长链聚酰胺酸的缩聚动力学研究

以长链二胺4，4’-二(4-氨基苯氧基)二苯砜(BAPS)为单体，在N，N'-二甲基甲酰胺(DMF)中分别与3种二酐于室温下反应，合成了3种长链聚酰胺酸(PAA)。利用GPC研究了PAA相对数均聚和度(Xn)及其分布随缩聚时间的变化关系。结果表明：该反应为自催化逐步缩聚反应，反应级数为三级；在初始阶段，缩聚速率常数随二酐电子亲和性(EA)的递增而增加。     

2,6-双(4-氨基苯氧基)苯腈的合成及其聚酰亚胺

从4-氨基酚和2,6-二氯苯腈出发,合成了2,6-双(4-氨基苯氧基)苯腈单体,总收率为55%。由该单体与4,4′-(六氟亚丙基)双-邻苯二甲酸酐共聚合,经热环化脱水反应得可溶性聚酰亚胺,可溶于NMP、DMF、DMAc等溶剂。     

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.     

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。     

含三(4-氨基苯基)苯的超支化聚酰亚胺的合成及表征

合成了三胺单体1,3,5-三(4-氨基苯基)苯(TAPB),将其与3,3′,4,4′-二苯酮四酸二酐(BTDA)缩合,采用化学亚胺化和热亚胺化两种方法合成了一种新型超支化聚酰亚胺(HBPIs).经红外光谱和核磁共振确认产物结构.对聚合物的性能进行分析,结果表明,聚合物的溶解性得到很好的改善.     

改性聚酰亚胺树脂复合材料的研究

以4，4-二苯甲烷双马来酰亚胺、二氨基二苯甲烷、环氧树脂为主要原料合成性能优良的改性聚酰亚胺树脂体系；以此树脂为基体、玻璃纤维布为增强材料制作的复合材料具有玻璃化温度高、机械强度好、介电常数低等优异的综合性能，可用于制作耐高温、高强度绝缘材料。     

1，4-双（4-氨基苯氧基）-2，5-二特丁基苯及其聚酰亚胺的合成与性能研究

在有机溶剂体系中,2,5-二特丁基对苯二酚与对氯硝基苯在碳酸钾的作用下进行缩合反应,得到了1,4-双（4-硝基苯氧基）-2,5-二特丁基苯晶体（14BNPODTB）,随后,在钯/碳-水合肼的还原体系中反应,获得了高纯度的白色1,4-双（4-氨基苯氧基）-2,5-二特丁基苯（14BAPODTB）晶体产物。利用差示扫描量热计（DSC）,熔点仪,傅立叶转换红外光谱仪（FTIR）等分别对其进行了表征。另外,也进行了聚合试验,获得了聚酰胺酸树脂（14BAPODTB-440DA／PMDA—PAA）溶液,涂膜,热亚胺化,制得了聚酰亚胺薄膜（14BAPODTB-440DA／PMDA—PI）,并对其性能进行了研究。     

3,5-双(4-氨基苯氧基)苯甲酸的合成及其聚酰亚胺薄膜的性能研究

合成3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA)。其方法为3,5-二羟基苯甲酸(35DHBA)和对氯硝基苯(PCNB)通过缩合反应,合成得到了3,5-双(4-硝基苯氧基)苯甲酸(35BNPBA);然后,进一步还原,得到3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA),基于35BAPBA单体,制得多种结构的含羧基芳香族聚酰亚胺薄膜,并对这些薄膜的性能进行研究。制得的3,5-双(4-氨基苯氧基)苯甲酸(35BAPBA)的熔点为245.8℃,且纯度高。各类薄膜的透过率均可达80%以上,具有良好的紫外吸收性能;吸水性均小于3%,具有优异的疏水性能;其拉伸强度在15~56MPa之间。     

高效液相色谱法测定1,3,5-三(4-氨基苯氧基)苯的含量

提出了高效液相色谱法测定1,3,5-三(4-氨基苯氧基)苯(TAPOB)的分离方法。采用Hypersil BDS C18柱(4.6 mm×200 mm,5μm),流动相为V(甲醇)∶V(水)=80∶20,检测波长245 nm。在0.08~0.24 mg/m L范围内,方法线性良好(r=0.999 8),回收率为98.33%~113.02%,重现性RSD≤0.91%(n=5),可简便、快速地测定TAPOB的含量。     

