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。     

一种新星型大分子——六对甲酰胺乙酸甲酯苯氧基环三磷腈的合成及其热性能、水解性能的表征

本文以六氯环三磷腈（HCCP）为原料合成了一种以甘氨酸甲酯苯氧基为侧基的新星型环三磷腈化合物六对甲酰胺乙酸甲酯苯氧基环三磷腈（HGPCP）及其中间体,并采用^1H NMR,^13CNMR,^31PNMR,FFIR和元素分析技术对其结构进行了确认．通过TGA、DSC、FrIR技术和测定水解液的紫外光谱,水解残余物剩余质量,残余物的磷含量方法分别对化合物的热性能和水解性能进行了表征．通过比较HGPCP在酸碱环境下的水解结果,发现水解504h,样品的水解过程尚处于化合物侧链断裂阶段,其37℃在酸性缓冲溶液（pH1．0）下较中性缓冲溶液（pH1．0）更易水解．由于其可能在高温下生成交联结构,六对醛基苯氧基环三磷腈（HCPCP）,六对羧基苯氧基环三磷腈（HCPCP）和HGPCP在800℃时碳残余量分别为75％、47％和47％,都表现出良好的热稳定性．     

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。     

新型含磷腈环氧树脂的合成及其阻燃性能

六氯环三磷腈与对羟基苯甲醛经亲核取代反应制得六对醛基苯氧基环三磷腈(HAPCP);HAPCP经高锰酸钾氧化得六对羧基苯氧基环三磷腈(HCPCP);以苄基三乙基氯化铵为催化剂,HCPCP与环氧氯丙烷经开环闭环反应合成了一种新型的含磷环氧树脂(PN-EP),其结构和热稳定性经1H NMR,IR和TGA表征。结果表明,PN-EP的初始分解温度为278℃,在700℃时残炭量为40.5 wt%,具有很好的热稳定性和成炭性能。采用二氨基二苯甲烷对PN-EP进行固化,并通过极限氧指数(LOI)和垂直燃烧(UL-94)对其阻燃性能进行测试。结果表明:PN-EP固化物通过UL-94 V-0级测试,氧指数33%。     

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%。     

聚[(2-氯二乙氧基)x(三氟乙氧基)2-x]磷腈制备及核磁共振谱分析

以2-氯乙氧基乙醇、三氟乙醇和六氯环三聚磷腈为原料,合成2-氯二乙氧基和三氟乙氧基的混合取代聚磷腈。利用31P NMR对反应过程和聚合物的纯化过程进行跟踪,提供了六氯环三聚磷腈、聚二氯磷腈、以及这两种物质的2-氯二乙氧基、三氟乙氧基单一取代和共混取代产物的31P NMR谱图,并通过对这些核磁共振谱数据的对比分析。研究了聚合、取代反应进程和聚合物的提纯程度,建立了用31P NMR对其取代反应和纯化过程进行监测的方法。在以85%H3PO4为外标时,六氯环三聚磷腈的共振峰为δΡ21.30,聚二氯磷腈为δΡ16.61,三氟乙氧基取代环三聚磷腈是δΡ17.97,2-氯二乙氧基在不同位置上取代环三聚磷腈的共振峰是δΡ20.90、δΡ20.48和δΡ12.86处的三连峰,δΡ20.10、δΡ19.65和δΡ8.72处的五连峰则是2-氯二乙氧基和三氟乙氧基在不同位置上取代环三聚磷腈的共振峰,聚[(2-氯二乙氧基)x(三氟乙氧基)2-x]磷腈的共振峰是一个宽峰δΡ7.25。此外,δΡ-7.22对应聚二(2-氯二乙氧基)磷腈,δP-6.88对应聚二(三氟乙氧基)磷腈。对六氯环三聚磷腈和聚二氯磷腈而言,三氟乙氧基都是一种强的亲核取代基团,能够完全取代其上的氯,且取代产物易于通过丙酮-苯的溶解沉淀法去除小分子杂质而得到纯化,而2-氯二乙氧基能完全取代聚二氯磷腈上的氯,但对六氯环三聚磷腈只能部分取代,且须通过更多次的溶解沉淀才能从聚合物中去除杂质。     

聚磷腈荧光纳米粒子的制备及表征

以六氯环三磷腈(HCCP)和荧光素(FL)为单体、乙腈为溶剂、三乙胺(TEA)为缚酸剂,在室温超声作用下,通过沉淀聚合,成功制备了具有良好荧光性能的聚磷腈纳米粒子(PZF)。通过红外光谱、X射线能谱分析(EDS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对PZF的化学结构和组成元素进行了分析。结果表明:制备的PZF是实心结构且粒径均一,具有良好的荧光性能;在365nm紫外光下照射不同时间后PZF的荧光强度几乎没有发生变化,说明制备得到的PZF具有强耐光漂白性。     

磷腈化合物阻燃高分子材料研究进展

磷腈化合物是一类骨架由磷、氮单双键交替排列而成,侧基由有机基团组成的有机-无机化合物.由于其结构特殊、性能优异而被应用于防火阻燃、生物医用、高分子导体及液晶、燃料及催化剂等各种领域.磷腈有高含量的磷、氮元素,因而具有优异的阻燃性能.近年来,环三磷腈阻燃剂被越来越广泛地应用于高分子阻燃材料中.本文阐述了近10年来具有不同取代基的环三磷腈阻燃剂的合成及应用,重点介绍了其对环氧树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚烯烃、聚酯等高分子材料的阻燃性能及热稳定性的影响,并对其影响规律和阻燃机理进行了总结,对其应用前景进行了展望.     

