含苯并噁唑环双偶氮光导颜料的制备及性能

以2-(4'-氨基苯基)-6-氨基苯并噁唑为重氮组分,以N-(2-氯苯基)-N'-(3-羟基-2-萘甲酰)脲为偶合组分合成双偶氮化合物.通过紫外可见吸收光谱和红外吸收光谱对产物的结构进行了鉴定.并以合成的双偶氮化合物为电荷产生材料制成功能分离型有机光导体,测试结果表明,在15℃下用DMF处理有利于低结晶度光敏性产物的生成,在可见光区的吸收较强.制备的光导体具有较好的光导性能,V0=770V,VR=40V,E1/2=7.6 lx·s.     

6—硝基苯骈咪唑新型合成方法及在射线感光材料中的应用

本文介绍一种合成6-硝基苯骈咪唑的新方法,以硝酸钾和硫酸代替发烟硝酸作为苯骈咪唑的硝化剂,反应收率较高,反应产物分离和提纯较简便。用此法合成的产物应用于配制医用和工业射线片冲洗药液,可获得正常的防灰雾效果。     

尼龙6的催化水热解聚工艺与动力学

在553K-603K条件下,以水为反应介质,引入环境友好的杂多酸催化剂研究尼龙6的解聚反应,比较了催化和非催化条件对解聚的影响。对固体产物进行红外光谱和热失重分析,液相产物采用色谱-质谱联用仪和液相色谱定性与定量分析。结果表明,磷钨酸可提高尼龙6的解聚速率和ε-己内酰胺产率。解聚产物除ε-己内酰胺外,还含有少量的6-氨基己酸和低聚物。探讨了尼龙6的催化解聚动力学,求得解聚速率常数和反应活化能。     

淀粉与丙烯腈和AMPS接枝共聚制备高吸水性树脂

用淀粉、丙烯腈、2-丙烯酰胺-2-甲基丙磺酸(AMPS)为原料,采用[Mn(H2P2O7)3]3-为引发剂,经过接枝、皂化,快速合成了高吸水性树脂.运用响应面分析的方法,考察了糊化时间、糊化温度和2-丙烯酰胺-2-甲基丙磺酸用量对生产工艺及最终产物性能的影响,其中较适宜的条件为:AMPS的摩尔百分含量为5.36%,糊化温度为85.9℃,糊化时间为31 min,在这种情况下,整个工艺过程需要约2.5 h,最终产物的吸水量为1328 gH2O/g.热重分析显示产物是热稳定的,差示扫描量热分析表明,水凝胶中有不同状态的水存在.产物具有较快的吸水速度.     

制备HDI及IPTS的新方法

采用毒性较小的固体光气(BTC)代替光气与己二胺和γ-氨基丙基三乙氧基硅烷反应合成了1,6-己二异氰酸酯(HDI)以及γ-异氰酸酯丙基三乙氧基硅烷(IPTS),研究了原料配比、加料温度、反应温度以及反应时间等对实验产物的影响.实验表明,-NH-和固体光气的比例为3:1,加料温度为-20℃,反应温度为60℃,反应时间为3h时能够得到目标产物.用红外光谱和质谱对产物进行了表征,结果显示合成产物具有异氰酸酯的显著特征,纯度较高.因此采用BTC代替光气合成HDI和IPTS是一条切实可行的路线.     

1,1-二(对-二乙氨基苯基)-4-(α-萘基)-4-苯基-1,3-丁二烯的合成及其光电性能研究

以α-溴代萘和苯乙酮为主要原料合成了1-(α-萘基)-1-苯基-3-氯丙烯,该化合物与4,4'-双(二乙氨基)二苯甲酮经Grignard反应,脱水后得到目标产物1,1-二(对-二乙氨基苯基)-4-(α-萘基)-4-苯基-1,3-丁二烯(CT),产品纯度98.86%,收率36.4%.通过质谱与核磁共振对产物的结构进行了表征,并对其进行X-射线单晶衍射分析,确定了分子构型.以Y-TiOPc为电荷产生材料,CT为空穴传输材料制备的功能分离型光导体光导性能参数为:V0=-850V,VR=-20V,Rd=17.5V,E1/2=0.60lx·s,表明CT具有优良的空穴传输特性.     

