含DOPO的双酚A-单苯并嗪合成、表征及其固化特性

以双酚A、苯胺、多聚甲醛为原料,合成了双酚A-双苯并嗪(DBOZ),再用其与DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)反应,合成了含DOPO的双酚A-单苯并嗪(DBDO)。采用红外、核磁共振(氢谱核磁共振和碳谱核磁共振)等分析手段对DBOZ和DBDO的化学结构进行了表征;采用差示扫描量热仪对DBOZ和DBDO的固化特性进行研究,使用热重分析分析了所得聚苯并嗪的热稳定性。结果表明:在N2气氛中,DBOZ在205℃左右开环聚合,热分解温度为312℃,在373℃分解速度达到最快,在800℃时的残碳率为37.19%;在N2气氛中,DBDO的热分解温度为353℃,在443℃分解速度达到最快,在800℃时的残碳率为39.60%。     

含双DOPO的双酚A-双苯并(口恶)嗪合成、表征及其固化特性

以双酚A-双苯并(口恶)嗪(DBOZ)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物 (DOPO)为原料,合成了双酚A-双DOPO(2DO),再用其与苯胺、多聚甲醛反应,合成了含双DOPO的双酚A-双苯并(口恶)嗪(2DD).采用红外、核磁共振等分析手段对2DO和2DD的化学结构进行了表征,采用差示扫描量热仪对DBOZ和2DD的固化特性进行研究,使用热重分析仪分析了所得聚苯并(口恶)嗪的热稳定性.结果表明:在N₂气氛中,含双DOPO的双酚A-双苯并(口恶)嗪热分解温度为353℃,在442℃分解速率达到最快,800℃时的残碳率为40.40%,300℃的质量变化为3.97%.与未引入DOPO的双酚A-双苯并(口恶)嗪树脂相比,其热分解温度提高了将近41℃,最大分解速率提高了将近70℃,残碳率提高了将近3.21%.     

含双DOPO的双酚A-单苯并(口恶)嗪合成、表征及其与环氧树脂共聚物的阻燃性能

以含双DOPO-双酚A、苯胺和多聚甲醛为原料,合成了含双DOPO的双酚A-单苯并(口恶)嗪(1DD)。采用红外、核磁(氢谱核磁和碳谱核磁)等分析手段对1DD的化学结构进行了表征;采用DSC对1DD的固化特性进行研究,使用TG分析了所得聚苯并(口恶)嗪的热稳定性。再将1DD与环氧树脂以0.5/1的质量比进行共混,按照一定的程序进行升温固化,得到共聚物P1DD-ER。采用UL94垂直燃烧实验、极限氧指数仪(LOI)测试了共聚物的阻燃性能。结果表明:含双DOPO的双酚A-单苯并(口恶)嗪树脂的起始熔点约为185℃,在222℃处有一个很明显的放热峰。固化后的树脂从348℃开始分解,在463℃分解速率达到最快,在800℃时的残碳率为35.78%。制备的苯并(口恶)嗪可以用作环氧树脂的固化剂,且其共聚物具有很好的阻燃性能,LOI可以达到37,UL94等级为V-0。     

苯并(口恶)嗪的无溶剂法合成及表征

采用无溶剂二步法制得了双酚A型苯并口恶嗪,用红外光谱和核磁氢谱对它进行了表征,并将它的初级产品和溶剂法制得的苯并口恶嗪的初级产品的成环率进行了比较。并通过比较发现,无溶剂二步法制得的苯并口恶嗪的成环率高。     

苯并(口恶)嗪的合成及其固化行为的研究

用无溶剂法合成了一种单环苯并噁嗪。使用傅立叶红外光谱对此苯并噁嗪进行结构表征,并使用差热分析法及热重法对其热性能进行了分析。结果表明此单环苯并噁嗪在加热条件下可开环聚合,聚合产物聚苯并噁嗪具有优良的热性能。在不同固化条件下其性能有明显变化。通过对不同固化条件下制得的一系列聚苯并噁嗪的傅立叶红外光谱图、热失重谱图和差热分析谱图对其结构、固化行为和耐热性能进行了分析。并确定了此单环苯并噁嗪的最佳固化条件。     

新型低黏度苯并(口恶)嗪树脂

介绍了1种新型低黏度苯并口恶嗪树脂,用旋转黏度计研究了这种树脂的黏度,用DSC和凝胶化时间测试等研究了其固化反应行为,并对树脂浇注体和复合材料进行了力学性能测试。实验结果表明,这种树脂具有良好的工艺性能和较高的力学性能,可作为树脂传递模塑成型RTM的高性能复合材料基体树脂或高性能封装用树脂。     

