新型环磷腈类化合物的合成

六氯环三磷腈(1)分别与间苯二胺(2)和二苯氨基脲(3)经亲核取代反应合成了两个新型的环磷腈类化合物——六间苯二胺环三磷腈(4)和六二苯氨基脲环三磷腈(5),其结构经1H NMR,31P NMR和IR表征。合成4的最佳反应条件为:1 7.2 mmol,n(2)∶n(1)=6.17,于70℃反应12 h,产率72.68%。合成5的最佳反应条件为:1 2.8 mmol,n(3)∶n(1)=6.10,于70℃反应12 h,产率46.57%。     

六对羧基苯氧基环三磷腈的合成及其热性能

羧基苯氧基磷腈及其衍生物由于具有优良的生物活性并能降解成无毒产物,因而在生物医用材料的应用上潜力巨大。本文采用两步法合成了六对羧基苯氧基环三磷腈(HCPCP),首先以六氯环三磷腈和对羟基苯甲醛为原料,采用亲核取代反应制得六对醛基苯氧基环三磷腈（HAPCP）,再用KMnO4氧化法合成HCPCP。通过红外光谱、高效液相色谱、核磁共振及元素分析等确证了产物的结构;用TGA和DSC对其热性能进行了研究。     

杂质对六氯环三聚磷腈热聚合的影响

利用红外光谱、磷核磁共振谱、广角X射线衍射、差示扫描量热、凝胶色谱等分析手段,研究了六氯环三聚磷腈(HCCP)在存放过程中产生的杂质,以及不同纯化方法对这些杂质的去除效果,探讨了这些杂质对HCCP单体真空热开环聚合反应的影响.HCCP在存放过程中接触空气中的水汽在环上氯基团处易被水解,产生Trimer-1、Gem-2、Dimmer-3等杂质,重结晶能去除Gem-2、Dimmer-3和少量的Trimer-1,升华能较好地去除Trimer-1.杂质Gem-2、Dimmer-3中的羟基引发聚二氯磷腈交联,生成不可溶的交联态聚二氯磷腈,而Trimer-1则会降低聚合速度,并在聚合物中引入磷氧基和亚胺基杂链,从而影响后续聚磷腈取代产物的性质,表现为聚合物中晶态发生变异,结晶度降低,玻璃化温度、晶态转化温度和熔融温度出现差别.用重结晶结合升华的方法对HCCP单体进行纯化后,应用FTIR或31P-NMR分析来验证纯化效果,以确保能控制聚合速度和时间,使聚合顺利进行.     

六苯氧基环三磷腈的合成及其在层压板中的阻燃应用

以六氯环三磷腈（HCCTP）粗产物、苯酚、NaOH为反应原料,四丁基氯化铵（TBAC）为相转移催化剂,氯苯和水为溶剂,合成了六苯氧基环三磷腈（HPCTP）,考察了反应温度、反应时间、反应溶剂、物料配比对收率的影响。结果表明,在最佳原料配比n(NaOH): n(苯酚): n(TBAC): n(HCCTP粗产物)=7.5: 6.3: 0.15: 1,30 ℃反应4 h,回流反应6 h,HPCTP的收率达到75％。采用红外光谱、核磁氢谱、碳谱、磷谱、X射线衍射分析、示差扫描量热分析、热重分析测试技术对产物进行了表征分析,并首次用于苯并噁嗪树脂玻璃布层压板,当HPCTP的质量分数为10％时,燃烧等级达到V-0级,平行击穿电压为47 kV,热态弯曲强度为596 MPa。     

新型环三磷腈大分子的合成与性能研究

以六对羧基苯氧基环三磷腈为原料,通过羧基活化与缩合反应合成了一种新型的环三磷腈生物大分子(1),其结构经1H NMR,13C NMR,IR和MS表征。用UV,分子荧光光谱仪和共聚焦激光显微镜研究了1的水解性能和荧光性能。结果表明,1既具有生物可降解性,又具有荧光特性。     

六氯环三磷腈交联寡聚乙烯亚胺的制备及基因载体应用

将六氯环三磷腈与分子量为600的超支化寡聚乙烯亚胺在干燥氯仿中反应,合成了可降解的交联型聚合物.利用1HNMR表征了聚合物的结构,并用GPC测试了聚合物的分子量.研究了其作为非病毒基因载体的性能,聚合物载体与DNA形成的复合物颗粒粒径为150nm,Zeta电位为30～40mV,凝胶阻滞电泳显示聚合物/DNA在质量比为0.4时能够将DNA完全阻滞.体外转染实验结果表明,载体对HeLa细胞的最佳转染效率为PEI-25K的3倍;聚合物浓度为20μg/mL时,细胞存活率仍然大于80%,材料的细胞毒性低,生物相容性好,具有良好的生物医学应用前景.     

