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．     

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。     

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%。     

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%。     

聚对苯基苯酚取代磷腈的合成与表征

环状三聚六氯化磷腈在α-氯代萘中开环聚合得到聚氯化磷腈.后者与对苯基苯酚钠反应合成了标题聚合物.测定了该聚合物的IR、~1H NMR谱.GPC估计其数均分子量为6×10~4.扭辫分析表明,该聚合物的玻璃化转变温度与粘流温度分别为0℃和130℃,硫化温度为210℃.     

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。     

2,2,4,4—四对羟甲基酚氧基—6,6—二苯基三聚磷腈的合成

通过Friedel－Crafts反应，将本基引入到六氯环三磷腈上，然后由亲核取代反应和氢化还原反应，合成了2，2，4，4-四对羟甲基酚氧基-6，6-二苯基三聚磷腈，探索了各步的合成、分离方法，并对化合物的结构进行了表征．     

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。     

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[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈合成和气体分离性能研究

以六氯环三聚磷腈为原料通过真空热开环聚合制得线型聚二氯磷腈(PDCP),再通过对PDCP进行亲核取代合成制备了新的聚膦腈类高分子--聚[(四氟丙氧基)2-x(三氟乙氧基).]膦腈,聚合物经过四氢呋喃-苯反复溶解-沉淀得到纯化产物.通过31P-NMR、1H-NMR和FTIR对其结构进行了表征;DSC法测定其玻璃化转变温度...     

新型单组份磷-氮膨胀型阻燃剂的热分解动力学

利用热重分析法研究了在不同升温速率下新型单组份磷-氮膨胀型阻燃剂六(4-(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)-羟甲基苯氧基)环三磷腈(DOPOMPC)在氮气气氛和空气气氛中的热分解动力学.采用Kissinger和Flynn-Wall-Ozawa(FWO)法分别计算出DOPOMPC在相应气氛下的活化能和指前因子.     

Synthesis and thermal stability of a novel phosphorus-nitrogen containing intumescent flame retardant

A novel phosphorus-nitrogen containing intumescent flame retardant （P-N IFR） was prepared via the reaction of dichlor-opentate with N-methylaniline. The structure of the product was confirmed by ^1H NMR, ^31p NMR, MS and IR. TGA analysis showed it has effective thermal stability.     

Effect of a novel phosphorous-nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly(butylene terephthalate)

A novel phosphorus-nitrogen containing intumescent flame retardant (P-N IFR) was prepared via the reaction of a caged bicyclic phosphorus (PEPA) compound and 4,4′-diamino diphenyl methane (DDM) in two steps. The product was added to poly(butylene terephthalate) (PBT) to obtain halogen-free flame retarded polyester. UL-94 test, thermogravimetry and in situ infrared spectroscopy were used to characterize the flammability, thermal degradation properties and the char-forming process. It was shown that the phosphorus-nitrogen containing compound could improve both the flame retardancy and thermal stability more effectively than other P-N flame retardants. Furthermore, it was a good char-forming agent incorporated with the co-addition of polyurethane (PU) when the combustion occurred. The formation of P-N structure was incorporated in the char layer.     

干法制备磷-氮膨胀型阻燃剂的研究

以磷酸、五氧化二磷、季戊四醇和三聚氰胺为原料,采用干法(不添加任何溶剂)合成了一种磷-氮膨胀型阻燃剂。IR分析发现合成阻燃剂具有与磷酸酯三聚氰胺盐类似的P=O和P-O-C双环结构。反应温度、时间和原料配比对酯化反应有明显的影响。酯化反应温度宜控制在120-130℃之间,反应时间2.5小时,加入五氧化二磷可以提高酯化反应的转化率,磷酸与五氧化二磷的摩尔比控制在2:1为宜。热重分析表明,该阻燃剂的起始分解温度为190℃左右,700℃时的成炭率约为30%。该阻燃剂受热后膨胀倍数约为30-50倍,SEM分析发现,阻燃剂膨胀炭层外表面连续、平滑、颗粒之间连结紧密,炭层为内部为多孔结构,空隙大小分布均匀,孔径约为150-200μm之间,这样的泡层结构能更好的起到隔热的效果。     

新型单组分磷氮膨胀阻燃剂的合成

以新戊二醇与三氯氧磷为原料,合成了5,5-二甲基-1,3-二氧杂己内磷酰氯;进而将5,5-二甲基-1,3-二氧杂己内磷酰氯分别与苯并咪唑类衍生物反应,得到三种新型单组分磷氮膨胀阻燃剂(Ⅲa-c).利用IR1、HNMR、质谱及元素分析等表征了Ⅲa-c三种化合物的结构;并利用热重分析考察了三种化合物的热稳定性能.结果表明,目标产物Ⅲa-c均有较好的成炭性和热稳定性,600℃时残炭质量分数分别达26.93%、23.62%及18.75%.     