苯并(口恶)嗪改性环氧酸酐体系的固化机理及动力学

利用一种二胺型苯并(口恶)嗪改性环氧酸酐体系。通过FT-IR和DSC分析了改性体系的固化机理。结果表明：共混树脂体系在固化时存在两个反应,首先是环氧树脂与足量的酸酐在咪唑作用下在100℃先开始固化,并在150℃固化2 h后固化完全,之后苯并(口恶)嗪在180℃发生开环聚合。用非等温DSC法研究了该共混体系的固化动力学。采用Flynn-Wall-Ozawa方法求出了共混体系在固化时两个固化反应的活化能,分别为65.27 kJ·mol^-1和92.8 kJ·mol^-1,并利用Friedman方法判断了两个反应都是自催化反应,计算得到自催化模型曲线与实验曲线能较好地吻合。     

含苯磷苯并噁嗪的合成与表征

以含磷中间体(BPPP)、苯胺和甲醛溶液为原料合成了一种新型含苯磷苯并噁嗪单体,通过H谱(1H-NMR)和傅里叶红外光谱(FT-IR)对其化学结构进行了表征,利用差示扫描量热仪和热重分析仪分别研究了其热固化行为及聚合物的热稳定性.结果表明:含苯磷苯并噁嗪的固化过程从135℃开始放热,到261℃放热结束,固化峰值温度为226.5℃;含苯磷苯并噁嗪在不添加任何催化剂的情况下能完全聚合,而且该聚合物具有很好的热稳定性.     

苯并恶嗪树脂的合成及其改性的研究进展

综述了近年来国内外在苯并恶嗪树脂基础研究与应用领域内的最新进展情况;介绍了苯并恶嗪树脂的合成及其改性方法,并对苯并恶嗪树脂的发展趋势进行了展望.     

5-硝基螺(口恶)嗪的合成及其光致变色

螺(口恶)嗪是一类重要的光致变色化合物,与研究最多的螺吡喃化合物相比,其主要优点是热稳定性高、抗疲劳性强。做为光致变色光存贮材料,它是一类值得重视的化合物,但关于此类化合物的研究却还很少。限制此类化合物在光致变色光存贮材料中应用的最大困难是它们的最大吸收(一般在650nm左右)与现有半导体激光器的光源波长(一般大于750nm)不相适应。     

Epoxy resin cured by bisphenol A based benzoxazine

Bisphenol A based benzoxazine was prepared from bisphenol A, formaline, and aniline. This benzoxazine was used as a hardener of the epoxy resin. Curing behavior of the epoxy resin and the properties of the cured resin were investigated. Consequently, curing reaction proceeded without a curing accelerator. The molding compound showed good thermal stability under 150°C, which corresponded to the temperature in the cylinder of injection molding. Above 150°C, the curing reaction proceeded rapidly. The cured epoxy resin showed good heat resistance, water resistance, electrical insulation, and mechanical properties compared with the epoxy resin cured by the bisphenol A type novolac. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1903–1910, 1998     

Studies on new type of phenolic resin (IX) curing reaction of bisphenol A‐based benzoxazine with bisoxazoline and the properties of the cured resin. II. Cure reactivity of benzoxazine

Bisphenol A‐based benzoxazine that contained oligomers (oligo‐Ba) was prepared from bisphenol A, formaline, and aniline. Curing reaction of oligo‐Ba with bisoxazoline and the properties of the cured resin were investigated. Consequently, the ring‐opening reaction of benzoxazine ring occurred, and then the phenolic hydoroxyl group generated by the ring‐opening reaction of benzoxazine ring reacted with oxazoline ring. It was found that the cure induction time and cure time of the molten mixture from oligo‐Ba and bisoxazoline could be reduced and also the cure temperature could be lowered, compared with those from bisphenol A‐based benzoxazine, which contained no oligomers (Ba), and bisoxazoline. The melt viscosity of the molten mixture from oligo‐Ba and bisoxazoline was kept 0.1–10 [Pas] at 140°C even after 40 min, the molten mixture from oligo‐Ba and bisoxazoline showed good flowability below 140°C as well as that from Ba and bisoxazoline. However, above 160°C the curing reaction of oligo‐Ba with bisoxazoline proceeded more rapidly than that of Ba with bisoxazoline. The cured resin from oligo‐Ba and bisoxazoline showed good heat resistance and water resistance, compared with the cured resin from Ba and bisoxazoline. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2331–2339, 2001     

New thermosetting resin from terpenediphenol‐based benzoxazine and epoxy resin

Terpenediphenol‐based benzoxazine was prepared from terpenediphenol, formaline, and aniline. Curing behavior of the benzoxazine with epoxy resin and the properties of the cured resin were investigated. Consequently, the curing reaction did not proceed at low temperatures, but it proceeded rapidly at higher temperatures without a curing accelerator. The properties of the cured resin both from neat resins and from reinforced resins with fused silica were evaluated, respectively. The cured resins showed good heat resistance, mechanical properties, electrical insulation, and especially water resistance, compared with the cured resin from bisphenol A type novolac and epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2266–2273, 1999     