PCl5与NH4Cl反应生成六氯环三磷腈的链引发反应机理的理论研究

采用密度泛函理论(DFF)方法研究了五氯化磷与氯化铵反应生成六氯环三磷腈的链引发过程的微观反应机理.在GGA-HCTH/DND理论水平下优化了反应路径上存在的反应物、中间体、过渡态及产物的几何构型,并通过频率分析确认了过渡态的结构.计算结果表明,该链引发是一个非常复杂的反应过程,反应路径上存在多种中间体和过渡态,并且这...     

环三磷腈类阻燃剂的合成及应用研究进展

简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理;介绍了环三磷腈阻燃剂的阻燃机理;着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂,以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用,同时综述了其应用材料的热稳定性能和阻燃性能,并对其发展趋势作了总结和展望。     

六苯氧基环三磷腈的热解及其对环氧树脂的阻燃机理

采用极限氧指数仪和锥形量热仪测试了以六苯氧基环三磷腈(HPCP)阻燃环氧树脂的燃烧性能,结果显示,与纯环氧树脂相比,阻燃环氧树脂的极限氧指数值(LOI)明显提高、热释放速率峰值(pk-HRR)和总热释放量(THR)明显下降、环氧树脂的点燃时间提前以及分解速度加快.采用热失重(TGA)、热重红外联用(TGA-FTIR)、X射线光电子能谱(XPS)和热裂解气相色谱质谱联用(Py-GC/MS)研究了HPCP及其阻燃环氧树脂的热解路线和阻燃机理.结果表明,在阻燃环氧树脂过程中,一方面,HPCP分子中的苯氧基团首先解离并发生歧化反应,由此产生的苯氧基及其歧化产物的焠灭效应在环氧树脂中发挥气相阻燃作用,剩余的磷腈环和苯环基团会进一步裂解产生小分子碎片;另一方面,环氧树脂基体在HPCP的作用下提前分解,产生了基于双酚A结构的大分子碎片并在HPCP裂解产物作用下加速炭化,从而使更多的基体组分以残炭的形式被固定在凝聚相中,提高了阻燃环氧树脂的残炭产率,发挥了凝聚相阻燃作用.     

环三磷腈-DOPO大分子阻燃剂的 合成及阻燃环氧树脂性能

通过取代反应、 缩合反应和加成反应等合成了一种无机-有机杂化大分子阻燃剂 六-[4-(N-苯基氨基-DOPO-次甲基)苯氧基]环三磷腈(DOPO-PCP), 并利用傅里叶变换红外光谱、 ¹H和 ³¹P核磁共振波谱对其进行结构表征. 将DOPO-PCP用于环氧树脂(DGEBA)阻燃, 得到环氧树脂阻燃固化物, 通过极限氧指数(LOI)、 垂直燃烧测试(UL-94)、 热重分析与锥形量热(Cone)测试等对阻燃环氧树脂固化物的热稳定性及燃烧性能进行分析; 利用扫描电子显微镜及Mapping观察并分析了燃烧碳层的形貌与元素分布. 研究结果表明, 产物的结构符合设计的DOPO-PCP分子结构; 当DOPO-PCP在DGEBA中添加量(质量分数)达12.2%时, 磷含量为1.3%, 制得的阻燃环氧树脂固化物垂直燃烧测试通过UL-94 V-0级, LOI值为36.2%; Cone测试结果表明, DOPO-PCP的添加有效降低了DGEBA燃烧时热量与烟气的释放, 且在高温下碳残余量显著增加. 研究表明DOPO-PCP兼具气相和凝固相阻燃机理, 对DGEBA有良好的阻燃性能.     

