2，2-双（2-噁唑啉）改性回收PET的研究

以扩链剂2，2-双(2-噁唑啉)对回收PET进行扩链增粘，从特性粘度和羧值的变化考察了其扩链效果，并用DSC法研究了不同添加量噁唑啉对PET热性能的影响。结果表明：双噁唑啉对PET有一定的扩链效果，且影响PET的冷结晶行为。     

1,3-双(2-噁唑啉基)苯的合成工艺优化

以间苯二甲腈、乙醇胺为原料,无水醋酸锌或氯化锌为催化剂,合成了1,3-双(2-噁唑啉基)苯,优化了工艺条件.优化条件为:n(间苯二甲腈)∶n(乙醇胺)∶n(催化剂)=1.00∶4.00∶0.04,反应5h,温度120～125℃.优化条件下,产品含量99.2％,反应收率94.7％,产品结构经核磁、红外和质谱确证.该工艺还提出了乙醇胺的回收方法,具有收率高、成本低、三废排放少等优势,宜于工业化生产.     

噁唑啉基扩链剂的合成及其应用研究

本文重点介绍了近年来噁唑啉扩链剂的研究进展及应用研究,并指出了噁唑啉基扩链剂今后的发展方向。     

双-2-噁唑啉化合物对PET的改性作用研究

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

双噁唑啉对尼龙6的化学改性研究

在Haake转矩流变仪中对1,3-双-(2-噁唑啉基)苯 (MPBO)和2,2-双-(2-噁唑啉) (BOZ)化学扩链尼龙6做了系统的研究.偶联结果表明:扩链剂(MPBO)和(BOZ)的用量均存在最佳值,用量不足时,偶联反应不充分;用量过量时,封端反应加剧,同时MPBO的扩链效果要比BOZ的差.当扩链剂的加入量均为最佳用量时,扩链后尼龙6的特性黏度分别从空白样的1.632 dL·g-1 提高到1.787 dL·g-1(MPBO)和2.031 dL·g-1 (BOZ),此时端羧基浓度分别从初始值的7.15×10-5 mol·g-1降低到 3.70×10-5 mol·g-1 (MPBO)和2.33×10·5 mol·g-1 (BOZ).反应温度对扩链反应速率的影响符合阿累尼乌斯公式,温度为260℃,扩链反应完成时间约为3 min.扩链产物在高温条件下存在热降解现象.     

尼龙6化学扩链

用挤出机熔融共混法,以双２口恶唑啉和双酰基双内酰胺化合物为扩链剂,对ＰＡ６进行化学扩链,使ＰＡ６的分子量由１６．７ｋｇ／ｍｏｌ提高到２１．０ｋｇ／ｍｏｌ,偶联效率最高可达７０％;同时考查了扩链剂用量、铜盐、共混温度与时间以及后热处理对扩链效果的影响。     

4,4′-双(苯并噁唑-2-基)二苯乙烯荧光增白剂(OB-1)的合成

以对甲基苯甲酸及其乙酯为原料,经过三氧化铬在乙酐中的氧化反应、在氯苯溶剂中以氯化亚砜为氯化试剂的侧链氯化反应和亚磷酸三乙酯为乙基化试剂的酯化反应,再经两步缩合反应,合成了荧光增白剂4,4′-双(苯并噁唑-2-基)二苯乙烯(OB-1).OB-1(由Ⅲ合成Ⅳ粗品)的收率由文献中平均90%提高到平均99%以上.通过对化合物的元素分析、红外光谱以及在DMF中紫外吸收光谱的测定,确定了目标产物的结构.经HPLC测定,w(OB-1)＞99%.     

4-(5-氨基-6-羟基-2-苯并噁唑基)苯甲酸的合成

系统地研究了AB型新单体：4-(5-氨基-6-羟基-2-苯并口恶唑基)苯甲酸（ABA）的合成方法以及产品析出时pH值条件对其分子形态及红外吸收的影响。以4-(5-氨基-6-羟基-2-苯并口恶 唑基)苯甲酸甲酯（MAB）为原料,60～100 ℃于碳酸钾水溶液中水解反应至溶液澄清,用还原性弱酸性盐的水液在pH值6.0析出结晶、制得纯度99.5%以上高质量的新单体、经FT-IR归属剖析确认为游离的酸式单体ABA,收率达85%;具有过程工艺简便,单体稳定性优异、且无残留DMF阻聚杂质以及聚合操作安全等特点,在制备聚合级AB型PBO单体中取得新进展。     

