含烯丙基的三元酚型苯并噁嗪的合成及性能

以合成的1,3,5-三(p-羟基苯基)苯(TP)、烯丙基胺和甲醛为原料,合成了一种新型的含烯丙基的三元酚型苯并噁嗪单体——1,3,5-三(3-烯丙基-3,4-二氢-2H-1,3-苯并噁嗪基)苯(tp-ala).采用核磁共振谱、傅里叶变换红外光谱、紫外-可见吸收光谱和差示扫描量热表征了tp-ala的结构和固化行为,用热失重分析、动态热机械分析和荧光光谱测试了固化物P-tp-ala的热性能及光学性能.结果表明,烯丙基的引入使P-tp-ala玻璃化转变温度高达322℃,5%的热失重温度为351℃,800℃残炭率达到61.4%,与不含烯丙基的三元酚型苯并噁嗪相比具有较好的耐热性.在233 nm激发波长下,P-tp-ala的荧光发射波长为350 nm,具有荧光性能.由于P-tp-ala中的芳香含量高,使其折射率高达1.6325,在防折射涂层方面有很好的应用潜力.     

1,2,3-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯的合成

以二溴新戊二醇与三氯氧磷为原料,三乙胺为催化剂,合成得到5,5-二溴甲基.1,3-二氧杂己内磷酰氯,再与邻苯三酚反应得到新型磷系阻燃剂1,2,3-三(5,5-二溴甲基-1,3-二氧杂已内磷酰氧基)苯,两步反应总产率71.3%.目标产物结构经元素分析、IR、MS、及1H NMR证实.热失重分析表明,目标产物具有较高的热稳定性和良好的成炭性,起始分解温度为295.25℃,500℃时炭残余量达27.75%.     

9,10-2H-9-氧杂-10-磷杂菲-10-氧化物基1,3-苯并噁嗪树脂的合成与表征

以水杨醛、对甲基苯胺(或对氟苯胺,对甲氧基苯胺)、9,10-2H-9-氧-10-磷杂菲-10-氧化物(DOPO)及甲醛为原料,通过三步反应合成了三个含DOPO基的1,3-苯并噁嗪化合物3a-3c.第一步,水杨醛与对位取代苯胺进行缩合反应生成亚胺(1a-1c);第二步,DOPO对亚胺进行加成反应得到仲胺(2a-2c);第三步,仲胺与甲醛在强酸性离子交换树脂催化下进行关环反应形成含DOPO的1,3-苯并噁嗪树脂.采用红外光谱、核磁共振谱和质谱等表征了化合物3a-3c,同时采用热失重分析技术测定了其热稳定性.结果表明,3a-3c由两对对映体组成,质谱条件下2a-2c和3a-3c均经裂解失去稳定的DOPO基团;3a-3c热降解反应包含两个热失重过程,分别在250和400℃下出现最大热释放速率.     

新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基- 2-氧)苯的合成及热分解动力学研究

以新戊二醇、三氯氧磷及1,3,5-三羟基苯等为原料, 经过两步反应合成新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂-2-氧代己内磷酰基-2-氧)苯, 采用元素分析、FT-IR、MS及1H NMR等技术确定了标题化合物的分子结构. 以TG-DTG为手段, 研究该新型磷系阻燃剂在氮气气氛中的热分解动力学; 利用Kissinger法、Flynn-Wall-Ozawa (FWO)法对其进行热分解动力学研究, 求出该阻燃剂的热分解动力学参数; 利用Coast-Redfern法研究该阻燃剂的热分解机理. 结果表明, Kissinger法所求得的表观活化能为171.72 kJ•mol－1, 指前因子ln A为37.57; Flynn-Wall-Ozawa法所求得的表观活化能为172.05 kJ•mol－1. 标题化合物的热分解动力学方程g(α)＝α1/4, 反应级数n＝1/4.     

