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%。     

新型单组分磷-氮膨胀型阻燃剂的合成及其阻燃性能

以氯化螺环磷酸酯(1)和对甲苯胺(2)为原料,经亲核取代反应合成了"三源"一体的新型单分子磷-氮膨胀型阻燃剂——季戊四醇螺环磷酰对甲苯胺(3),其结构经1H NMR和IR表征。考察了溶剂、原料配比、反应温度、反应时间和缚酸剂对3产率的影响。合成3的最佳反应条件为:乙腈为溶剂,三乙胺为缚酸剂,1 10mmol,n(1)∶n(2)=1∶3,于80℃反应4 h,产率79.3%。阻燃性能研究结果表明,3的初始分解温度为220℃,500℃成炭率达43.3%。     

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。     

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。     

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%.     

正交法研究六氯环三磷腈的合成

利用正交法研究了六氯环三磷腈的合成反应;针对较典型的四个因素,分别取四水平L16(45)正交表进行正交试验,确定了合成目标产物的主要影响因素和优化反应条件.结果表明,先将2/3的固体五氯化磷与2%无水氯化锌和30%吡啶(以五氯化磷物质的量计)混合,再缓慢滴加入剩余的五氯化磷氯苯溶液,最高产率可达84%以上;方差分析结果...     

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。     

1,3,5-三甲氧基苯的绿色合成工艺

以间苯三酚(PG)为原料,碳酸二甲酯(DMC)为甲基化试剂,在K2CO3/(Bu)4NBr催化下合成了1,3,5-三甲氧基苯,其结构经1H NMR,13C NMR和HR-ESI-MS确证。最佳工艺条件为:PG 10 mmol,n(DMC)∶n[(Bu)4NBr]∶n(K2CO3)∶n(PG)=12∶0.15∶1.5∶1,于160℃反应24 h,收率76.0%。     

2,3,6,7,10,11-六甲氧基苯并菲的合成工艺改进

以1,2-二甲氧基苯(1)为原料,二氯乙烷为溶剂,氯化铁为催化剂,合成了2,3,6,7,10,11-六甲氧基苯(2)。在142 mmol,n(FeC l3)∶n(1)=4∶1,50℃反应2 h的最佳反应条件下,2的收率达81.48%。     

A ferrocene dendrimer based on a cyclotriphosphazene core

A ferrocene dendrimer based on a cyclotriphosphazene core was prepared via a sixfold substitution reaction of N₃P₃Cl₆ with a diferrocenyl benzyl alcohol dendron. All twelve ferrocene units in the dendrimer were found to be electrochemically equivalent.     

The Synthesis of Cyclotriphosphazene Liquid Crystals

Generally,thermotropicliquidcrystalsareconstructedoforganiccomPoundsofanisotropicshaPe.Inthesearchfornewmoleculardesignsformesogensoforiginalshapes,onecanroughlyfollowtwodirections.Thefirstideaistovarythenumberofalkylchainsgraftedaroundagivencore.Thesecondideaofshapemodificationconsistsintheformationofclustersofafewidenticalmesogens,generallyatwin.Accordingtothesetwoideas,manynewkindsofliquidcrystalshavebeensysthesized.Hexakis(4-(4'-alkoxy)biphenoxy)cyclotriphosphazeneswerethemostinteresting…     

含烯丙基六苯氧基环三磷腈的合成及其在阻燃丙烯酸酯树脂中的应用

以六氯环三磷腈（HCCP）、苯酚和2-烯丙基苯酚为原料,合成了新型含烯丙基的环磷腈阻燃单体（2-烯丙基苯氧基）五苯氧基环三磷腈（APPCP),用红外光谱、核磁氢谱、质谱和元素分析表征其组成和结构。 将APPCP与丙烯酸酯单体共聚制备了阻燃丙烯酸酯树脂,测试了共聚丙烯酸酯树脂的热稳定性和阻燃性,当APPCP用量为20%时,共聚丙烯酸酯树脂燃烧等级（UL-94）可达V-0级,极限氧指数（LOI）高达31.2%,在空气中600 ℃时残留质量提高至23.2%。     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units

