含二氮杂萘酮联苯结构耐高温聚氨酯胶的合成

采用本体聚合,将自制的含有4—(4’—羟基苯基)—2,3—二氮杂萘—1—酮(DHPZ）^[1—3]作为单体引入双组分聚氨酯的固化剂中,合成了一类新型的含杂萘三联苯结构的聚氨酯胶粘剂。DHPZ的扭曲和非共平面杂环结构使聚合物难以实现长程有序。从而提高了其刚性和耐高温性能。常温拉伸强度不低于20MPa,而且具有较强的耐酸,耐水水解性能。以FT-IR,DSC,TGA等分析手段研究了聚合物的结构和耐热性能。结果表明,新型聚氨酯胶粘剂具有高的玻璃化转变温度（Tg=340～370K）,氮气氛中10%热质量损失温度为570K,在520K的温度下无热质量损失。该胶粘剂可以在高温条件下使用。     

含二氮杂萘酮结构环氧胶粘剂的研制

以低分子质量舍二氮杂萘酮结构环氧树脂与环氧树脂E44配合作为胶粘剂基料，低分子聚酰胺(H-4)为固化剂，试制了一种在常温及中温下都有较好粘接性能的环氧胶粘剂。当配方为m(E44)：m(ER)：m(H-4)=4:4:9时．在180℃下固化3h后，测其常温下的拉伸剪切强度为17．65MPa，80℃下为19．71MPa。并研究了固化工艺对粘接性能的影响。     

含杂萘酮联苯结构耐高温聚氨酯胶粘剂的合成

采用本体聚合，将自制的含有4-(4’-羟基苯基)-2，3-二氮杂萘—1-酮(DHPz)作为单体引入双组分聚氨酯的固化剂中，合成一类新型的含杂萘类联苯结构的聚氨酯胶粘剂。DHPz的杂萘类联苯结构提高了胶粘剂的结构刚性和耐高温性能。常温剪切强度不低于20MPa，而且具有较强的耐酸、耐水解性能。以FT-IR、DSC、TGA等分析手段研究了聚合物的结构和耐热性能。结果表明，新型的聚氨酯胶粘剂具有较高的玻璃化转变温度(Tg＝170—200℃)，在氮气氛围中10％热失重温度为300℃，250℃无失重。该胶粘剂可在较高温度下使用。     

含二氮杂萘联苯结构聚氨酯的合成与性能研究

以聚己内酯二醇(PCL)、4-(4'-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)、4,4'-二苯基甲烷二异氰酸酯(MDI)及1,4-丁二醇为原料,采用一步法设计合成了含二氮杂萘联苯结构聚氨酯溶液。采用红外光谱仪、X射线衍射仪、热重分析仪以及万能力学试验机,考察了DHPZ含量对聚氨酯胶膜耐高温性能和力学性能的影响。结果表明,二氮杂萘联苯结构提升了聚氨酯膜的耐热性能,DHPZ质量分数从0到5%,初始热分解温度(T_d~(1%))可提高10～20℃;当DHPZ质量分数为2%时,聚氨酯膜力学性能较优,其拉伸强度达到67. 1 MPa,断裂伸长率为860%,弹性模量为4. 5 MPa。     

新型含二氮杂萘酮结构——聚氨酯清漆的合成及性能

针对传统通用型聚氨酯涂层材料耐高温性欠佳的缺点，本文通过分子结构设计，将全芳环非公平面、扭曲的二氮杂耐酮联苯结构引入聚氨酯主链中，首次合成了含二氮杂萘酮联苯结构聚氨酯树脂，研究其结构性能关系，并将其应用于涂料领域。以TDI、TMP和自制的4-(4’-羟基苯基）-2，3-二氮杂萘-1-酮(DHPZ)为原料，以简便的工艺制备了结构新颖的含二氮杂萘酮结构的单组份聚氨酯清漆PUv-C。以傅立叶红外变换手段(FT-IR)表征了聚氨酯涂层树脂的结构。以差示扫描量热仪(DSC)和热重分析仪(TGA)等分析手段研究了聚氨酯涂层树脂的耐热性能。     

