新型环氧树脂固化剂的合成与表征

在无水碳酸钾和强极性非质子有机溶剂中,采用2,2-双(4-羟基苯基)丙烷(BHPP)和2,4-二硝基氯苯(24DNCB)为主原料,通过缩合反应得到2,2-双[4-(2,4-二硝基苯氧基)苯基]丙烷(BDNPPP);在钯/炭、水合肼和有机溶剂的作用下,BDNPPP被进一步还原,得到了新型环氧固化剂2,2-双[4-(2,4-二氨基苯氧基)苯基]丙烷(BDAPPP),并对其进行了系统的表征。     

AM/DAAM二元共聚物的合成与表征

用一种氧化还原体系的引发剂,采用水溶液聚合法合成了丙烯酰胺-N-(1,1-二甲基-3-氧代丁基)丙烯酰胺(AM/DAAM)二元共聚物。实验中分别考察了原料中单体配比、反应时间、引发剂用量对共聚物的特性粘数的影响;同时采用定量的方法考察了共聚物的溶解性能。结果表明,当DAAM在共聚物中的摩尔百分含量为33.64%时,聚合物的特性粘数比相同条件下合成的聚丙烯酰胺提高9.9倍;当共聚物中DAAM的含量为15%时,共聚物的溶解速率是相同条件下合成的聚丙烯酰胺的4倍。通过对各种组成共聚物在不同盐溶液中的特性粘数的测定,结果显示该共聚物具有良好的耐盐性能。另外,采用红外光谱、核磁共振氢谱对共聚物进行了定性和定量的表征。     

VTMS/MMA/St三元共聚物的合成与表征

以甲基丙烯酸甲酯（MMA）、苯乙烯（St）、乙烯基三甲氧基硅烷（VTMS）为单体通过乳液聚合制备了含有机硅氧烷的三元共聚物乳液;研究了单体配比与转化率之间的关系．并表征了共聚物的结构,测试了共聚物的热性能。结果表明,共聚物中成功地引入丁有机硅链节．聚合过程中部分硅氧烷部分发生水解,共聚物的热稳定性和玻璃化温度有一定提高。     

BDPM/St/GMA三元共聚物的制备及热性能研究

以N-[(4-溴-3,5-二氟)苯基]马来酰亚胺(BDPM)、苯乙烯(St)和甲基丙烯酸缩水甘油酯(GMA)为原料,通过溶液聚合制备了N-[(4-溴-3,5-二氟)苯基]马来酰亚胺/苯乙烯/甲基丙烯酸缩水甘油酯(BDPM/St/GMA)三元共聚物,采用红外光谱(FTIR)对其结构进行了表征,通过元素分析和环氧值测定以及热分析研究了原料物质的量比对共聚产物性能的影响。结果表明:随着BDPM含量增加,产物的环氧值降低,热稳定性提高。共聚产物在空气和氮气条件下的热解机理不同,在氮气中具有更好的热稳定性。Flynn-Wall-Ozawa法求得BDPM/St/GMA的热分解表观活化能为143.55 kJ/mol,具有优良的热稳定性。     

HPM/St/MA三元共聚物的合成及其热分解动力学

采用溶液聚合法制备了N-(4-羟基苯基)马来酰亚胺/苯乙烯/马来酸酐三元共聚物,通过红外光谱对其结构进行了表征,并利用TG和DTG技术对该共聚物的热性能和热分解动力学进行了研究。结果表明,由Fly-nn-Wall-Ozawa法求得三元共聚物的热分解表观活化能为147.38 kJ,指前因子为2.62×1010;Crane法求得的反应级数为0.95。该共聚物热分解受单机理控制,初始热分解温度为660 K,最大热分解温度为707 K,在740 K时热分解基本结束,较二元共聚物St/MA其耐热性明显提高。     

一种新型联苯型多苯氧基聚酰亚胺的合成及其表征

以2,2-双(3-苯基-4-羟基苯基)丙烷(双OPP-A)、对硝基氯苯、无水碳酸钾为基本原料,在冠醚作为相转移催化剂的作用下缩合制得2,2-双[3-苯基-4(4-硝基苯氧基)苯基]丙烷(BPNPOPP);在此基础上,采用水合肼还原得到2,2-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)单体.将其与均苯四甲酸二酐(PMDA)通过缩聚反应、热环化制备了一种联苯型多苯氧基聚酰亚胺.结果表明:缩合制备BPNPOPP,收率达到97.8%以上.还原制备BPAPOPP单体,熔点160.6～161.3℃.此种单体制备的聚酰亚胺玻璃化转变温度为233.2℃,易于加工;热分解温度(质量损失率10%)为503.8℃,具有很好的耐热性能;拉伸强度达到111.8 MPa,断裂伸长率为6.68%,薄膜的热膨胀系数为49.7×10-6K-1,是一种性能优良的材料.     

