烯丙基苯并口恶嗪的合成及其固化行为的研究

对3,3,4,4-四氢-3-苯基-1,3-(1′-烯丙基-2′,3′-)苯并口恶嗪(简称烯丙基苯并口恶嗪)的合成方法及其固化行为进行了研究,利用1H-NMR、FT-IR、NR、DSC等对其组成、结构和固化行为进行了表征和推断。结果表明,以甲苯为溶剂,采用溶液法合成烯丙基苯并口恶嗪成环率最高,说明溶液法是一种有效的合成方法。     

苯并噁嗪树脂——一类新型热固性工程塑料

综述了四川大学在苯并口恶嗪树脂研究和产品应用开发等 5个方面的进展 :a.不同组成和性能的苯并口恶嗪的合成 ;b .苯并口恶嗪化反应和固化动力学 ;c .苯并口恶嗪固化过程的体积变化 -膨胀固化 ;d .纤维增强苯并 口恶嗪树脂性能及应用 ;e.以苯并 口恶嗪为粘合剂的制动材料性能及应用。     

咪唑催化苯并噁嗪树脂固化的研究

研究了以咪唑为催化剂的苯并口恶嗪树脂的固化反应。通过平板小刀法测凝胶化时间、等温DSC和程序升温DSC等方法,表征了含有咪唑的苯并口恶嗪树脂的固化反应过程,计算了该体系的固化动力学参数。结果表明,咪唑的引入使苯并口恶嗪树脂的固化初始温度从242℃降到了130℃左右,DSC曲线出现催化固化和热固化2个放热峰;咪唑对苯并口恶嗪树脂的催化作用在一定用量范围内随着用量的增加而增加;通过等温DSC分析,含有咪唑的苯并口恶嗪树脂在150℃下的固化反应是不完全的,经过高温后处理才能固化完全;经过等温动力学计算,咪唑催化苯并口恶嗪的固化反应级数为1.72,活化能为86.3kJ/mol。     

苯并噁嗪及其碳纤维复合材料固化动力学研究

采用非等温DSC技术研究了不同升温速率下苯并口恶嗪/碳纤维复合材料的固化过程。以Avrami方程分析计算了2种固化体系的动力学参数和表观反应活化能。结果表明:Avrami指数n随固化温度的变化能反映出苯并口恶嗪固化过程的2个阶段———凝胶粒子形成和增长阶段及扩散控制阶段。用Avrami速率常数计算得到的表观活化能与文献值基本一致,但能更清楚地反映出碳纤维对苯并口恶嗪固化反应动力学的影响,即催化作用和延缓作用。     

1种低黏度高热可靠性苯并口恶嗪电子封装材料

将1种单环苯并口恶嗪、1种双环苯并口恶嗪和1种含醛基的单环苯并口恶嗪3种树脂混合,获得80℃下粘度为171 mPa.s的新型树脂。经150℃固化后,其Tg为146℃,线膨胀系数为4.3×10-5,耐潮性优于常规环氧塑封料,可用于电子封装。通过DSC和FTIR研究其固化反应,通过BrookfieldII粘度计表征其工艺性,通过TMA和DMA表征其热性能。     

苯并口恶嗪/环氧树脂共聚固化过程研究

采用FT-IR、DSC研究苯并口恶嗪与环氧树脂通过熔融搅拌混合均匀后,固化过程中2种树脂发生开环共聚合的可能性。结果表明:苯并口恶嗪与环氧树脂熔融混合后,在高温区(180℃,200℃)发生了共聚反应,苯并口恶嗪开环过程形成的中间体可以作为环氧树脂的固化剂使用。玻璃化转变温度随着共聚体系中环氧树脂含量的增加先升高,环氧树脂质量分数超过30%后降低,当苯并口恶嗪与环氧树脂的质量比为70/30时,Tg达到最高(218℃),熔融共混在一起程度上提高了共聚体的玻璃化转变温度。     

酚醛改性苯并噁嗪树脂耐烧蚀材料的研究

对不同组成苯并口恶嗪/酚醛共混树脂体系进行了研究,内容包括共混树脂的反应动力学参数计算、共固化机理、热分解动力学以及耐烧蚀性能等。结果表明:酚醛与苯并口恶嗪树脂共混后可以改变苯并口恶嗪的固化机理,酚醛树脂的加入使口恶嗪分子由热开环变为活泼氢开环,在较低温度下就可以反应,降低了固化反应温度。同时共混树脂可以使固化过程收缩率和小分子挥发物比传统的酚醛树脂低,可以减少烧蚀试样的表面裂纹,致密的碳化层具有一定附着强度,提高了共混树脂烧蚀性能。该共混体系可以作为宇航领域中1种性能优良的耐烧蚀树脂体系。     

研究与述评

<正>201710022屏蔽涂层用对苯二胺苯并恶嗪的热固化性能研究[刊,英]/Poorteman,Marc等//Progress in Organic Coatings.-2016,97.-99~109采用苯酚和对苯二胺苯并恶嗪(P-pPDA)等组分配制的溶液,在1050铝合金上旋涂制备了聚苯并恶嗪涂膜,随后对涂膜进行了热处理,使苯并恶嗪单体聚合。     

