3，3’-二乙基-4，4’-二苯甲烷型多马来酰亚胺树脂的合成与性质研究

以邻硝基乙苯为原料,通过四步反应合成出一种重要的热固性树脂——3,3'-二乙基-4,4'-二苯甲烷型多马来酰亚胺(PEDM)。PEDM的软化点为88～93℃,远低于3,3'-二乙基-4,4'-二苯甲烷型双马来酰亚胺BEDM树脂的熔点:203～204℃(数字显微熔点仪)或212℃(DSC)。同时,PEDM在三氯甲烷、丙酮等低沸点溶剂中具有良好的溶解性。PEDM树脂较低的软化点和良好的溶解性有利于加工成型和提高材料性能,因而具有较好的应用前景。     

双(3-乙基-4-马来酰亚胺基苯)甲烷改性聚苯醚树脂的研究

以综合性能优异的烯丙基化聚苯醚(PPO)为基础树脂,采用质量分数为10%的双(3-乙基-4-马来酰亚胺基苯)甲烷(BEDM)作为烯丙基化PPO的交联剂,无引发剂热聚合得到一种均一透明的、介电常数(ε)和介电损耗角正切(tanδ)均低、玻璃化转变温度(Tg)较高、吸水率低的新型热固性PPO树脂。对烯丙基化PPO/BEDM体系的非等温固化动力学进行研究,计算得到其固化反应级数为0.95,固化反应表观活化能为160.43kJ/mol,以及频率因子和反应速率常数等数据。同时确定了该体系的固化工艺参数。BEDM改性烯丙基化PPO固化树脂的Tg为208.24℃,ε(1MHz)为2.87,tanδ(1MHz)为0.011,吸水率为0.28%,能满足高性能印制电路板用树脂的要求,具有较好的应用前景。     

多马来酰亚胺改性聚苯醚树脂的热分解动力学研究

采用热重分析法对自制的3,3′-二乙基-4,4′-二苯甲烷型多马来酰亚胺(PEDM)改性烯丙基化聚苯醚(PPO)固化树脂的热分解动力学进行了研究。结果表明:在热作用下,共聚交联体系在PPO的苯氧醚键处首先断链,并按无规断链或自由基引发断链方式迅速进行,交联网络被破坏成许多线形分子链,但其他键受影响很小,热分解表现为一级反应,且失重速率很快;随温度升高,当体系的苯氧醚键基本上断裂完毕后,线形分子链上的马来酰亚胺环的羰基或其他能量相近的键也开始逐渐断裂,此时热分解也表现为一级反应,但速率比第1步慢得多。     

α,ω-双(2,6-二甲基羟苯基)聚苯醚树脂

论述了α,ω-双(2,6-二甲基羟苯基)-聚(2,6-二甲基-1,4-酚氧)(PPO-2OH)型聚苯醚的通用及新型合成方法。这些方法是以2,6-二甲基苯酚通过铜铵络合催化的氧化聚合为基础。通过合成方法的改性可以得到低分子质量双端羟基聚苯醚(PPO-2OH)。概述了各种合成PPO-2OH的方法,例如2,6-二甲基苯酚(DMP)同四甲基双酚A(TMBPA)氧化共聚;单官能团PPO和3,3,5,5-四甲基联苯二醌(TMDPQ)反应;单官能团PPO同甲醛缩合反应,论述了PPO-2OH的改性方法,如引入烯丙基基团,同其他热固性树脂共混改性和互穿聚合物网络如环氧树脂等。还介绍了此种分子质量端羟基聚苯醚的工业应用。     

3,4-二甲氧基苯丙酮的合成研究

研究了以呋喃酚的副产物4-(2-甲基烯丙基)-1,2-苯二酚为原料,经醚化、臭氧化得附加值较高的精细化工产品3,4-二甲氧基苯丙酮。分析了醚化、臭氧化反应过程中可能出现的副反应。探索了醚化反应的氢氧化钠用量、反应温度和臭氧化反应的反应温度、臭氧用量等条件,优化条件为醚化反应n(NaOH)∶n(4-(2-甲基烯丙基)-1,2-苯二酚)=2.25∶1.00,反应温度为90℃,臭氧化反应温度℃、n(O_3)∶n[1,2-二甲氧基-4-(2-甲基烯丙基)苯]=3∶1时,合成3,4-二甲氧基苯丙酮总收率达72.8%,产品结构经LC-MS,~1H NMR确证。     