MMA/AN/DVB乳液交联聚合动力学

为制备甲基丙烯酸甲酯(MMA)-丙烯腈(AN)-二乙烯基苯(DVB)刚性微粒,在75℃、过硫酸钾(KPS)作引发剂、恒搅拌速率下研究了MMA/AN/DVB乳液共聚动力学,考察了KPS用量、单体配比、交联剂DVB对共聚速率的影响.结果表明乳液共聚速率Rp与KPS浓度的0.699次幂成正比,而且随着AN质量分数增加而下降.引发剂浓度指数偏离Smith-Eward理论模型可解释为体系中单体AN具有较大的水溶性,使成核胶粒数目增加的结果.当DVB用量在3%～5%时,聚合速率随DVB用量的增加而略有下降, 在DVB用量为6%时,共聚速率明显上升.随交联剂DVB用量增加,共聚物粒径变大且分布变宽.     

含哌嗪类化合物的合成与研究

以对羟基苯甲酸乙酯为起始原料,合成了新化合物4-[2-羟基-3-(N-甲基-4-哌嗪)丙氧基]苯甲酸及4-[2-(N-甲基-4-哌嗪)乙氧基]苯甲酸。产品结构经1HNMR、元素分析进行表征。     

磺酰胺类染料中间体的合成与表征

以乙酰苯胺、间苯二胺为主要原料,经磺酰化、酰胺化、脱乙酰基,合成了替代致癌染料中间体N,N'-1,3-苯基二-(4-氨基)苯磺酰胺,并优化了酰胺化反应条件。产物分别经元素分析、红外、质谱和核磁表征确证了结构。     

N-[2-(4-氨基苯基)丙基]乙酰胺的合成工艺

以2-苯基丙胺盐酸盐为原料经酸碱中和、酰化、硝化、还原4步合成得到N-[2-(4-氨基苯基)丙基]乙酰胺,探讨了投料方式、还原方法、催化剂等因素对收率的影响,并通过MS、~1H NMR和~(13)C NMR对其结构进行表征。总收率达50%,纯度为97.3%。     

PMI-St-AN耐热改性剂的合成及应用

以提高聚氯乙烯(PVC)的耐热性能为目的,用悬浮聚合的方法,合成了N-苯基马来酰亚胺-苯乙烯-丙烯腈三元共聚物型耐热改性剂。通过差热分析、元素分析、凝胶渗透色谱分析等手段对共聚物的玻璃化转变温度、组成及其分布、分子量及其分布进行了表征。初步考察了丙烯腈的加入对N-苯基马来酰亚胺-苯乙烯交替共聚体系共聚合规律的影响。将合成的耐热改性剂用于PVC共混改性,取得了较好的效果。     

Thermal degradation kinetics and mechanisms of PMEPP and MEPP/MMA copolymer

In this study, 2-methacryloxyethyl phenyl phosphate (MEPP), a phosphorus-containing flame retardant, was synthesised via the esterification of phenyl dichlorophosphate (PDCP) with 2-hydroxyethyl ethylene methacrylate (HEMA), followed by hydrolysis. A two-stage bulk polymerisation process prepared MEPP/methyl methacrylate (MEPP/MMA) copolymers containing various amounts of MEPP. The condensed-phase and volatized products produced at various temperatures during the thermal degradation of MEPP/MMA copolymer were monitored by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis with Fourier transform infrared spectroscopy (TGA/FT-IR). Finally, we propose the possible mechanisms for the thermal degradation of MEPP/MMA copolymer according to the analytical results of the condensed-phase and volatilized products.     