1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)新法合成、晶体结构和热性能研究

研究了1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)的合成新方法,以乌洛托品和硝基胍为原料,通过Mannich反应得到2-硝亚胺基-六氢化-1,3,5-三嗪盐酸盐(NIHT·HCl),用HNO3/AC2O硝化可得Keto-RDX,并采用核磁共振、红外、质谱以及元素分析等进行了结构表征.培养了Keto-RDX单晶,晶体结构解析表明:晶体属于正交晶系,空间群Pnma,晶胞参数a=1.0057(17)nm,b=1.3483(2)nm,c=0.5982(10)nm,V=0.8112(2)nm3,Z=4,Dc=1.933 g/cm3,μ=0.188 mm-1,F(000)=480.差示扫描量热(DSC)法和热失重(TG/DTG)法分析表明,Keto-RDX分解峰温为211.4℃(DSC),在185.00～202.79℃为固相分解阶段,峰温为198.61℃,质量损失为21.45%,在202.79～230.00℃为液相分解阶段,质量损失为77.83%,峰温为213.78℃,热稳定性较RDX差.     

在线热裂解/气相色谱-质谱分析3-吡啶甲酸茴香酯的热裂解产物

采用在线热裂解/气相色谱-质谱(Py/GC-MS)联用技术对3-吡啶甲酸茴香酯进行热裂解分析。通过酰氯化和酯化反应合成了新型目标化合物3-吡啶甲酸茴香酯,其分子式为C14H14NO3。目标化合物的结构经核磁氢谱(1H NMR)、核磁碳谱(13C NMR)、红外光谱(IR)和高分辨质谱(HRMS)进行确证,并通过热重-微热重-差示扫描量热(TG-DTG-DSC)分析方法对目标化合物的热稳定性进行分析。在空气氛围中,将目标化合物分别于300,600,900℃下进行热裂解,并通过气相色谱-质谱法对其挥发性热裂解产物进行定性和半定量分析。研究显示:目标化合物共经历了两次失重过程。第一次失重在129.9~158.9℃之间,失重2.3%;第二次失重在158.9~274.9℃之间,失重达90.1%,230.1℃时失重率最大。热裂解共产生44种产物,包括具有香味特征的大茴香醛、对甲基苯酚、松油醇、D-香茅醇、大茴香醚和茴香醚等化合物。其中裂解温度对裂解产物的种类和相对含量具有明显影响。300℃时α-二去氢菖蒲烯的相对含量最高,600,900℃时,相对含量最高的分别是大茴香醛和对甲基苯酚。苯甲醛、茴香醚和大茴香醚的相对含量随着温度的升高呈先增加后降低趋势;而对甲基苯酚含量则随着温度的升高而增加。根据主要裂解产物及其相对含量的变化,对目标化合物的裂解机理进行了初步探讨。     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

三氯化稀土催化下二乙氧基缩苯乙酮与乙酰氯的反 应: 合成1, 3, 5-三芳基苯 的新方法

报道催化量的三氯化钐存在下,乙酰氯与二乙氧基缩苯乙酮反应,高产率地得到1,3,5-三苯基苯。采用不同的溶剂及不同的稀土氯化物该反应均能顺利进行。此方法是一种合成1,3,5-三芳基苯类化合物的方便和有效的方法。文中对反应机理进行了讨论。     

1,3,5-苯三甲醛的合成与应用研究进展

介绍了1,3,5-苯三甲醛的合成与应用。在1,3,5-苯三甲醛的众多合成方法中,以氧化还原方法最常见,此外水解、聚合等方法各具优点,在满足高产率和绿色化学方面有了更多选择。1,3,5-苯三甲醛是一种具有广泛开发应用前景的化学合成中间体,以其为原料合成的大分子物质具有优异的化学、物理特性和生物活性,在催化、光电、抗病毒,以及分子吸附和药物包材等方面具有广泛的应用。     