疫苗温度标签的制备及显色动力学

目的 以2,4-己二炔-1,6-二烷基脲为原料制备疫苗温度标签,并对其重结晶和共结晶的制备,以及显色动力学规律进行研究,为疫苗温度标签的商业化应用提供理论指导.方法 通过使用不同溶剂对2,4-己二炔-1,6-二乙基脲的重结晶,以及不同比例的2,4-己二炔-1,6-二乙基脲和2,4-己二炔-1,6-二丙基脲的共结晶进行实验,确定最适宜的配方,并对其显色动力学规律进行研究,利用分光密度仪对光密度值进行测定,进而通过计算得到反应活化能.结果 不同溶解度的溶剂重结晶2,4-己二炔-1,6-二乙基脲后的固相聚合反应速率不同,通过实验发现以m乙醇:m水=3:1的混合溶液为溶剂重结晶,以及mKE:mKPR=2:1共结晶得到的产物热反应性较好,颜色变化较为鲜明,且通过计算得到该固相聚合反应的活化能为31.94 kJ/mol.结论 将2,4-己二炔-1,6-二烷基脲作为新型的化学型疫苗温度标签,其视觉响应信号易于识别;通过重结晶和共结晶的改性来匹配不同种类的疫苗,可直观反映疫苗在冷链运输、保存和使用环节的质量.     

离子液体溴代1-丁基-3-甲基咪唑盐合成的红外光谱分析

本实验建立以红外光谱法,利用特征吸收频率处的红外吸收率测得合成离子液体1-丁基-3-甲基咪唑六氟磷酸盐的中间产物溴代1-丁基-3-甲基咪唑盐的含量,应用于探索1-丁基-3-甲基溴代咪唑盐合成的最佳反应条件,结果表明反应温度为65℃,时间50分钟时产物得率高.     

聚[3-(6-溴己基)噻吩]的合成与表征

以3-溴噻吩、正丁基锂和1,6-二溴己烷为原料,经过改良的Li-Br交换反应、溴化反应、GRIM法成功合成了聚[3-(6-溴己基)噻吩]。通过傅里叶变换红外光谱(FT-IR),核磁共振波谱(1 H-NMR)、GPC、紫外吸收分光光谱(UV-Vis)及荧光发射光谱(PL)对中间产物及聚合物进行了结构和性能表征。结果表明,所合成聚合物与目标产物的结构一致。聚合物的数均分子量为5725,多分散系数为1.39,在氯仿溶液中最大吸收波长在398nm,最大发射波长在553nm。     

6-乙酰基-1,1-双二茂铁基丁烷与格氏试剂的反应及其产物的研究

本文通过6-乙酰基-1,1-双二茂铁基丁烷与甲基格氏试剂和苯基格氏试剂的反应,得到四种新的反应产物,并利用元素分析,红外光谱,核磁共振氢谱等测试手段对各反应产物进行了表征。通过条件实验确定了最佳反应原料比例,并对两种格氏试剂的反应及其产物进行了讨论。     

Mechanically strong, flexible polyimide aerogels cross-linked with aromatic triamine

Polyimide gels are produced by cross-linking anhydride capped polyamic acid oligomers with aromatic triamine in solution and chemically imidizing. The gels are then supercritically dried to form nanoporous polyimide aerogels with densities as low as 0.14 g/cm(3) and surface areas as high as 512 m(2)/g. To understand the effect of the polyimide backbone on properties, aerogels from several combinations of diamine and dianhydride, and formulated oligomer chain length are examined. Formulations made from 2,2'-dimethylbenzidine as the diamine shrink the least but have among the highest compressive modulus. Formulations made using 4,4'-oxydianiline or 2,2'dimethylbenzidine can be fabricated into continuous thin films using a roll to roll casting process. The films are flexible enough to be rolled or folded back on themselves and recover completely without cracking or flaking, and have tensile strengths of 4-9 MPa. Finally, the highest onset of decomposition (above 600 °C) of the polyimide aerogels was obtained using p-phenylene diamine as the backbone diamine with either dianhydride studied. All of the aerogels are suitable candidates for high-temperature insulation with glass transition temperatures ranging from 270-340 °C and onsets of decomposition from 460-610 °C.     