新型含氟聚醚酰亚胺的合成与表征

利用对苯二酚、2-氯-5-硝基三氟甲苯合成得到1,4-双(2-三氟甲基-4-硝基苯氧基)苯,再在钯/炭、水合肼和有机溶剂的作用下,合成得到了1,4-双(2-三氟甲基-4-氨基苯氧基)苯,并对其性能进行了表征,包括其本身的熔点、红外吸收特征等。合成得到的1,4-双(2-三氟甲基-4-氨基苯氧基)苯与4,4'-二氨基二苯醚、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐反应,制得了含氟聚醚酰亚胺,并对其性能进行了表征。     

Synthesis and characterization of soluble random copolyimides

Random copolyimides with different proportions of a diamine component were prepared by polymerizing different compositions of diamines with various dianhydrides and imidized thermally to 260°C. The imidization percent of poly(amic acid) was characterized at various temperatures by infrared spectroscopy. The homopolyimide based on bis[4‐(3‐aminophenoxy)phenyl]sulfone and pyromellitic dianhydride was the only one soluble. By changing the compositions of bis[4‐(3‐aminophenoxy)phenyl]sulfone and other diamines with pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone, soluble random copolyimides could be prepared. By random copolymerization, the thermal properties and viscosities of homopolyimide could be controlled. All the soluble polyimides prepared in this work were amorphous because of the lack of stereoregularity. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 272–277, 1999     

一种新型含砜基青成色剂的合成

采用对羟基苯硫酚和溴丁酸甲酯为原料合成含砜基型青成色剂N-{[3-羟基-4-(3,4-二氯苯甲酰氨基)-6-氯]苯基}-2-([4-十二烷氧基苯基)砜基]-丁酰胺,总收率43%,发色后吸收曲线与标样相同,感光性能接近标样。     

Synthesis and properties of flourine-containing polyimides

A series of new flourine-containing polyimides have been synthesized from the condensation of 2,2,-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amino-phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, or 2,2bis[4-(4-amino-2-trifluoro-methylphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane with various aromatic dianhydrides. The electric constant at 1 KHz in the flourine-containing polyimides decreases from 3.51 to 2.72 as flourine content increases. The poly(amic acid)s had inherit viscosities of 0.52–1.23 dL/g, depending on the diamines and dianhydrides. Most of the resulting polymers showed an amorphous nature and afforded flexible and tough films. The amount of moisture absorption decreases as flourine content in polyimides increases. The glass transition temperatures of these polyimides were in the range of 287–328°C, and the 10% weight loss temperatures were above 542°C in the nitrogen. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 609–617, 1997     

以BAPP为原料的热塑性PI薄膜的合成及性能

以芳香长链二胺2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)为二胺原料,与最具商业价值的四种酸酐均苯四甲酸二酐(PMDA)、3,3′,4,4′-联苯四酸二酐(BPDA)、3,3′,4,4′-二苯酮四酸二酐(BTDA)、3,3′,4．4′-二苯醚四酸二酐(ODPA)为二酸酐原料,采用二步溶液缩聚法制得了一系列均聚和共聚聚酰亚胺薄膜。利用FTIR表征了聚酰亚胺的结构,并用DSC、TOA、TMA DMA等手段测得了不同聚酰亚胺的Tg、5%与10%热失重温度、线膨胀系数、拉伸强度、断裂延伸率、热压粘接T型剥离强度等性能数据。     

Synthesis,characterizations and thermal behavior of methyl methacrylate and N‐(p‐carboxyphenyl) methacrylamide/acrylamide copolymers

The synthesis, characterization, and thermal properties of copolymers of methyl methacrylate (MMA) and N‐(p‐carboxyphenyl) methacrylamide/acrylamide (CPMA/CPA) are described. The copolymerization was carried out in solution by taking different mole fractions (0.1–0.5) of CPMA/CPA in the initial feed using azobisisobutyronitrile as an initiator and dimethylformamide as a solvent at 60°C. The copolymer composition was determined from ¹H‐NMR spectra by taking the ratio of the proton resonance signal due to the  OCH₃ of MMA (δ = 3.59 ppm) and the aromatic protons (δ = 7.6–7.8 ppm) of CPMA/CPA. The monomer reactivity ratios of MMA:CPMA and MMA:CPA were determined using the Fineman Ross and Kelen Tudos methods and were found to be 1.32 ± 0.01 [MMA], 1.11 ± 0.02 [CPMA], 2.60 ± 0.01 [MMA], and 0.20 ± 0.01 [CPA]. Incorporation of these comonomers in the MMA backbone resulted in an improvement in the glass‐transition temperature and thermal stability. The percent char also increased with the increase of CPMA/CPA content in the copolymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 259–267, 2000