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。     

聚酰胺6扩链改性及其超临界CO2模压发泡研究

以扩链剂KL–E4370、抗氧剂1010对线型尼龙6(PA6)进行改性,制备出具有高熔体强度的改性PA6材料。采用固态发泡的发泡方法,通过超临界CO₂模压发泡制备相应发泡材料。通过差示扫描量热仪,流变仪来表征改性材料的可发泡性,并通过扫描电子显微镜来观测发泡材料的泡孔形貌。探究不同工艺条件对PA6泡沫泡孔结构的影响,分析了不同泡孔结构对发泡材料力学性能的影响。在饱和压力为10~20 MPa、发泡温度为223~231℃的范围内制备的PA6泡沫泡孔直径在18.3~143.6μm之间,泡孔密度为7.42×10⁶~1.75×10⁹个/cm³,发泡倍率为5.6~22.4。所得PA6泡沫的拉伸强度为1.5~5.8 MPa,断裂伸长率为22%~51%,压缩强度为0.03~2.47 MPa。     

Organization of poly(2-ethyl-2-oxazoline)-block-poly(2-phenyl-2-oxazoline) copolymers in water solution

Diblock copolymers were prepared from 2-ethyl-2-oxazoline and 2-phenyl-2-oxazoline via living cationic polymerization using sequential addition of the monomers. Copolymer assemblies in aqueous solutions and on surface were studied with respect to changes in the hydrophilic-hydrophobic balance induced by increasing the length of the hydrophobic poly(2-phenyl-2-oxazoline) segment while the hydrophilic poly(2-ethyl-2-oxazoline) chain was kept constant with an average of 60 monomer units. The copolymer with a short segment of four 2-phenyl-2-oxazoline units assembled into highly hydrated aggregates that decreased twice in size after drying. Their structure was destroyed and network morphologies were formed upon spin-coating. The increase of the length of the hydrophobic segment resulted in aggregates that dissociated to micelle-sized particles when subjected to mechanical shear by spin-coating or filtering. These observations imply that the aggregates are multi-core structures originating from the assembly of primarily formed micelles. The copolymer self-assembly was evidenced by a combination of techniques: DLS, SLS, AFM and SEM.     

全生物降解PBS的扩链改性研究

采用新型扩链剂2,2′-双(2-噁唑啉)(BOZ)对聚丁二酸丁二醇酯(PBS)进行扩链,研究了BOZ加入量、稳定剂加入量、时间、温度对扩链反应的影响。结果表明,选择最佳条件,扩链后的PBS的相对分子质量较未扩链PBS的相对分子质量大为增加,而且扩链PBS相对分子质量分布与未扩链PBS基本一致,说明PBS扩链后的线性度与起始PBS相同,没有支化或交联反应发生。     

高位阻双酚2,2'-亚甲基双(4,6-二叔丁基苯酚)的合成

以2,4-二叔丁基苯酚和甲醛为原料,乳液缩合法合成2,2′-亚甲基双(4,6-二叔丁基苯酚)(MB46)。分别考察了催化剂和表面活性剂种类及用量、水的用量及反应时间等对反应的影响,实验结果表明,表面活性剂的种类对反应有很大的影响,采用阴离子表面活性剂十二烷基硫酸钠效果较好。在2,4-二叔丁基苯酚10．3g、甲醛2．5mL的合成条件下,最佳工艺参数为：十二烷基硫酸钠0．1g,水的用量为40mL,反应时间为7h,硫酸用量为0．6mL。     

2,2-双(2-噁唑啉)与苯酐联用改性回收PET的动态热性能研究

以扩链剂2,2 双(2 噁唑啉)(BOZ)与苯酐(PA)联用改性回收PET,系统地考察了增黏改性后回收PET动态流变性能和动态力学性能的影响。结果表明,BOZ与PA联用的改性效果明显优于单用BOZ改性回收PET体系;但因扩链剂的加入,在PET分子链中引入的柔性链段而导致聚合物弹性模量下降。     

Facile synthesis and characterization of novel bis(2-S-alkylpyridines) and bis(3-aminothieno[2,3-b]pyridines) incorporating 1,3-diarylpyrazole moiety