取代苯胺对含烯丙基的苯并恶嗪的性能影响

以甲基苯胺和苯胺与多聚甲醛、烯丙基双酚A合成了含烯丙基的苯并恶嗪(BA),采用红外及核磁氢谱对其结构进行了表征。其与单官能度苯并恶嗪(PAF)在溶液中共混并加热固化。通过DSC,TGA及DMA对BA及共混物、固化物的热性能进行了研究。结果表明,BA固化峰值温度>250℃,与PAF共混后固化温度下降,且随PAF加入量的增加而下降。共混后固化后热稳定性较好,其中含间位取代苯胺的烯丙基苯并恶嗪与PAF共混树脂的热稳定和弯曲强度最高,热失重5%和10%时的温度分别为308℃、384℃,玻璃化转变温度为171℃,弯曲强度24 MPa。     

天然产物Trichodermamide类似物的合成

以8a-甲氧基-4,4a,5,8-四氢-1,2-苯并口恶嗪-3-羧酸乙酯(1a)为起始原料,经NaOH醇溶液和酸处理,在4-pyrrolidinopyridine和碳化双(环己基亚胺)(DCC)的存在下与3-氨基-7,8-二甲氧基香豆素(2)进行了酰胺化反应,合成了天然产物Trichodermamides的类似物T-1,总收率为61.6%,T-1通过了1HNMR,13CNMR,IR和元素分析等光谱学的结构表征;同时水解反应研究发现,含苯并口恶嗪双环结构的化合物1a可水解脱去酯基,而口恶嗪双环8a位上连有两个O的缩酮类似结构可稳定地保留。     

Syntheses, thermal properties, and phase morphologies of novel benzoxazines functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites

We have successfully synthesized a novel benzoxazine ring-containing polyhedral oligomeric silsesquioxane (BZ-POSS) monomer by two routes: (1) hydrosilylation of a vinyl-terminated benzoxazine using the hydro-silane functional group of a polyhedral oligomeric silsesquioxane (H-POSS) and (2) reaction of a primary amine-containng POSS (Amine-POSS) with phenol and formaldehyde. The benzoxazine-containing POSS (BZ-POSS) monomer can be copolymerized with other benzoxazine monomers through ring-opening polymerization under conditions similar to that used for polymerizing pure benzoxazines. Thermal properties of these POSS-containing organic/inorganic polybenzoxazine nanocomposites have been improved over the pure polybenzoxazine analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The BZ-POSS monomer is poorly miscible with the benzoxazine monomer and tends to aggregate and forms its own domains, both before and after polymerization. At a higher BZ-POSS content, gross aggregation occurs and results in a lower than expected improvement in the thermal properties.     

Poly(benzoxazine-co-urethane)s: A new concept for phenolic/urethane copolymers via one-pot method

Historically, applications for traditional phenolic resin/polyurethane materials are limited due to the inherently weak thermal stability of urethane-phenolic linkage and slow reaction rate. A novel concept has been developed to produce phenolic resin/polyurethane copolymers via benzoxazine chemistry. Through one-pot synthesis, a series of linear poly(benzoxazine-co-urethane) materials has been synthesized via the reaction of a newly developed dimethylol functional benzoxazine monomer with 4,4′-methylene diphenyl diisocyanate and poly(1,4-butyleneadipate). The structure of the copolymers has been characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR). The copolymers in the film forms have been further thermally treated for crosslinking to produce crosslinked poly(benzoxazine-co-urethane) via the ring opening polymerization of cyclic benzoxazine moieties in the main-chain. The tensile properties of the films have been studied and compared with those of traditional high performance materials. The thermal properties of the crosslinked copolymers have also been studied by dynamic mechanical analysis, and thermogravimetric analysis (TGA).     

Highly branched benzoxazine monomer based on cyclotriphosphazene: Synthesis and properties of the monomer and polybenzoxazines

A hyperbranched organic-inorganic hybrid benzoxazine monomer based on cyclotriphosphazene (CP) has been synthesized, which possesses six organic benzoxazine moieties distributed on the inorganic ring of CP. The high molecular weight (1491 g/mol) monomer showed excellent solubility in common organic solvents. Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) were used to study the thermal ring-opening polymerization reaction of the novel benzoxazine monomer. FT-IR spectrum implied that the characteristic absorption peaks of the benzoxazine ring disappeared completely after curing at 240 °C for 1 h, which illustrated that the completion of polymerization reaction. DSC plots indicated that the melting point of the new monomer was 77 °C and an exothermic peak was 225 °C owing to the ring-opening polymerization of the monomer. Due to its highly steric crosslinking structure with rigid and thermal stable inorganic CP as the core, the polybenzoxazine based on the new monomer showed excellent thermal stability and mechanic properties. The char yield of the polymer at 850 °C was 66.9% in nitrogen, and the T_g of the polybenzoxazine was 152 °C.     