含氟杂萘联苯型聚醚酰亚胺共聚物的合成

2，2′-双(3，4—二羧酸)六氟丙烷二酐和2—(4—氨基苯基)—4—[4—(4—氨基苯氧基)苯基]—2，3—二氮杂萘—1—酮分别与4，4′-二氨基二苯醚、4，4′—二氨基二苯砜在间甲酚中进行“一步法”溶液共聚合，制备了2种共聚聚醚酰亚胺。通过差示扫描量热法、热失重，傅里叶变换红外光谱、核磁共振氢谱对聚合物进行了表征。聚合物具有优异的耐热性能，玻璃化转变温度高于300℃，热失重温度高于500℃。同时，聚合物在常用非质子有机极性溶剂中具有优良的溶解性能。     

含二氮杂萘酮环氧树脂体系的固化反应动力学研究

以 4- (4-羟基苯基 ) - 2 ,3 -二氮杂萘 - 1-酮 (DHPZ)为固化剂 ,用示差扫描量热法 (DSC)对环氧E44 /DHPZ体系的固化反应过程作了系统的研究 ,计算出固化反应的表观活化能为 10 4 0 4kJ/mol,固化反应近似为一级反应。通过固化剂份数对化学反应程度影响的研究 ,得知当DHPZ份数为 4 5～ 5 5时固化反应完全     

含二氮杂萘酮结构环氧树脂胶粘剂的研制

以双氰胺 (DCDA)为固化剂 ,以咪唑 (MZ)为固化促进剂 ,研制了一种含二氮杂萘酮结构的环氧树脂 (ER)胶粘剂 ,其成分为ER∶DCDA∶MZ∶SiO2 ∶Al=10 0∶7∶1∶3∶60 ,固化工艺为 12 0℃下固化 40min时 ,拉伸剪切强度为 17.8MPa ,有良好耐热性     

注塑级含二氮杂萘酮联苯结构的聚醚酮/聚四氟乙烯共混物的性能研究

通过熔融共混制备了聚四氟乙烯质量分数低于30%的注塑级含二氮杂萘联苯结构聚醚酮/聚四氟乙烯(PPEK/PTFE)共混物,并对其摩擦性能、力学性能、热性能和密度进行了研究。PTFE的加入,使得共混物的摩擦性能比纯PPEK得到大幅度的改善,且随着PTFE含量的增加,共混物的摩擦性能逐步提高;共混物的力学性能则随PTFE含量的增加有所降低,但依然处于较高的水平;不同配比共混物的耐热性能则与纯PPEK相当,热变形温度大约为244℃;共混物的密度随PTFE含量的增加而呈线性增大趋势。     

含二氮杂萘酮结构耐热胶粘剂的研究

研究了一种含二氮杂萘酮结构耐热型环氧固化剂，与低分子质量聚酰胺复合使用得到的环氧胶粘剂具有良好的耐热性，固化工艺为140℃／2h 180℃/3h,150℃有25MPa以上的拉伸剪切强度，以及极好的高温保持率，可达到100％。详细研究了表面处理方式和固化工艺对其在常温和150℃下拉伸剪切强度的影响。     

新型双马来酰亚胺改性环氧树脂体系性能研究

用含二氮杂萘联苯结构的双马来酰亚胺(DHPZ-BM I)与4,4'-二氨基二苯砜(DDS)为复合固化剂固化环氧树脂(E-51)。采用示差扫描量热仪(DSC)研究了该体系的固化反应动力学,求得固化反应表观活化能Ea=63.28 kJ/mol,碰撞因子A=1.55×106s-1,反应级数n=0.89,该体系与链延长型双马来酰亚胺PPEK-BM I(DP=15)/DDS/E-51体系的固化反应动力学数据几乎相同,证明二者的固化反应过程相同。采用热失重分析仪(TGA)分析研究了上述2种固化体系的热分解动力学,前者的热分解活化能达215.04 kJ/mol,为后者的1.5倍以上,说明DHPZ-BM I/DDS/E-51是1种热稳定性能良好的耐高温环氧树脂体系。     

Synthesis and properties of novel phosphorus‐containing bismaleimide/epoxy resins