Improving the flame retardancy of polyamide 6 by incorporating hexachlorocyclotriphosphazene modified MWNT

A nitrogen‐, phosphorus‐ and chlorine‐containing flame retardant, hexachlorocyclotriphosphazene (HCTP), has been covalently grafted onto the surface of multi‐wall carbon nanotubes (MWNT) to obtain MWNT‐HCTP. Polyamide 6 (PA6)/MWNT composites were then prepared via melt compounding. The flammability of PA6/MWNT composite was characterized by cone calorimetry, limiting oxygen index (LOI) and UL‐94 tests. The results showed that peak heat release rate of samples containing 3 wt% MWNT‐HCTP was only 460 kW/m², which decreased by 35.2% compared with that of a neat PA6 sample. The LOI value was increased from 22.7% to 26.5%, and UL‐94 test performance was also significantly improved by the presence of MWNT‐HCTP. Scanning electron microscope (SEM) and optical microscope analysis showed that modified MWNT had a better dispersion and compatibility in PA6 than unmodified MWNT. The composition of residue chars and volatile products was investigated by SEM/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric‐FTIR, respectively. It was proposed that grafted HCTP was mainly functioned in the condensed phase, where P, N can synergistically promote char formation and Cl element can catch free radicals to terminate the chain reaction during combustion of the PA6 composite. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of HZSM-5 zeolites with excellent DME aromatization properties by orthogonal test

Abstract

The synthesis conditions of HZSM-5 zeolite, including crystallization temperature, crystallization time and raw material ratio, were investigated by L₃₂ (4⁸) orthogonal test to specifically optimize its performance in dimethyl ether (DME) aromatization for the first time. Based on the total yield of aromatic products, the synthesis conditions of HZSM-5 zeolite with the best DME aromatization properties were obtained by comprehensive analysis and validation experiments. The relationship between the aromatization performance, crystalline structure, pore structure, and acidity of HZSM-5 zeolite were analyzed. The results showed that the HZSM-5 zeolite accompanied by hierarchical structure, an appropriate Brønsted and Lewis acid content and uniform crystal morphology, was successfully synthesized under optimized conditions. Over this unmodified and un-doped catalyst, the conversion of DME approached to 99.3% and the total yield of aromatics reached was 53.5%.     

Melt polymerization of hexachlorocyclotriphosphazene in the presence of organotin (IV) compounds

The melt polymerization of hexachlorocyclotriphosphazene to poly(dichlorophosphazene) has been studied in the presence of organotin (IV) compounds. Unlike other typical Lewis acids, diethyltin (IV) chloride, Et₂SnCl₂, has shown to be an inhibitor for the thermal polymerization of the trimer, raising the activation energy to 70 kcal/mol. Diethyltin(IV) chloride remarkably delayed the rate of polymerization and efficiently inhibited the crosslinking reaction, thus leading to an improvement in the yield of the linear polymer without sacrifice to its molecular weight. © 1993 John Wiley & Sons, Inc.     

Interfacial synthesis of bisphenol A tetrachlorocyclotriphosphazene from bisphenol A and hexachlorocyclotriphosphazene

The effect of solvent purity on the synthesis and yield of bisphenol A tetrachlorocyclotriphosphazene (BATCCP) has not been described in the literature. The purpose of this research was to synthesize BATCCP hybrid monomers and to evaluate the effect of solvent purity on the BATCCP production. BATCCP monomers were prepared by an interfacial procedure in a water/toluene system as a function of time with the assistance of a phase transfer catalyst, tetraoctylammonium bromide. ¹H and ³¹P NMR confirmed the production of BATCCP monomer by the appearance of chemical shifts at 7.18 and 5.35 ppm in the ¹H NMR and 23.4 and 13.9 ppm in the ³¹P NMR, respectively. Distillation of the toluene, not suggested in previous reports of HCCP hybrid synthesis, resulted in an improvement of actual % yield to 40% and stability of the product throughout the 1440 min reaction as confirmed by MALDI, compared with an 11% actual yield at 15 min, decaying to 2% over a 1440 min reaction when the synthesis was performed with ‘anhydrous toluene’ as provided commercially without further distillation.     

正交试验结合响应面法优化诃子多糖提取工艺

采用正交试验结合响应面法优化诃子多糖的提取工艺,以诃子多糖的提取率为指标,以固液比、提取温度、提取时间和提取次数为因素,正交试验初步筛选工艺参数,响应面法做进一步优化.结果表明,多糖提取的最佳工艺条件为固液比1∶28,提取温度69℃,提取时间1h,提取次数3次,各项指标相对误差均小于2%,应用响应面法可减少诃子多糖提取时间.     