3-(4-Hydroxyphenyl)-1-phenyl-1H-pyrazole-4-carbaldehyde (1) is condensed with acetophenone to afford the corresponding unsaturated carbonyl compound 4 whose potassium salt is reacted with 1,4-dibromobutane to afford the bis-unsaturated carbonyl compound 3. Both carbonyl compounds 3 and 4 are reacted with 2-cyanoethanethioamide, through Michael addition reaction followed by cyclocondensation, to prepare the starting materials bis(pyridine-2(1H)-thione) derivative 5 and pyridine-2(1H)-thione derivative 8. Two synthetic routes to synthesize the target materials 7 and 14 are described to get the most efficient method for preparation and maximum yield%. The first route came from the direct alkylation of the bis(pyridine-2(1H)-thione) derivative 5 using iodomethane (6a) and benzyl chloride (6b) to afford the corresponding bis(2-S-alkylpyridine) derivatives 7a,b. The reaction of 5 with halo-containing compounds 10a–d to synthesize the target materials bis(3-aminothieno[2,3-b]pyridine) derivatives 14a–d failed under various reaction conditions. The second route involves the reaction of pyridine-2(1H)-thione derivative 8 with 6a,b and 10a–d to afford the corresponding 2-S-alkylpyridine derivatives 9a,b and 3-aminothieno[2,3-b]pyridine derivatives 13a–d, through the formation of 2-S-alkylpyridine derivatives 12a–d followed by a Thrope-Ziegler reaction, whose potassium salts reacted with 1,4-dibromobutane to afford the corresponding target materials 7a,b and 14a–d, respectively. The structures of target molecules were elucidated using elemental analyses and spectral data.     

Synthesis and characterisation of poly(arylene sulphides): Part 11. Preparation of poly(1,4-phenylene sulphide) directly from bis(4-bromophenyl) disulphide

Reaction conditions for the preparation of poly(1,4-phenylene sulphide) (PPS) directly from bis(4-bromophenyl) disulphide (BBD) have been established. Reactions were performed in a boiling quinoline/pyridine solvent mixture (91% by vol. quinoline) in the presence and absence of copper powder. Reaction products were fractionated and the fractions characterised using elemental analysis, IR and NMR spectroscopy, viscometry, hot-stage microscopy, differential scanning calorimetry, thermogravimetry and curing studies. The yields and properties of the polymeric fractions are compared to those of similar fractions obtained from preparation of PPS by solution polymerisation of copper(I) 4-bromobenzenethiolate under conditions which correspond to those employed in this work. PPS was not produced, and BBD was almost quantitatively recovered when copper was absent from the reactants. Reactions performed using an equimolar ratio of copper to BBD produced PPS of molar mass approximately 2–4 × 10³ gmol^?1 in 76% yield after 8h reaction. However, this PPS was contaminated with an insoluble infusible material which had a deleterious effect on the physical properties of derived cured PPS materials. The yield of PPS decreased and the quantity of contaminant increased as reaction time increased. PPS of molar mass approximately 10⁴g mol^?1 was obtained in 50–60% yield, free from insoluble infusible material, when the molar ratio of copper: BBD was increased to 2:1; it exhibited normal properties on curing.     

Compatibilization of Poly(2,6-dimethyl-l,4-phenylene oxide) and Poly(2,6-dichloro-l,4-phenylene oxide) with Sulfonated Polystyrene and its Na and Zn-neutralized Ionomers

Compatibility of acidic (H), Na, and Zn neutralized sulfonated polystyrene ionomer blends with Poly(2,6-dimethyl- 1,4-phenylene oxide) (PPO) and Poly(2,6-dichloro- 1,4-phenylene oxide) (PDCIPO) was investigated by Dilute Solution Viscometry (DSV) and Differential Scanning Calorimetry (DSC). The intrinsic viscosities of the blends, are measured in suitable solvents. The degree of compatibility of the blends is characterized by Δb parameter. According to the results, PPO is completely miscible, except for Na-neutralized 1.7 mol% sulfonated polystyrene (Na1.7SPS) which is completely immiscible with PPO and PDClPO. PDClPO is completely miscible with Zn-neutralized sulfonated polystyrene (Zn4.8SPS) and partially miscible with acid sulfonated polystyrene (4.8SPS). Received: 12 August 2001/Revised version: 21 January 2002/Accepted: 11 March 2003 Correspondence to Leyla Aras     

Miscibility and interpolymer complexation of poly(2-methyl-2-oxazoline) with hydroxyl-containing polymers

Poly(2-methyl-2-oxazoline) (PMOx) was found to be miscible with poly (styrene-coallyl alcohol), poly(hydroxyether of bisphenol-A), poly (2-hydroxypropyl methacrylate) and poly(p-vinylphenol) (PVPh), when cast from N,N-dimethylformamide solutions and to form interpolymer complexes with PVPh in methanol solutions. The hydrogen bonding interactions between PMOx and hydroxyl-containing polymers were studied by infrared spectroscopy and compared with the corresponding blends of poly(2-ethyl-2-oxazoline) (PEOx). Except with phenoxy, PMOx interacts more strongly with hydroxyl-containing polymers than PEOx does.