A novel soluble phosphorus‐containing bismaleimide (BMI) monomer, bis(3‐maleimidophenyl)phenylphosphine oxide (BMIPO), was synthesized by the imidization of bis(3‐aminophenyl) phenylphosphine oxide, in which its structural characterization was identified with ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectra. The BMIPO resin, with five‐membered imide rings and high phenyl density, was an excellent flame retardant with a high glass‐transition temperature (T_g), onset decomposition temperature, and limited oxygen index. In phosphorus‐containing BMI/epoxy/4,4′‐methylene dianiline (DDM)‐cured resins, homogeneous products were obtained from all proportions without phase separation. Because of the higher reactivity of BMIPO/DDM relative to that of 4,4′‐bismaleimidodiphenylmethane (BMIM)/DDM, the increase in the BMIPO/BMIM ratio in this blending resin increased the recrosslinking hazards of the postcuring stage and so lowered the T_g value and thermal stability. The thermal stability of the BMI/epoxy‐cured system was lower than that of the epoxy‐cured system because of the introduction of a phosphide group into BMIPO, whereas for the T_g value and flame retardancy, the former was significantly higher than the latter: the higher the BMIPO content in the blend, the higher the flame retardancy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2080–2089, 2002; DOI 10.1002/app.10607     

Synthesis and properties of poly(aryl ether sulfone)s containing the phthalazinone moiety

Three series of poly(aryl ether sulfone)s (PAESs) containing the phthalazinone moiety in the polymer backbone were synthesized by solution polycondensation of bis(4-chlorophenyl) sulfone with three commercial bisphenols and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. Bisphenol-A, hydroquinone, and bis(4-hydroxyphenyl) sulfone, or bisphenol-S, were selected as the commercial bisphenols for copolymerization. The synthesized polymers exhibited very high glass transition temperatures and excellent thermooxidative properties. They also showed superior mechanical properties and fair rheological properties. The introduction of relatively flexible moieties, such as benzene rings, onto the poly(phthalazinone ether sulfone) (PPES) chain led to a decrease in glass transition temperature with respect to the phthalazinone homopolymer. However, the processability of PPES was improved dramatically by the addition of these commercial bisphenols. The properties of synthesized PAESs can be tailored by changing the molar ratios of bisphenols to phthalazinone monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:137–143, 1998     

Synthesis and properties of novel aromatic copolyamides containing chloro‐substituted phthalazinone moiety in the main chain

A series of novel copolyamides were synthesized by the direct polycondensation of 1,2‐dihydro‐2‐(4‐carboxyphenyl)‐4‐[3‐chloro‐4‐(4‐carboxyphenoxyl)phenyl]‐phthalazinone ( 1 ), terephthalic acid (TPA) with three commercial diamines. The inherent viscosities of the polyamides were between 0.82 and 1.86 dL/g. When the molar ratios of 1 and TPA were higher than 1 : 1, the polymers were soluble in some polar aprotic solvents such as N‐methyl‐pyrrolidone and N,N‐dimethyl acetamide etc. These polymers were amorphous with 10% weight loss temperatures in N₂ above 490°C and their glass transition temperatures were above 269°C. Some films of the polymers were pale yellow and transparent with tensile strengths up to 147.8 MPa, initial modulus up to 2.56 GPa and elongations at break values up to 9.8%, which depended on the repeating unit structures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

烯丙基酚醛改性双马来酰亚胺树脂的制备与性能

合成并表征了烯丙基酚醛树脂,再将其与双马来酰亚胺共聚制备了烯丙基酚醛改性双马树脂。通过DSC和FTIR分析了该树脂的固化行为,研究了其工艺性,利用TGA和DMA评价了其固化物的耐热性。结果表明,烯丙基酚醛树脂改性双马树脂可用于RTM等成型工艺,其固化物Tg约为330℃,初始热分解温度约400℃,5%失重温度达410℃,10%失重温度423℃。该树脂耐热性优异,可用作耐高温先进复合材料的基体树脂。     