聚双(对羟基苯甲酸甲酯)磷腈的合成及表征

通过一步法合成线性聚二氯磷腈(PDCP),并用对羟基苯甲酸甲酯与线性聚二氯磷腈(PDCP)反应合成聚双(对羟基苯甲酸甲酯)磷腈,运用~1HNMR、~(13)C NMR、~(31)P NMR及FT-IR对其结构进行了表征。DSC和TGA实验表明该聚合物的T_g有了明显的提高且具有较好的热稳定性。     

新型2-(2-羧基苯基)咪唑[4,5-f][1,10]邻菲咯啉的合成及其荧光性能

以1,10-邻菲咯啉和邻羧基苯甲醛为原料,经氧化和缩合反应合成了一种新型的桥连配体——2-(2-羧基苯基)咪唑[4,S-f][1,10]邻菲咯啉(1),其结构经1H NMR,IR,MS和元素分析表征.用FL研究了1的荧光性能,结果表明,1具有较强的荧光,发光纯度较好.     

Synthesis,thermal property and hydrolytic degradation of a novel star-shaped hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene

A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by ¹H NMR, ¹³C NMR, 31P NMR, FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA), differential scanning calorimentry (DSC) and FTIR, while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss, and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions, it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37°C. And the sample hydrolytic degradation still remains at the stage of side groups’ break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP), hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%, 47% and 47% at 800°C, respectively, probably due to cross-linking between molecules.     

Synthesis,Characterization, and Activity of Cyclotriphosphazene-Cyclene Conjugates

Abstract

Two novel cyclotriphosphazene derivatives were synthesized from hexachloro cyclotriphosphzene. Their structures were characterized by ¹H, ³¹P, and ¹³C NMR spectroscopy as well as by IR spectroscopy and electrospray ionization-mass spectrometry (ESI-MS). The Zn complex of 4d was effective in hydrolytic DNA cleavage reactions.     

Preparation and Characterization of Hexakis[2-methoxy-4-(2,3-dimethylphenylimino)phenylato]cyclotriphosphazene

Hexakis[2-methoxy-4-(2,3-dimethylphenylimino)phenylato]cyclotriphosphazene was prepared by the reaction of hexakis[2-methoxy-4-formylphenoxy]cyclotriphosphazene and 3,4-dimethylaniline. The structure of new cyclotriphosphazene derivative was determined by elemental analysis, IR, ¹H NMR, ¹³C NMR spectra, thermal analysis, and X-ray diffraction.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis,characterization, and thermal properties of biodegradable polyetheresteramide copolymers based on 11-aminoundecanoic acid

In this work, new aliphatic polyetheresteramide copolymers based on e-caprolactone, 11-aminoundecanoic acid, and poly(ethylene glycol) (PEG) were synthesized by the melt polycondensation method. The copolymers obtained were characterized by ¹H NMR, differential scanning calorimetry, thermogravimetric analysis/differential thermogravimetry, and wide-angle X-ray diffraction. Water absorption and hydrolytic degradation behavior was also studied. With the increase in PEG content, water absorption and the hydrolytic degradation rate increased accordingly.     

Thermally stable and flame‐retardant aromatic phosphate and cyclotriphosphazene‐containing polyurethanes: synthesis and properties

A novel flame retardant (4‐diphenylphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene (PPPZ) was prepared and characterized by FT‐IR, ³¹P‐NMR and ¹H‐NMR spectroscopy. Polyurethanes that contained aromatic phosphate groups attached to cyclotriphosphazene, with various phosphorus contents, were prepared from PPPZ, poly(propylene glycol), 1,4‐butanediol, and 2,4‐toluene diisocyanate by one‐step polymerization. The polymers prepared were characterized by FT‐IR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and oxygen index (LOI) measurements. The effect of the concentration of PPPZ on the thermal behavior of the polyurethane was studied. The results indicated that the glass transition temperature (T_g) of the polyurethane increased with the concentration of PPPZ. The PPPZ‐containing polyurethanes exhibited slightly higher temperatures of degradation and higher char yields than PPPZ‐free polyurethanes. Moreover, the LOI of the polyurethanes increased with increasing PPPZ content. Also studied was the possible mechanism of the flame retardancy. Copyright © 2005 John Wiley & Sons, Ltd.     