4-（2＇-氟-4＇-氰基苯氧基）苯酚的合成新方法

4-（2＇-氟-4＇-氰基苯氧基）苯酚是合成苯氧丙酸类高效除草剂的重要中间体。研究了4-（2＇-氟-4＇-氰基苯氧基）苯酚合成的新方法。该方法以3,4-二氟苯腈和对羟基苯甲醚为主要原料,首先合成4-（2＇-氟-4＇-氰基苯氧基）苯甲醚,再经三溴化硼还原得到4-（2＇-氟-4＇-氰基苯氧基）苯酚。通过红外、核磁及质谱等分析手段对其化学结构进行了鉴定,两步反应总收率为64%,产品纯度95.2%,克服了文献报道的合成方法产量小、收率低的缺点。     

均四甲苯的制备及应用

综述了均四甲苯的制备工艺、反应机理、分离提纯方法以及以均四甲苯为原料制备均苯四甲酸二酐(PMDA)的方法。     

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     

均四甲苯的制备方法及应用研究

均四甲苯是一种重要的有机化工原料,主要用于生产均苯四甲酸二酐,因而也是生产聚酰亚胺绝缘薄膜的最经济、最理想的原材料。聚酰亚胺在耐热性工程塑料中占有极为重要的位置,是目前热塑性工程塑料中耐热性最好的品种之一,广泛应用于航空、航天、机电及电子等领域。详细介绍了均四甲苯的性能和用途、生产方法、反应机理及分离提纯的方法。通过比较可知,四甲苯异构化制备均四甲苯的工艺,具有原料利用率高、经济效益好等优点,经济可行。     

Synthesis,characterization, thermal and optical properties of soluble polyimides derived from an unsymmetrical diamine

A new unsymmetrical diamine monomer, 2,4‐diaminophenyl [4′‐(2′′,6′′‐diphenyl‐4′′‐pyridyl)phenyl]ether, was successfully synthesized by nucleophilic substitution of 1‐chloro‐2,4‐dinitrobenzene with 4‐(2′,6′‐diphenyl‐4′‐pyridyl) phenol. The diamine monomer was characterized by FTIR, ¹H and ¹³C NMR, and elemental analysis techniques and used for the preparation of novel polyimides (PIs) by reaction with commercially available tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bicyclo[2.2.2]‐oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride. These PIs with inherent viscosities ranged from 0.43 to 0.48 dL/g were readily soluble in many organic solvents and afforded tough and flexible films by solution casting. These polymers exhibited T_gs between 237 and 294°C, and 10% weight loss temperatures in excess of 500°C with up to 56% char yield at 600°C in air. Their maximum fluorescence emission in dilute (0.2 g/dL) NMP solution appeared at 450 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

含噁唑环均苯型聚酰亚胺的制备和表征

为了提高聚酰亚胺材(PI)料的耐热性能,以2,6-二(对氨基苯)苯并[1,2-d;5,4-d]二噁唑为单体,采用两步法与均苯四甲酸二酐(PMDA)合成出了新型聚酰亚胺薄膜.采用红外光谱、热分析等手段对其结构与性能进行了表征.测定了聚酰亚胺的预聚体-聚酰胺酸(PAA)的特性黏度达到1.18dL/g,玻璃化温度343℃,在空气中热失重温度为626℃,表现出优异的热氧化稳定性.评价了聚酰亚胺在各种溶剂中的溶解性能,均不溶于常规的极性溶剂,甚至在浓硫酸中也不溶解.经红外光谱测定,聚酰胺酸基本转化成聚酰亚胺.     