3-丁烯醛缩二乙醇的合成研究

以烯丙基氯与金属镁反应制得烯丙基氯化镁,再与原甲酸三乙酯反应,合成了3-丁烯醛缩二乙醇。研究了反应条件对反应的影响,确定了反应的最佳工艺条件:在乙醚中,-10～-5℃,n(镁粉)∶n(烯丙基氯)=1.0∶1.0反应,制得了烯丙基氯化镁,收率80%;将烯丙基氯化镁与原甲酸三乙酯按物质的量比1∶1反应,回流6h,用饱和氯化铵水溶液水解,蒸除乙醚,再减压蒸馏,制备了3-丁烯醛缩二乙醇,收率75.6%,含量98%以上。产品经元素分析、核磁共振、红外光谱等进行了确认。     

3，3’-二甲基-4，4’-（2-氨基噻唑偶氮）联苯与季铵型阳离子表面活性剂的显色反应及其应用

研究了3,3ˊ-二甲基-4,4ˊ-(2-氨基噻唑偶氮)联苯(DATABP)在pH为12.0～12.5的强碱性介质中与溴化十六烷基三甲铵(CTMAB)、溴化十六烷基吡啶(CPB)及溴化十四烷基吡啶(TPB)3种的反应.实验表明DATABP与各表面活性剂均形成络合比为1∶1的绿色络合物.对CTMAB、CPB及TPB体系,络合物的最大吸收波长分别为620 nm、630 nm 和640 nm,表观摩尔吸光系数分别为5.60×103、5.52×103和3.07×103L·mol-1·cm-1.用所建立的方法测定了水中的CPB,结果满意.     

二甲基二烯丙基氯化铵的合成

以二甲胺、烯丙基氯为原料,在相转移催化剂存在下进行反应,得到二甲基烯丙基胺(叔胺)和二甲胺盐酸盐。然后,分离出叔胺和二甲胺盐酸盐。叔胺在丙酮溶液中再和烯丙基氯反应得到二甲基二烯丙基氯化铵(DMDAAC);二甲胺盐酸盐用强碱性离子交换树脂处理得到二甲胺水溶液,可作原料套用。考察了仲胺烃基化和叔胺烃基化的反应温度、反应时间以及加料方式对产物收率的影响。最终得到了不含氯化钠的固体二甲基二烯丙基氯化铵。收率由文献中所报道的56 1%提高到70 2%。     

酸性阳离子交换树脂催化制备6,6’-二羟基-3,3,3’,3’-四甲基-1,1’-螺二氢茚的工艺研究

利用双酚A结晶残液为原料,以磺化聚氯代苯乙烯-二乙烯基苯强酸性阳离子交换树脂为催化剂,通过固定床连续催化制备6,6’-二羟基-3,3,3’,3’-四甲基-1,1’-螺二氢茚。反应器中装填50mL(22 g,E=1.8 mmol H+/mL)干树脂,在T=150℃、WHVS=0.48 h-1条件下,连续反应1000 h,反应液中6,6’-二羟基-3,3,3’,3’-四甲基-1,1’-螺二氢茚质量浓度可达43.5%,催化剂交换量保持为3.8 mmol/g。产物经重结晶纯化后熔点215～217℃,纯度≥99.98%(HPLC)。通过HPLC、IR、NMR等方法分析产物含量及结构,用STATISTIC统计软件对反应条件进行了优化。研究结果对于改进双酚A生产工艺中的残液处理方式,填补国内在新型双酚类单体生产空白具有重要的意义。     

2-(3,4-二甲氧基苯基)-3-甲基丁腈的合成研究

以呋喃酚的副产物4-(2-甲基烯丙基)-1,2-苯二酚为原料,经醚化、异构化、反马氏加成和腈化反应得附加值较高的精细化工产品即维拉帕米(verapamil)的关键中间体2-(3,4-二甲氧基苯基)-3-甲基丁腈,总收率达60.8%。产品及各中间体结构经~1H NMR确证。     