丙氧基化双酚A缩水甘油醚的合成与固化性能

以丙氧基化双酚A（D33）、环氧氯丙烷（ECH）和液碱为主要原料,采用两步法工艺合成了丙氧基化双酚A缩水甘油醚（DGEPBA）。考察了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响。结果表明：开环催化剂三氟化硼-乙醚（BF₃-Et₂O）,质量分数0.1%,D33与ECH的质量比为1∶2.0,反应温度70℃,反应时间2.5h;闭环催化剂苄基三乙基氯化铵质量分数0.2%,D33与NaOH的质量比为1∶2.2,反应温度40℃,反应时间6h时,产物环氧值为0.291eq/100g,产率95.4%,黏度为1180mPa·s。通过FTIR和¹H NMR对产物结构进行表征,并将不同质量分数的DEEBAPO掺入到E-51环氧树脂中,与二乙烯三胺（DETA）进行固化,并对其固化物力学性能进行测试。因为DGEPBA的掺入,使得E-51固化物在抗拉伸、抗冲击方面均有明显提高。热失重（TGA）分析表明固化物热稳定性稍有提高,扫描电镜（SEM）显示断裂面为韧性断裂。     

Synthesis and properties of a novel bio‐based benzoxazine resin with excellent low‐temperature curing ability

A novel bio‐based benzoxazine resin (diphenolic acid/furfurylamine benzoxazine resin, PDPA‐F‐Boz) was prepared by using bio‐based diphenolic acid, furfurylamine and paraformaldehyde as raw materials. The structure of DPA‐F‐Boz monomer was characterized by Fourier transform infrared spectroscopy, ¹H NMR and ¹³C NMR, and then its curing reaction and the thermal stability of the cured PDPA‐F‐Boz were analyzed. Compared with the traditional fossil‐based benzoxazine (bisphenol A/aniline benzoxazine, BPA‐A‐Boz) and the bio‐based benzoxazine (diphenolic acid/aniline benzoxazine, DPA‐A‐Boz), DPA‐F‐Boz monomer showed the lowest curing temperature, and PDPA‐F‐Boz had the highest residual char ratio at 800 °C and the lowest degradation rate at the peak temperature. Meanwhile, the total heat release, peak heat release rate and heat release capacity of PDPA‐F‐Boz were much lower than those of PBPA‐A‐Boz and PDPA‐A‐Boz. Thus, PDPA‐F‐Boz showed excellent low‐temperature curing ability and thermal stability. © 2019 Society of Chemical Industry     

Study of the characterization and curing of a phenyl benzoxazine using 15N solid-state nuclear magnetic resonance spectroscopy

A difunctional 1,3-benzoxazine compound, 2,2′-(3-phenyl-4-dihydro-1,3,2-benzoxazine)propane ( B-a ), derived from bisphenol-A, ¹⁵N-enriched aniline, and formaldehyde was synthesized and characterized using ¹⁵N-NMR and ¹³C-NMR spectroscopies. The observed resonances in the solid-state ¹⁵N- and ¹³C-NMR spectra showed good agreement with the calculated chemical shifts which are based on the chemical structure. The B-a samples were cured at 150 and 200°C. The polymerization inspired peak intensity changes and line-width broadenings in the NMR spectra. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1401–1411, 1998     

双酚二胺型苯并噁嗪树脂的合成及表征

以双酚、甲醛和二胺为主要原料,以甲苯为溶剂,合成了苯并嗪(BOZ)中间体。采用红外光谱(FT-IR)技术对其结构进行了表征,同时采用差示扫描量热(DSC)法和热重分析(TGA)法对其固化过程及热稳定性能进行了研究。结果表明:双酚二胺类BOZ体系具有较宽的固化峰,其在200℃左右开始开环固化,具有良好的加工性能;700℃时的残炭率均超过40%(其中AFMDA体系为65%),耐温指数为185℃,说明该双酚二胺类BOZ体系是一种良好的耐高温材料,可以用于耐高温胶粘剂的制备。     

Synthesis and characterization of a hybrid material based on a trimethoxysilane functionalized benzoxazine

A polybenzoxazine/polysiloxane hybrid has been prepared by sol–gel process and ring‐opening polymerization. For this purpose, first a functionalized benzoxazine was synthesized from bisphenol A, paraformaldehyde and 3‐(trimethoxysilyl) propylamine, with initial molar ratio 1 : 4 : 2, and 95% yield. The structure of the monomer was characterized by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance. The sol–gel process and curing behavior have been studied by FTIR spectroscopy and differential scanning calorimetry. The dynamic mechanical thermal analysis of the hybrid material (Bz‐PSi) showed higher T_g and storage modulus respect to the conventional polybenzoxazine (Bz‐BA). Also, the thermogravimetric analysis revealed a better thermal stability. The high limiting oxygen index (LOI) values (about LOI = 32) confirmed similar effective flame retardance properties of the hybrid material respect to conventional benzoxazine. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012