Fast in vitro hydrolytic degradation of polyester urethane acrylate biomaterials: structure elucidation, separation and quantification of degradation products

Synthetic biomaterials have evoked extensive interest for applications in the field of health care. Prior to administration to the body a quantitative study is necessary to evaluate their composition. An in vitro method was developed for the quick hydrolytic degradation of poly-2-hydroxyethyl methacrylate (pHEMA), poly(lactide-co-glycolide50/50)1550-diol (PLGA(50:50)(1550)-diol), PLGA(50:50)(1550)-diol(HEMA)(2) and PLGA(50:50)(1550)-diol(etLDI-HEMA)(2) containing ethyl ester lysine diisocyanate (etLDI) linkers using a microwave instrument. Hydrolysis time and temperature were optimized while monitoring the degree of hydrolysis by (1)H NMR spectroscopy. Complete hydrolytic degradation was achieved at 120°C and 3 bar pressure after 24 h. Chemical structure elucidations of the degradation products were carried out using (1)H and (13)C NMR spectroscopy. The molecular weight (MW) of the polymethacrylic backbone was estimated via size-exclusion chromatography coupled to refractive index detection (SEC-dRI). A bimodal MW distribution was found experimentally, also in the pHEMA starting material. The number average molecular weights (M(n)) of the PLGA-links (PLGA(50:50)(1550)-diol) were calculated by high pressure liquid chromatography-time-of-flight mass spectrometry (HPLC-TOF-MS) and (1)H NMR. The amounts of the high and low MW degradation products were determined by SEC-dRI and, HPLC-TOF-MS, respectively. The main hydrolysis products poly (methacrylic acid) (PMAA), ethylene glycol (EG), diethylene glycol (DEG), lactic acid (LA), glycolic acid (GA) and lysine were recovered almost quantitatively. The current method leads to the complete hydrolytic degradation of these materials and will be helpful to study the degradation behavior of these novel cross-linked polymeric biomaterials.     

Studies on hydrolytic degradation of poly(ester-anhydride)s based on oligosuccinate and aliphatic diacids

This paper describes synthesis, characteristics and hydrolytic degradation of functional poly(ester-anhydride)s based on oligo(3-allyloxy-1,2-propylene succinate) (OSAGE) and aliphatic diacids (DA). The polymers were obtained by polycondensation of OSAGE with adipic (ADP), sebacic (SBA) or dodecanedicarboxylic acid (DDC). The carboxyl groups in OSAGE and in diacids were converted to mixed anhydride groups by acetylation with acetic anhydride. After that, prepolymers thus obtained were condensed in vacuum to yield poly(ester-anhydride)s. The structure of copolymers was confirmed by NMR spectroscopy. Influence of the kind of diacid and the OSAGE to diacid ratio on selected properties of poly(ester-anhydride)s were examined. Poly(ester-anhydride)s were subjected to hydrolytic degradation at 37 °C, in aqueous phosphate buffer solution of pH 7.41 (PBS). The course of degradation was monitored by determination of weight loss of samples, ¹H NMR and DSC. Fracture surfaces of samples during degradation were examined by scanning electron microscopy.     

Synthesis, characterization and hydrolytic degradation of linear and crosslinked poly[(glycino ethyl ester)(allyl amino)phosphazene]

Polyorganophosphazenes substituted by glycino ethyl ester and allylamine with different ratios were synthesized and their structures were characterized by ¹H NMR, ³¹P NMR and FTIR. Via the crosslink reaction, a novel biodegradable crosslinked polyorganophosphazene material was obtained. DSC and FTIR spectra indicated the occurrence of crosslink. Hydrolysis studies were also performed to compare the crosslinked polymers with linear ones. The co-substituted polyorganophosphazenes with more allylamine at pendant groups exhibited a lower degradation rate than poly[bis(glycino ethyl ester)phosphazene] and crosslinked polyphosphazenes had an even lower degradation rate. SEM photographs characterized the surface of polyphosphazenes films after hydrolytic degradation, confirming that uncrosslinked ones had outstanding hydrolytic evidences at the surface while the crosslinked ones only had sporadic small erosion holes, remaining much smoother.     

Reactions of platinum nitrile complexes with cyclotriphosphazenes containing pyridylalkylamino groups

Reactions of platinum(II) and platinum(IV) nitrile complexes with polydentate ligands, such as pentaphenoxy(2-pyridylmethylamino)cyclotriphosphazene, pentaphenoxy(3-pyridylmethylamino)cyclotriphosphazene, and pentaphenoxy(2-pyridylethylamino)cyclotriphosphazene, were studied. Platinum(IV) is reduced to platinum(II) upon complex formation; the pyridine and alkylamine nitrogen atoms coordinate to platinum(II) to form chelate rings. The compounds obtained were characterized by ¹H and ³¹P NMR and IR spectroscopy, FAB mass spectrometry, and other methods.