A new colorimetric test for detection of hydroxyl groups in solid-phase synthesis

A new colorimetric test (methyl red-DIC test) for monitoring the presence of hydroxyl groups on resins for use in solid-phase synthesis was developed. The resin became orange-red when the carboxyl group of methyl red formed ester linkages with the resin’s hydroxyl groups. This new test can be used not only for qualitative analysis but also quantitative analysis by using pictures of the relationship between color depth and hydroxy loading rates.     

含双螺环三聚磷腈单元的苯并噁嗪树脂的结构和热稳定性

以双螺环取代三聚磷腈基双苯甲酰氯和4-氨基(N-苯基)苯并噁嗪单体为原料合成了一种含双螺环取代三聚磷腈结构单元的苯并噁嗪树脂单体(HCP-5);采用傅立叶变换红外光谱仪(FT-IR)和核磁共振谱仪(1 H NMR,13 C NMR,31P NMR)表征了苯并噁嗪树脂单体的结构,基于FT-IR和示差扫描量热法研究了其固化行为,并利用热重分析和示差热重分析研究了HCP-5树脂单体、均聚物及其与双酚A型苯并噁嗪树脂(Bz)共聚物的热稳定性.结果表明,HCP-5均聚物具有很好的热稳定性和成炭性,其在317℃下的热失重为5%,在800℃下的残炭率为50%,可用于普通苯并噁嗪树脂改性.此外,HCP-5/Bz(1∶1;质量分数)共聚物在332℃下的热失重为5%,在800℃下的残炭率为48%.     

Solid-phase synthesis of 2-amino-3-chloro-5- and 8-nitro-1,4-naphthoquinones: a new and general colorimetric test for resin-bound amines

Treatment of resin-bound primary or secondary alkyl and arylamines with 2,3-dichloro-5-nitro-1,4-naphthoquinone leads to the rapid formation of intensely colored (red) beads. The resulting 2-amino-3-chloro-5- and 8-nitro-1,4-naphthoquinones can be cleaved rapidly from acid-labile supports in high yields and purities. The reaction is of value as a sensitive and general qualitative test for amino groups on-resin that can be followed by cleavage for characterization and quantification of the chromogen(s) responsible for the color.     

三聚磷腈的制备新工艺

三聚磷腈是生产聚磷腈和环磷腈的主要原料 ,通过采用有机亲核试剂取代活性氯原子 ,可以生成多种化合物 ,具有多种用途 ,可以用作新型高效阻燃剂、侧链液晶、特种橡胶和电子材料等 [1,2 ] .自 1 960年 Lund等以五氯化磷和氯化铵为原料合成出三聚磷腈以来 ,主要集中在原料的选择和产品的分离提纯上 .可以选用 NH3和 HCl代替NH4 Cl作为原料 [3] ,也可选用 PCl3和 Cl2 代替PCl5作为原料 [4 ] ,使产品的收率得以提高 ;还可选用不同的催化剂来进行催化反应 [5] ,缩短了反应时间 .我国目前三聚磷腈的合成 ,大多数仍然采用传统的以五氯化磷和…     

正交试验优化-顶空固相微萃取-气相色谱-串联质谱法测定水中戊二醛

建立了顶空固相微萃取-气相色谱-串联质谱测定水中戊二醛的方法。设计5因素4水平完整的正交试验,通过极差分析获得顶空固相微萃取优化条件。10 mL,pH 1的水样加入6 g NaCl,经非极性PDM S,100μm纤维头于75℃萃取25 min,210℃解析进样0.2 min。采用VF-5(60 m×0.25 mm×0.25μm)色谱柱程序升温分离,选择多反应监测(M RM)模式采集质谱信息。以m/z 82/54为定量离子,以m/z 82/39为定性离子,外标法定量。结果表明,戊二醛质量浓度在0.02~0.6 mg/L范围内线性良好,相关系数(r)>0.9996,方法检出限7μg/L,定量限20μg/L。低(0.04 mg/L)、中(0.1 mg/L)、高(0.4 mg/L)3个水平加标回收率为87.4%~103.7%,相对标准偏差(RSD)<6%。方法适用于测定水中的戊二醛。