and functionalized α‐keto esters, in high yield with a remarkable diastereo‐ and enantioselectivity. The influence of ligand structure, counterion and allyl vinyl ether double bond configuration on the stereoselectivity of the rearrangement was briefly investigated. We propose an explanation for the rate accelerating effect of the Lewis acid as well as a stereochemical model which serve to explain and predict the stereochemical course of the copper bis(oxazoline) catalyzed Claisen rearrangement.     

Swelling and drug release profile of poly(2‐ethyl‐2‐oxazoline)‐based hydrogels prepared by gamma radiation‐induced copolymerization

Poly(2‐ethyl‐2‐oxazoline) and acrylic acid were copolymerized in different compositions using γ‐rays‐induced polymerization and cross‐linking to obtain a series of pH‐sensitive hydrogels. The preparation parameters that may affect the copolymerization process such as the feed solution composition and irradiation dose were optimized. Swelling characteristics of the obtained polymeric hydrogels were evaluated. The results show the significant effects of the hydrogel composition, soaking time, and pH on the swelling equilibrium. The diffusion parameters obtained at pH 1 and 7 show the possibility of using the prepared hydrogels in the field of colon‐specific drug delivery systems. Ibuprofen as a model drug was loaded into (poly(2‐ethyl‐2‐oxazoline)/acrylic acid) copolymer hydrogel to investigate their drug release behavior at different pH values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rubber toughening of polystyrene through reactive blending

Acrylonitrile-butadiene rubber having carboxylic acid groups (XNBR) and polystyrene having oxazoline groups, were melt blended in a Rheomix mixer under optimized conditions, The ratio of rubber to polystyrene phase was kept constant at 1:4 by weight. The concentration of the reactive oxazoline groups in the polystyrene phase was varied by mixing polystyrene (PS) with a copolymer of styrene and vinyl oxazoline (OPS). A torque rise observed during blending was found to be related to the concentration of oxazoline-carboxylic acid pairs. This torque rise, and independently measured increases in viscosity, both indicate inter-polymer crosslinkihg. Scanning electron microscopy was used to observe the morphology of the blends. Improved rubber phase dispersion was observed with increasing oxazoline concentration. Instrumented impact strength measurements were made using an unnotched Charpy technique. The plastic yielding was then quantified with the use of a ductility ratio. The impact strengths and ductility of the reactive blends are found to be up to 73% greater than those of the corresponding non-reactive blends. Increasing the OPS concentration beyond 5% results in decreasing impact strength, for as the compatibility increases, the rubber particle size decreases below an effective size for rubber toughening. Similar impact improvement is observed when the major PS phase is substituted with high impact polystyrene (HIPS) containing some OPS.