基于离子交换与激光打印技术在含氟聚酰亚胺薄膜表面制备银-铜金属线

以4,4’-六氟亚异丙基-邻苯二甲酸酐(6FDA)和4,4’-二胺基二苯醚(4,4’-ODA)为原料制备了含氟聚酰亚胺薄膜,然后通过水解、激光打印、离子交换、化学还原等技术得到银和铜双金属的图案化聚酰亚胺薄膜。通过X-射线衍射仪、四点探针测试仪、光学显微镜、扫描电子显微镜等仪器系统研究了薄膜表面金属的形成过程及水解时间与导电性的关系。实验结果表明,随着水解时间的增加,金属线条的导电性逐渐增加,电导率最大达到500s/cm。     

Processing and properties of carbon fiber/Triple-A polyimide composites fabricated from imide oligomer dry prepreg

Triple-A polyimide (TriA-PI) concept, “amorphous, asymmetric, and addition type”, was originally proposed by Yokota in 1999 for high temperature polymer matrix composites. The first version polyimide “TriA-PI-1” was developed from a-BPDA (2,3,3′,4′-biphenyltetracarboxylic dianhydride), 4,4′-oxydianiline (4,4′-ODA), and phenylethynyl phthalic anhydride (PEPA). The cured polyimide exhibits excellent mechanical properties with high glass transition temperature.In this study, a new prepreg system, namely imide-oligomer dry prepreg was developed by impregnating imide-oligomer into unidirectional carbon fiber bundles directly. Carbon fiber/TriA-PI-1 composites were fabricated from the imide-oligomer dry prepreg, and mechanical properties were evaluated. It was demonstrated that the TriA-PI-1 composite exhibits excellent compressive and tensile strengths at 300 °C as well as room temperature. It was easy to make a high quality composite laminate without complicated process using imide-oligomer dry prepreg.     

6FDA-TMPDA-DABA/TiO2杂化膜的制备、表征和气体渗透性能

以硅藻土-莫来石陶瓷膜管为支撑体,以TiO2为过渡层,通过溶胶凝胶法利用具有大量支链的聚酰亚胺和TiO2溶胶制备了系列不同TiO2含量的聚酰亚胺/TiO2杂化膜.聚酰亚胺是利用4,4'-六氟亚异丙基-邻苯二甲酸酐(6FDA)、2,4,6-三甲基-1,3-苯二胺(TMPDA)和3,5-二氨基苯甲酸(DABA)在溶液中进行亚胺化完成的.采用FTIR、TG/DTA、DSC、TEM、BET和气体渗透测定对系列膜进行了表征和测试.结果表明:聚酰亚胺通过支链上的羧酸基和TiO2相键连织构成了具有规则孔道的空间网状结构,并且随着TiO2含量的增加孔径逐渐减小;杂化膜具有较高的热稳定性和有机无机兼容性;相对于聚酰亚胺膜,杂化膜对H2、CO2和H2O相对于N2具有较高的分离性,TiO2含量为25%(质量分数)的杂化膜对H2/N2、CO2/N2和H2O/N2的分离因子分别达到56.6、31.3和55.3.     

Development of polyimide–nanosilica filled EPDM based light rocket motor insulator compound: Influence of polyimide–nanosilica loading on thermal,ablation, and mechanical properties

Thermal protection materials are necessary to protect structural components of launch vehicles during lift-off of launching system. The present study deals with the development of a novel thermally protected light rocket motor insulator compound (RMIC) of polyimide–silica filled EPDM nanocomposites. The insulation compound prepared for the studies comprised of aromatic polyimide and nanosilica particles. The addition of these materials in rocket insulator compound enhanced the multifunctional thermal and insulation characteristics. EPDM when grafted with maleic anhydride, contributed polarity in the non-polar EPDM matrix. Nanosilica contributes specifically better erosion resistance. SEM and TEM micrograph of EPDM nanocomposites exhibits good dispersion of nanosilica in polyimide–EPDM matrix. Nanocomposite formation was characterised by FTIR. Density, co-efficient of thermal expansion, thermal conductivity, ablation rate, specific heat, maximum thermal degradation, char yield and mechanical properties of the RMIC have been measured. This developmental study may find wide scope for commercial exploitation.     