Bis(4-oxybenzoic acid) tetrakis(phenoxy) cyclotriphosphazene (IUPAC name: 4-[4-(carboxyphenoxy)-2,4,6,6-tetraphenoxy-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-yl]oxy-benzoic acid) was synthesized and direct polycondensed with diphenylether or 1,4-diphenoxybenzene in Eaton's reagent at the temperature range of 80–120°C for 3 hours to give aromatic poly(ether ketone)s. Polycondensations at 120°C gave polymer of high molecular weight. Incorporation of cyclotriphosphazene groups in the aromatic poly(ether ketone) backbone greatly enhanced the solubility of these polymers in common organic polar solvents. Thermal stabilities by TGA for two polymer samples of polymer series ranged from 390 to 354°C in nitrogen at 10% weight loss and glass transition temperatures (T_g) ranged from 81.4 to 89.6°C by DSC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1227–1232, 1998     

一种无计有机聚合物中间体——六(甲基丙烯酸羟乙酯)三聚膦腈的合成

六氯三聚膦腈;一种无计有机聚合物中间体——六(甲基丙烯酸羟乙酯)三聚膦腈的合成     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units. II

A new monomer di(4‐carboxyphenoxy) tetrakis(4‐fluorophenoxy)cyclotriphosphazene 1 was synthesized in a two‐step reaction sequence. The direct polycondensation of 1 and/or 4,4′‐dicarboxydiphenylether with aromatic ethers was carried out in P₂O₅/methanesulfonic acid (Eaton's reagent) at 120 °C for 3 h to give two series of aromatic poly(ether ketone)s containing cyclotriphosphazene units. The effect of the introduction of the cyclotriphosphazene group on the solubility and thermal properties of these polymers was discussed with relation to the cyclotriphosphazene contents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2300–2305, 2000     

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.     

两亲性环三磷腈的制备、自组装及应用

合成了一种新的两亲性环三磷腈衍生物, 该化合物通过自组装能形成具有一定规则孔道的微观结构, 具有包载功能. 采用红外光谱、 差热分析和扫描电子显微镜等对产物的结构、 结晶态及微观形貌进行了表征, 同时测试了其细胞毒性. 用该化合物包载姜黄素及磁性纳米粒子, 获得了具有磁靶向功能的载药体系, 研究了载药体系的结晶态、 微观形貌、 热稳定性及磁学性能, 并阐明了载药机制.     

Synthesis and Characterization of Side Group-Modified Tetradentate Cyclotriphosphazene Derivatives

Abstract

A series of novel side group-modified cyclotriphosphazene derivatives were synthesized by the reaction of hexachlorocyclotriphosphazene [N₃P₃Cl₆] with 2,2′-diphenol and the potassium salt of 4-hydroxybenzaldehyde, and subsequent reduction of aldehyde groups to alcohol groups by the use of sodium borohydride. The bromination reaction was carried out with PBr₃ to give N₃P₃(O₂C₁₂H₈) (p-BrCH₂-C₆H₄-O-)₄. This compound was employed in reactions with macrocyclic polyamides, imidazole, or morpholine to produce title compounds. The target compounds were characterized by ¹H NMR, ³¹P NMR, ¹³C NMR, and electrospray ionization mass spectrometry.

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.     

A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties

A novel flame‐retardant epoxy resin, (4‐diethoxyphosphoryloxyphenoxy)(4‐glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epichlorohydrin with (4‐diethoxyphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene and was characterized by Fourier transform infrared, ³¹P NMR, and ¹H NMR analyses. The epoxy resin was further cured with diamine curing agents, 4,4′‐diaminodiphenylmethane (DDM), 4,4′‐diaminodiphenylsulfone (DDS), dicyanodiamide (DICY), and 3,4′‐oxydianiline (ODA), to obtain the corresponding epoxy polymers. The curing reactions of the PPCTP resin with the diamines were studied by differential scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in the following order: DDM > ODA > DICY > DDS. In addition, the thermal properties of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame retardancies were estimated by measurement of the limiting oxygen index (LOI). Compared to a corresponding Epon 828‐based epoxy polymer, the PPCTP‐based epoxy polymers showed lower weight‐loss temperatures, higher char yields, and higher LOI values, indicating that the epoxy resin prepared could be useful as a flame retardant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000