The investigation of intumescent flame-retarded polypropylene using poly(hexamethylene terephthalamide) as carbonization agent

A novel intumescent flame retardant, containing ammonium polyphosphate (APP), and poly(hexamethylene terephthalamide) (PA6T), was prepared for flame retarding polypropylene (PP). The flame retardation of the PP composites was characterized by limiting oxygen index (LOI). The thermal degradation of the composites was investigated by means of thermogravimetric analysis (TG) and TG coupled with Fourier transform infrared spectroscopy (TG-FTIR). The morphology of the char obtained after combustion of the composites was studied by scanning electron microscopy. It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA6T/APP/PP (5/25/70) system increasing from 17.5 to 32. Meanwhile, the TG and TG-FTIR work indicated that PA6T could be effective as a carbonization agent and there was a synergistic reaction between PA6T and APP, which effectively promoted the char formation of the PP composites. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame retarded PP composites.     

Synthesis of a novel hybrid synergistic flame retardant and its application in PP/IFR

A novel inorganic-organic hybrid synergistic flame retardant was prepared by sol-gel reaction and characterized by NMR and FT-IR. It showed that the fire resistance of polypropylene/intumescent flame retardant (PP/IFR) composites could be improved with the combination of hybrid synergistic flame retardant. The char morphology and structure of PP composites were characterized by SEM and Raman spectra. The influence of the hybrid flame retardant on the thermal degradation process of PP composites was analyzed by FT-IR and the rheological behavior of the PP composites was also evaluated. The thermal stability of PP composites was characterized by TGA, weight loss difference and integral procedural decomposition temperature (IPDT). It indicated that the hybrid synergistic flame retardant had good synergistic effect with IFR.     

Self-extinguishing polypropylene with a mass fraction of 9% intumescent additive II – Influence of highly oriented fibres

Recently, noticeably enhanced flame retardancy of multilayered self-reinforced composites, flame retarded with common ammonium polyphosphate based intumescent system, was described. In this paper the observed novel flame retardant synergism between intumescent additive system and highly oriented polymer fibres is further studied. The ignitability and combustion behaviour of flame retarded multilayer self-reinforced composites were compared to flame retardant compounds, prepared by simple melt compounding, of identical low additive contents, both when the heat was applied parallel (UL-94 tests) and perpendicular (cone calorimetric tests) with the direction of the embedded oriented tapes in self-reinforced composites. SEM and EDS analyses supported the different foaming process of the two types of samples to be understood, while the structure and character of the finally (after combustion) obtained charred layers were examined by compression tests. Considering the results of all the applied testing methods, the complex picture of the mechanism behind the enhanced flame retardant efficiency of flame retarded self-reinforced composites could be clarified.     

The synergistic effect of adjuvant on the intumescent flame-retardant ABS with a novel charring agent

A laboratory-made poly-N,N′-ethyleneterephthalamide (PETA) was used as a novel charring agent and it was combined with ammonium polyphosphate (APP) to prepare the intumescent flame retardant (IFR). For improving the flame retardant efficiency of IFR on acrylonitrile–butadiene–styrene copolymer (ABS), several adjuvant (Adj), such as zeolite 4A (4A), aluminum phosphinate (AlPi), organic montmorillonite, and 2,2′-bis(2-oxazoline), was added, and the synergistic effect was investigated by the limiting oxygen index (LOI), the UL-94 (vertical flame) test, the thermogravimetric analysis (TG), and the scanning electron microscopy (SEM). The results showed that the LOI values of ABS/IFR/Adj (70/30/2) system exceeded 30, and they passed the V-0 rating in the UL-94 test. The TG data demonstrated that the thermal stability and the mass residue of ABS/IFR/Adj were effectively enhanced. Besides, the SEM indicated that adjuvant promoted the formation of the compact, uniform, dense, and intumescent charred layer after burning. After that, the synergistic effect of AlPi and 4A on APP/PETA was investigated by Thermogravimetry-Fourier transform infrared spectroscopy.     

Thermal and flame retardant properties of novel intumescent flame retardant polypropylene composites

Novel intumescent flame retardant polypropylene (PP) composites were prepared based on a char forming agent (CFA) and silica-gel microencapsulated ammonium polyphosphate (Si-MCAPP). The thermal and flame retardancy of flame retardant PP composites were investigated by limiting oxygen index, UL-94 test, cone calorimetry, thermogravimetric analysis, scanning electron micrograph, and water resistance test. The results of cone calorimetry show that the flame retardant properties of PP with 30 wt% novel intumescent flame retardants (CFA/Si-MCAPP = 1:3) improve greatly. The peak heat release rate and total heat release decrease, respectively, from 1,140.0 to 156.8 kW m^?2 and from 96.0 to 29.5 MJ m^?2. The PP composite with CFA/Si-MCAPP = 1:3 has the excellent water resistance, and it can still obtain a UL-94 V-0 rating after 168 h soaking in water.