含戊二烯酮结构新型光敏聚酰亚胺的合成与表征

用4,4’-(六氟亚异丙基)-邻苯二甲酸酐(6FDA)与光敏性二胺1,5-二(氨基苯基)-1,4-戊二烯-3-酮(BAPO)合成新型的可溶性光敏聚酰亚胺(PSPI)。用FT-IR,1H-NMR,GPC对聚合物进行了表征,同时对聚合物的溶解性能、热性能和光敏性能进行了探讨。结果表明,所合成的聚合物在常见的有机溶剂DMF、NMP和DMSO中,显示了极好的溶解性能;具有优良的热稳定性能,其玻璃化温度为268℃,5%的热失重率的温度为467℃;聚合物的感光性通过UV-Vis光谱进行了研究。     

含碳硼烷单元聚酰亚胺材料的制备及其耐热机制

聚酰亚胺是先进复合材料重要的基体材料之一。在聚酰亚胺主链中成功引入碳硼烷笼状单元,制备出一系列有机-无机杂化的聚酰亚胺材料。从单体设计入手,设计合成了含邻碳硼烷单元的二胺单体(DNCB),再与4,4’-二氨基二苯醚(ODA)和3,3’,4,4’-苯甲酮四羧酸二酐(BTDA)进行共聚反应,合成前驱体聚酰胺酸(PAA)溶液并制备PAA薄膜,再经高温热亚胺化处理得到含碳硼烷单元的聚酰亚胺。对制备的聚酰亚胺材料的耐热性能和耐热氧化稳定性进行了系统研究,结果表明,碳硼烷单元的引入使聚酰亚胺基体的热稳定性和热氧化稳定性得到显著提升。当二胺单体中DNCB摩尔分数为40%时,N₂气氛下,5wt%热失重温度T_5%提升近13℃,T10%提升近43℃,质量残留率高达82.6wt%;空气氛围下,T_5%提升近36℃,T_10%提升近64℃,质量残留率高达83.1wt%。X-射线光电子能谱(XPS)及扫描电镜(SEM)结果表明在聚酰亚胺主链中引入碳硼烷笼状单元后在高温环境中易在材料表面形成氧化硼(B₂O     

MA封端的光敏聚酰亚胺的合成与表征

光敏聚酰亚胺以其优良的性能在许多高新技术领域中得到了广泛的应用,是当今国内外学者的研究热点。采用均苯四酸二酐(PMDA)与4,4’-二氨基二苯醚(ODA)、顺丁烯二酸酐(MA)进行共聚,实验表明以MA封端效果较好,比较成功的在聚酰亚胺分子链中引入光敏基团,采用IR、TGA等测试手段对聚合物的结构与性能进行了表征和研究。     

The study on imidization degree of polyamic acid in solution and ordering degree of its polyimide film

Polyamic acid (PAA) based on pyromellitic dianhydride and 4,4′-oxydianiline (PMDA–ODA) can be chemically converted to copolyamic acid-imide (PA-I) which is a partially converted PAA at ambient temperature by treatment with a mixture of acetic anhydride and pyridine. A systematic investigation by rotation viscometer and FT-IR revealed that phase separation in PA-I solution occurred when imidization degree was about 26%. Imidization degree of PA-I solution could be controlled by using adequate acetic anhydride amount, initial PAA concentration and imidization time. PA-I solutions with different imidization degree were converted to corresponding polyimide films by thermal imidization. WAXD showed that as imidization degree in PA-I solution increased, the degree of morphologic ordering of final PI film was improved, while tensile strength and modulus increased and ultimate elongation reduced slightly.     

原位聚合聚酰亚胺改性尼龙树脂的制备与性能

塑料的高性能化已经成为当前研究的热点。选择耐水性优良的双酚A型二酐和双酚A型二胺作为反应单体,二步聚合得到分子量很高的端酸酐聚酰亚胺,利用酸酐的活性,接枝上酰基己内酰胺活性基团,聚合得到PI改性尼龙树脂,通过红外分析证明上述各步反应是成功的。聚酰亚胺(PI)改性尼龙的力学性能随着聚酰亚胺用量和分子量的增加而增加,明显优于一般工程塑料。微观分析聚酰亚胺分子并没有进入尼龙树脂的结晶相,而是形成致密的片晶存在尼龙基体中。