刚性配体1，3，5-三(1-咪唑基)苯与1，2，4-苯三甲酸构筑的金属配合物：水热合成及晶体结构

由水热法合成了2个配合物[Co(1,2,4-HBTC)(tib)](1)和[Ni4(1,2,4-BTC)2(tib)4(H2O)2]·(1,2,4-HBTC).9H2O(2)(1,2,4-H3BTC=1,2,4-苯三甲酸,tib=1,3,5-三(1-咪唑基)苯),并用元素分析、红外光谱、X-射线单晶衍射及热重分析等对其进行了表征。晶体结构分析结果表明:配合物1是由Co(Ⅱ)和tib连接形成的二维层状结构,1,2,4-HBTC2-作为端基配体与Co(Ⅱ)配位,而配合物2是通过1,2,4-BTC3-连接[Ni(tib)]2+二维网形成最终的二维多层结构,这2个化合物最终均被氢键连接形成三维超分子结构。     

聚苯氧基磷酸联苯二酚酯/聚磷酸铵膨胀阻燃剂对环氧树脂阻燃性能影响研究

以聚苯氧基磷酸联苯二酚酯(PBPP)与聚磷酸铵(APP)组成复合阻燃剂,对环氧树脂(EP)进行阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法研究改性环氧树脂的阻燃性能和阻燃机理.结果表明,PBPP/APP体系对EP具有较好的阻燃性能,阻燃剂添加量为10%时能使环氧树脂的氧指数提高到29.6%,垂直燃烧等级达到UL94 V-0级,残炭量大大增加;平均热释放速率下降45.7%,热释放速率峰值下降51.0%,有效燃烧热平均值下降21.1%;TGA、CONE、SEM等综合分析显示了PBPP/APP改性后的环氧树脂比纯环氧树脂具有更高的热稳定性,燃烧后能够形成连续、致密、封闭、坚硬的焦化炭层,在聚合物表面产生有效覆盖、隔绝了氧气,改善了环氧树脂的燃烧性能.     

三聚氰胺三聚硫氰酸盐的合成

以三聚氰胺和三聚硫氰酸为原料合成了一种新型含硫三聚氰胺基阻燃剂——三聚氰胺三聚硫氰酸盐(MSA),其结构和热性能经1H NMR,13C NMR,FT-IR,元素分析和TGA表征。确定了合成MSA的最优工艺条件为:去离子水为溶剂,三聚硫氰酸和三聚氰胺摩尔比为1∶1,反应时间为3 h。TGA分析表明:MSA失重5%时,温度为308.8℃,600℃时分解基本完全,残碳率为0.86%。     

磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、五硫化二磷(P2S5)为原料合成9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS),并将DOPS与聚磷酸铵(APP)组成复合阻燃剂,用于环氧树脂(EP)的阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法对改性后的环氧树脂的阻燃性能和阻燃机理进行了测试和分析.实验结果表明,DOPS/APP阻燃体系对EP具有很好的阻燃性能,且复配阻燃剂的阻燃效果比单一的阻燃剂阻燃效果好;其中,当阻燃剂的总添加量达到30%时即W_(DOPS)=10%、W_(APP)=20%时,阻燃EP复合材料的LOI值可达到29.2%,垂直燃烧等级达到UL-94 V-0级,残炭量可达49.3%.     

改性酚醛成炭剂的制备及其在氢氧化镁/聚酰胺6阻燃体系中的协效阻燃作用

氢氧化镁(MH)是一种重要环保型阻燃剂,针对MH阻燃效率低,添加量大,与树脂相容性差的特点,研制了硼改性酚醛基成炭剂(BPF)用于增强MH的凝聚相阻燃作用,以提高MH的阻燃效率.用XRD、红外、核磁等手段表征了BPF的化学结构.TGA研究表明BPF成炭性优异,750℃时残炭高达61%.阻燃PA6体系中,BPF与MH有显著的协效作用,材料能通过UL94-1.6 mm V0级别.BPF的阻燃增效机理分析表明,BPF燃烧时生成的B2O3可在燃烧材料表面富集形成玻璃态的有效阻隔层,使材料自熄.此外,BPF能显著提高材料加工流动性,具有较好增塑、润滑作用.BPF不会恶化材料力学性能,阻燃材料综合性能优良.     