Synthesis of linear polymers containing benzoxazine moieties in the main chain with high molecular design versatility via click reaction

Linear polymers with benzoxazine rings in the main chain have been synthesized applying click chemistry approach. These polymers possess molecular weights significantly higher than the benzoxazine polymers which have been chain extended via Mannich reaction. The number average molecular weight is estimated from size exclusion chromatography (SEC) to be between 20,000 and 40,000 Da. The structure of the polymers is confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). Differential scanning calorimetry (DSC) is used to study crosslinking behavior of the polymers. The nature of the low temperature exotherm DSC peak observed in this work and the previous work of other authors is studied by model reactions. It is due to thermal coupling of the residual propargyl and azide end groups in the absence of active catalyst. In addition, a novel diazide-functional benzoxazine monomer has been prepared, showing a tremendous flexibility for applying click reaction to obtain various polymer architectures. Three types of polymers have been prepared from dipropargyl- and diazide-functional benzoxazine monomers. These polymers have been characterized by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA).     

Ultrasound‐assisted synthesis of benzoxazine monomers: thermal and mechanical properties of polybenzoxazines

A series of benzoxazine monomers (P‐aea2–P‐aea8) were prepared from appropriate aromatic diamines containing linear aliphatic ether chains with phenol and formaldehyde through the Mannich reaction under ultrasonication and conventional methods. Based on the reaction performance, the ultrasonication method has been found to be more facile and convenient for the synthesis of benzoxazine monomer than the conventional method. The synthesized monomers undergo curing at a lower temperature than that of conventional benzoxazine (Ba‐A) monomer as evidenced from differential scanning calorimetric analysis. The presence of an aliphatic ether core in the benzoxazine monomer aids in lowering the curing temperature, which seems to vary linearly with chain length. Thermally polymerized benzoxazine (poly(P‐aea_s)) shows an enhanced tensile and flexural strength. Copyright © 2012 Society of Chemical Industry     

苯并噁嗪树脂的改性研究进展

介绍了一种新型热固型塑料苯并噁嗪树脂的分子结构设计,及通过共聚或共混制备或改性苯并噁嗪树脂的近年国内外研究成果,并展望了苯并噁嗪树脂的应用前景。     

一种含尿素的苯并恶嗪的合成及其玻璃布层压板的研制

采用无溶剂法和有溶剂法分别合成了一种新型的苯并恶嗪预聚体,通过核磁共振氢谱、傅立叶红外光谱和差示扫描量热分析对苯并恶嗪预聚体的结构和固化行为进行了研究。并以苯并恶嗪预聚体为胶液、无碱玻璃布为基材,经浸胶、烘焙、压制制得一种玻璃布层压板。该层压板具有优良的力学性能、耐热性能、电绝缘性能、耐水及耐化学药品性能等。     

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     

Solvent-free copolymerization of rigid and flexible bis-1,3-benzoxazines: Facile tunability of polybenzoxazine network properties

We report the copolymerization of a flexible aliphatic-bridged bisphenol-based benzoxazine monomer comprising ten methylene units (BZ(10)BA) with two rigid benzoxazine monomers (commercially available Araldite 35600 and 35900) via a solvent-free cationic ring-opening polymerization process. The effects of monomer feed composition on polymerization behavior, thermomechanical transitions, and thermal degradation properties are reported. DSC of the ring-opening copolymerizations showed that the copolymerization behavior – in terms of polymerization onset temperature and total exothermic transition – depend greatly on the composition of the monomer feed. Samples containing larger concentrations of BZ(10)BA exhibited higher onset temperatures with lower polymerization enthalpies. The thermomechanical properties of the copolybenzoxazine networks, as evaluated by DMA, show a strong dependence on the monomer feed ratio, where higher Araldite content resulted in a higher T_g of the network. The most salient feature of benzoxazine copolymerization was revealed in the tailorability in thermomechanical properties, which were varied by 149 °C simply by changing the monomer feed ratio and the T_g was observed to be accurately predicted using the Fox equation.     

Synthesis and characterization of 2‐oxazoline‐benzoxazine compound and its polymer

A novel 2‐oxazoline‐benzoxazine (POB) was synthesized with 2‐(hydroxylphenyl)‐2‐oxazoline, 1,3,5‐triphenylhexahydro‐1,3,5‐triazine and paraformaldehyde. The chemical structure of the monomer was confirmed by FTIR, ¹H‐NMR, ¹³C‐NMR, and MS. The curing behavior of the monomer was studied by DSC and FTIR, and the ring opening reaction of the monomer was found to occur from 187.5°C. The results of DMA and TGA demonstrated that the thermal properties of polymer for POB monomer (P‐m) are better than polymer for POB precursor (P‐p), because that the oligomer in benzoxazine precursor decreased the perfection of the polymer's network structure; it was also found that the thermal properties of P‐m and P‐p are much better than the common polybenzoxazine and the composite material of benzoxazine and 2‐oxazoline. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci , 2008.