基团法估算磺化聚苯醚的溶解度参数

以氯磺酸为磺化剂制备了一系列不同磺化度的磺化聚苯醚（SPPO）。采用基团贡献法估算出了聚苯醚（PPO）及SPPO的溶解度参数值，随着磺化度的增加，溶解度参数逐渐增加，估算的结果与SPPO在不同溶剂中的溶解行为基本吻合。     

Preparation,curing properties,and phase morphology of epoxy‐novolac resin/multiepoxy‐terminated low‐molecular‐weight poly(phenylene oxide) blend

The multiepoxy‐terminated low‐molecular‐weight poly (phenylene oxide) (PPOE) was synthesized by modifying the terminal hydroxyl group of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) with epoxy‐novolac resin (EPN). The curing kinetics, phase morphology, and thermal stability of the cured EPN/PPOE blends were investigated and compared to the unmodified EPN/PPO and EPN/EPPO (epichlorohydrin‐modified PPO) blends. As revealed by the Fourier transform infrared and differential scanning calorimetry analyses, PPOE took part in the curing reaction and formed a crosslinked structure with EPN. The curing rate of EPN/PPOE blends first increased and then decreased with the increase of PPOE fraction. PPOE had both catalytic and steric hindrance effects on the curing reaction. EPN/PPOE blends showed faster curing rate and higher degree of curing than the corresponding EPN/PPO and EPN/EPPO blends. The reactive blending improved the dispersion of PPOE in EPN matrix and the thermal stability of the blend. POLYM. ENG. SCI., 54:2595–2604, 2014. © 2013 Society of Plastics Engineers     

Low dielectric and flame‐retardant properties of thermosetting redistributed poly(phenylene oxide)

A curable low‐molecular‐weight poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) was prepared by the redistribution of regular PPO with maleic anhydride (MA) in toluene, using benzoyl peroxide as an initiator. The redistributed PPO (MA‐PPO), which contained alkene groups, was characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. The redistributed PPO oligomers with reactive double bonds were cured with triallylisocyanurate (TAIC) and/or a phosphorus‐containing allyl‐functionalized monomer (allyl‐DOPO). Electrical properties of cured resins were studied by using a dielectric analyzer. The glass transition temperatures were measured by dynamic mechanical analysis. The flame retardancy was determined by the UL‐94 vertical test. The effects of curing accelerator and the amounts of TAIC and allyl‐DOPO incorporated into the network on the dielectric properties, glass transition temperature, and flame retardancy of the resulting systems were investigated. The results indicated that MA‐PPO cured with TAIC exhibited low dielectric constants (2.23–2.58 at 1 GHz) and dissipation factors (0.0034–0.0039 at 1 GHz) but had high glass transition temperatures (171–197°C)_. The MA‐PPO/TAIC copolymerized with allyl‐DOPO could achieve a flame retardancy rating of UL‐94 V‐0 at about 1.35 wt % of phosphorus. The redistributed PPO/TAIC resins have potential applications in the fabrication of printed circuit boards. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers.     

The vibration welding of poly(butylene terephthalate) and a polycarbonate/poly(butylene terephthalate) blend to each other and to other resins and blends

Vibration welding is used to assess the weldability of poly(butylene terephthalate) (PBT) and a polycarbonate/poly(butylene terephthalate) blend (PC/PBT) to each other and to other resins and blends: PBT to PC/PBT, PBT to modified poly(phenylene oxide) (M-PPO), PBT to polyetherimide (PEI) and PEI to a 65 wt% mineral-filled polyester blend (65-PF-PEB), PBT to a poly(phenylene oxide)/polyamide blend (PPO/PA), PC/PBT to M-PPO, and PC/PBT to PPO/PA. Based on the tensile strength of the weaker of the two materials in each pair, the following relative weld strengths have been demonstrated: PBT to PC/PBT,98%; PBT to PEI, 95%; 65-PF-PEB to PEI, 92%; and PC/PBT to M-PPO, 73%. PBT neither welds to M-PPO nor to PPO/PA, and PC/PBT does not weld to PPO/PA.     