超支化聚磷酸酯阻燃剂对尼龙6的成炭促进作用

以三氯氧磷和双酚A为原料制备了具有超支化结构的聚磷酸酯阻燃剂(HPPEA),通过红外(FTIR),核磁(1H-NMR,31P-NMR)及热重分析表征了产物的结构和热稳定性.将HPPEA与三聚氰胺聚磷酸盐(MPP)进行复配,通过熔融共混法制备阻燃尼龙6,通过氧指数法和垂直燃烧法测试了其阻燃性能,采用热重分析(TGA)研究...     

A novel halogen-free flame retardant for glass-fiber-reinforced poly(ethylene terephthalate)

In order to prepare halogen-free flame-retardant glass-fiber-reinforced poly(ethylene terephthalate) (FR-GF-PET), a novel flame retardant containing three flame-retardant elements, P, N and S, was synthesized by melt condensation reaction. Its chemical structure was characterized by FT-IR and ¹H NMR spectra. FR-GF-PET was prepared by melt-mixing the flame retardant with GF-PET. The effects of the flame retardant on the flammability and thermally decomposing behaviors of GF-PET were studied via LOI, UL-94 and TGA tests. The results showed that despite a negative effect on the thermal stability of GF-PET, the incorporation of the flame retardant improved the flame retardancy of GF-PET largely. The LOI values of GF-PET increase linearly with the increase of flame retardant content. The GF-PET passed the V-0 rating in UL-94 tests when 15 wt% of the flame retardant was added to GF-PET. An interesting phenomenon was found, that is, with the increase of flame retardant content, the flame retardancy of the system increased but the char yield decreased, which was explained according to the evidences of XPS tests and the kinetics of thermally decomposing reaction.     

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.     

新型树状单分子磷-氮膨胀阻燃剂的合成及阻燃性能研究

以六氯环三磷腈、对羟基苯甲醚、新戊二醇以及三氯氧磷等为原料,合成一种新型树状单分子磷-氮膨胀阻燃剂六(4-(5,5-二甲基-1,3-二氧杂环己内磷酸酯基苯氧基))环三磷腈(VI).标题化合物结构经IR、MS及1H NMR证实.热失重分析表明标题化合物具有较高的热稳定性和良好的成炭性,氮气氛下的起始分解温度为270℃,600℃时炭残余量达45.2%.实验表明,标题化合物对环氧树脂呈现出良好的阻燃效果.     

Fire Retardancy of Aluminum Hydroxide Reinforced Flame Retardant Modified Epoxy Resin Composite

A novel phosphorous containing flame retardant epoxy resin is synthesized by modifying the epoxy resin initially with phosphoric acid and further with aluminum hydroxide (ATH) to enhance the fire retardancy of the modified epoxy resin. The several phosphorous modified epoxy resin to ATH mass ratios were used to study the effect of ATH addition on epoxy. Thermal and mechanical properties. The structure of the modified flame retardant epoxy resin was characterized using Fourier-transform infrared spectroscopy (FTIR) while thermal degradation behavior and flame retardant properties were examined using thermo-gravimetric analysis (TGA) and UL-94 testing. Furthermore, ultimate tensile strength and young modulus were analyzed to study the effect of ATH addition on mechanical properties. The findings indicated that fire retardancy of ATH reinforced modified ep oxy resin is higher than virgin and phosphorous modified epoxy resin and depicted eminent flame retardant properties with suitable mechanical properties.

     

Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus,nitrogen, and sulfur

A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.