Synthesis and properties of brominate bismaleimide monomers

Brominated bismaleimides were prepared by reacting 3(4)‐maleimidobenzoylchloride with various bisphenols, using chloroform as solvent and triethylamine as acid acceptor. These monomers were characterized by elemental analysis, infrared (IR), and proton nuclear resonance (¹H‐NMR) spectroscopy. Thermal properties of monomers were accomplished by differential scanning calorimetry (DSC) and dynamic thermogravimetric analysis (ATG). The properties of these compounds were compared with those of monomers derived from bisphenol A and bisphenol A chlorinated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3881–3885, 2006     

Synthesis and properties of chain‐extended bismaleimide resins containing phthalide cardo structure

Three novel bismaleimide (BMI) monomers containing phthalide groups in their structures, i.e. 3,3‐bis[4‐(4‐maleimidophenoxy)phenyl]phthalide, 3,3‐bis[4‐(4‐maleimidophenoxy)‐3‐methylphenyl]phthalide and 3,3‐bis[5‐isopropyl‐4‐(4‐maleimidophenoxy)‐2‐methylphenyl]phthalide, based on phenolphthalein, o‐cresolphthalein and thymolphthalein, respectively, were designed and synthesized. The chemical structures of the monomers were confirmed from ¹H NMR and ¹³C NMR spectroscopy and Fourier transform infrared spectroscopy. These monomers exhibit good solubility in common organic solvents, enabling easy solution processing. The thermal curing behavior of the monomers was investigated using differential scanning calorimetry, displaying broad exothermic peaks and large thermal processing windows. Thermogravimetric analysis and dynamic mechanical analysis were used to characterize the thermal stability and thermal mechanical properties of the resulting BMI resins. The results, in contrast to bisphenol A‐based BMI resin, indicate that the incorporation of the phthalide structure into the polybismaleimide network can effectively improve the thermal properties. Water absorption tests of the cured products demonstrate the chemical structure has an effect on moisture resistance. Copyright © 2010 Society of Chemical Industry     

Synthesis of new soluble aromatic poly(amide imide)s from unsymmetrical extended diamine containing phthalazinone moiety

The preparation of a new unsymmetrical kink non‐coplanar heterocyclic diamine, 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐[4‐(3‐phenyl‐4‐aminophenoxy)phenyl]‐(2H)phthalazin‐1‐one (3), from a readily available unsymmetrical phthalazinone bisphenol‐like (1) was described. The diamine can be directly polymerized with various aromatic bis(trimellitimide)s (4a–e) by using triphenyl phosphite and pyridine as condensing agents to give a series of new aromatic poly(amide imides) (5a–e) containing the kink non‐coplanar phthalazinone heterocyclic units with inherent viscosities of 0.57–1.06 dL/g. The polymers were readily soluble in a variety of solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide, dimethylsulfoxide, N‐methyl‐2‐pyrrolidinone, and even in pyridine and m‐cresol and could be cast to form flexible and tough films. The glass transition temperatures were in the range of 315–340°C, and the temperatures for 5% weight loss in nitrogen were in the range of 487–512°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1516–1520, 2004     

Copolymers derived from bismaleimide oligomer with active solvent

An oligomer from 4, 4′‐bis(maleimido)diphenyl methane and methylenedianiline were dissolved in active solvent N,N‐dimethyl acrylamide in a solid content up to 50–70%; the solution was poured in a sheet‐shaped module and irradiated by ⁶⁰Co with the dose from 20 to 350 kGy at room temperature. The polymerized sheet was postcured at 180°C to obtain a transparent red‐orange sheet with tensile strength above 100 MPa. The glass transition temperature before and after postcuring was around 100°C and 150–180°C, respectively. Styrene was used along with DMAA to decrease the water absorption for the copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2879–2882, 2004     

新型耐热胶粘剂苯胺二苯醚与双马来酰亚胺共聚物的研究

介绍了苯胺二苯醚与双马来酰亚胺共聚物的合成,采用ＴＧＡ、ＤＳＣ研究其耐热性,讨论了固化条件、不同配比、储存时间对剪切强度的影响。实验结果表明：ＡＮＤＰＯＢＭＩ树脂玻璃化温度在２７０℃左右,温度指数大于２２０℃,而且粘接性能良好,可用作新型耐热胶粘剂。