Mechanical and dielectric properties of cured 1,2‐bis(vinylphenyl)ethane resin modified with poly(phenylene oxide)

1,2‐Bis(vinylphenyl)ethane (BVPE) could be cured without curing agents at relatively low temperatures (～ 180°) in a nitrogen atmosphere. Cured BVPE (CBVPE) resin showed exceptionally low dielectric constant (? = 2.50 at 10 GHz) and low dielectric loss tangent (tan δ = 0.0012 at 10 GHz), and had excellent thermal resistance. Its 5 wt % weight‐loss temperature was 425°C in a nitrogen atmosphere and glass transition temperature was over 400°C. Poly(phenylene oxide) (PPO) was used to improve the toughness of CBVPE resin. PPO was an effective modifier to toughen CBVPE resin: when using 30 wt % of the modifier, the tensile strength and elongation of the modified CBVPE resin were 75 MPa and 26%, respectively. The modified CBVPE resin also showed excellent dielectric properties (? = 2.45 at 10 GHz, tan δ = 0.0015 at 10 GHz). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1252–1258, 2004     

Quaternized poly(phenylene oxide) anion exchange membrane for alkaline direct methanol fuel cells in KOH‐free media

A series of anion exchange membrane (AEM) electrolytes with quaternary ammonium moiety are fabricated from poly (phenylene oxide) for its application in alkaline direct methanol fuel cells (ADMFCs). In the first step, poly(phenylene oxide) (PPO) is successfully chloromethylated by substituting chloromethyl groups in the aryl position of polymer. In the second step, the chloromethylated PPO (CPPO) is further homogeneously quaternized and ion‐exchanged to form an AEM. From the second step, series of AEMs are prepared by changing the mole ratio of amine in relation to CPPO. The presence of quaternary ammonium group in the membrane was confirmed by elemental analysis. The fabricated membranes are subjected to cell polarization studies in ADMFCs, wherein quaternized poly(2,6‐dimethyl‐1,4‐phenylene oxide) (CPPO:amine of 1:8) membrane exhibits higher peak power density of 3.5 mW cm^?2 when compared with the other ratios of CPPO:amine in the absence of KOH solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43693.     

Miscibility and specific interactions in blends of poly(vinyl phenyl ketone hydrogenated) with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The miscibility behavior of poly(vinyl phenyl ketone hydrogenated) (PVPhKH) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) are studied by differential scanning calorimetry, thermomechanical analysis, and FTIR spectroscopy. Two miscibility windows between 10 to 40 and 60 to 90 wt % PPO are detected. Only the blend with 50 wt % PPO is immiscible. The best fit of the Gordon–Taylor equation of the experimental glass‐transition temperatures for miscible PVPhKH/PPO blends is shown. A study by FTIR spectroscopy suggests that hydrogen bonding interactions are formed between the hydroxyl groups of PVPhKH and the ether groups of PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1887–1892, 2004     

Properties and radiation resistance of aromatic polymer-based polyblends

Blends of either of two different poly(phenylene oxide) (PPO) derivatives with poly(2-vinylnaphthalene) (P2VN) were prepared by casting from chloroform. The content of P2VN in the blends ranged from 0 to 25 wt % for each PPO derivative. Two kinds of PPO derivatives, p–t-butylbenzoyl poly(phenylene oxide) (p–t-BB-PPO) and benzoyl poly(phenylene oxide) (B-PPO), were used. The effects of the addition of P2VN to PPO derivatives were investigated by their thermal stability, light-resistance, and tensile properties. Even though the addition of P2VN to the PPO derivatives decrease the mechanical properties, the radiation resistance was improved. The radiation resistance and tensile properties of B-PPO and its blends with P2VN were higher than those of the p–t-BB-PPO and its blends with P2VN. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1697–1705, 1999     

PBT的低烟阻燃性研究

研究了几种阻燃体系对PBT的阻燃抑烟效果，结果发现；用氢氧化镁(MH)和硼酸锌(ZB)与十溴联苯醚(DBDPO)—氧化锑或包覆红磷共同使用，可使燃烧过程的发烟量降低40％左右；聚苯醚(PPO)和一种磷酸酯阻燃剂配合使用；其阻燃抑烟作用及对力学性能的改善作用优于十溴联苯醚—氧化锑和包覆红磷体系。