Synthesis and characterization of polyimides from 4‐(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride

A novel rigid‐rod type dianhydride monomer with phosphine oxide moiety, 4‐(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride (POPPMDA), was synthesized via the Suzuki coupling reaction of 4‐(diphenyl phosphine oxide)phenyl boronic acid (POBB) and 1‐bromo‐2,3,5,6‐tetramethyl benzene (B4MB), followed by oxidation and cyclodehydration. The monomer was characterized by FTIR, NMR, EA, and melting point analyzer and utilized to synthesize polyimides with diamines such as bis(3‐aminophenyl)phenyl phosphine oxide (mDAPPO) and p‐phenylene diamine (pPDA) by varying their ratio. The polyimides were prepared via a conventional two‐step synthesis: preparation of poly(amic‐acid), followed by solution imidization. The polyimides were characterized by FTIR, NMR, DSC, TGA, and TMA, and their solubility, intrinsic viscosity, and adhesive properties were also evaluated. The polyimides exhibited high T_g (342–362°C), good thermal stability (>500°C), excellent adhesive property (134–107 g/mm), and low CTE (28–17 ppm/°C). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PMDA-6FHP-DR1／SiO2杂化纳米材料的结构设计和合成

以含氟的二胺5，5′—(六氟异丙基)—二—(2—氨基苯酚)及均苯四甲酸酐(PMDA)为单体，首先合成了经酰胺化的主链上带有活性羟基的含氟聚酰亚胺，再通过Mitsunobu反应将活性生色分子分散红1(DR1)共价链接到聚酰亚胺的侧链骨架上，合成了含氟聚酰亚胺．采用溶胶—凝胶(SOl—Gel)技术，并利用偶联剂γ—氨丙基三乙氧基硅烷(AFTES)制备带有发色团的和含有硅氧烷端分子的聚酰胺酸，其中的Si(OR)3基经水解、缩合后，与正硅酸乙酯(TEOS)在催化剂作用下反应，经杂化、凝胶后，得到光学透明且热稳定性高的有机／无机杂化材料．将制得的含氟聚酰亚胺／SiO2杂化材料，采用红外光谱(FT—IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、示差扫描量热法(DSC)，对材料的结构、表面形貌、热性能进行了表征．     

Preparation and characterization of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride-pyromellitic diahydride alternating polyimides

Four kinds of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA)-pyromelliitic dianhydride (PMDA) alternating polyimide (BTDA-PMDA API) were obtained by reacting 1 mol BTDA with 2 mol diamines to form BTDA chain-extended diamines (BTDA CED), followed by the addition of 1 mol PMDA to yield the BTDA-PMDA alternating polyamic acids (BTDA-PMDA APA), and finally by imidizing them thermally. BTDA CED were characterized by elemental analysis, infrared (IR), and ¹H-NMR spectroscopy. The structures of BTDA-PMDA APA and BTDA-PMDA API were investigated by IR and ¹H-NMR spectroscopy, and their thermal properties and interfacial tension were also studied. Furthermore, the characteristic properties of BTDA-PMDA API were compared with their corresponding homopolyimides from BTDA (BTDA HPI) and from PMDA (PMDA HPI). It was found that the alternating condensation polymerization is an effective method to modify polyimides interfacial tension with a small influence on the thermal stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1585–1593, 1997     

新型均苯型芳香族聚酰亚胺的研究

以二步法制备了一种新型均苯型芳香族聚酰亚胺。测定了聚酰亚胺的预聚体———聚酰胺酸特性粘度 (Iv)随反应时间的变化曲线 ,聚酰亚胺在N 甲基 2 吡咯烷酮 (NMP)中的特性粘度在 1.2dL/g左右 ,玻璃化温度高于2 5 0℃ ,在氧气中失重 5 %的温度在 5 0 0℃以上。经红外光谱测定 ,样品在 1780cm-1和 1380cm-1附近观察到聚酰亚胺的特征峰     

聚砜酰胺酸和聚砜酰亚胺的微波辐射合成

采用4，4'-二氨基二苯砜(DDS)与均苯四酸二酐(PMDA)为单体进行微波辐射溶液聚合反应，所得的聚酰胺酸进行固相微波辐射亚酰化。考察了微波辐射时间、反应温度、单体浓度、单体配比等因素对聚合物的特性粘数、转化率的影响，并与热聚合进行比较，用红外及核磁共振的测试方法对聚合物的结构进行了表征，通过红外光谱表征了聚酰亚胺的亚酰化度。实验结果表明：微波辐射不仅能缩短缩聚反应时间，还能提高缩聚物的特性粘数和转化率。固相微波辐射使聚酰胺酸的亚酰化时间缩短，亚酰化度增大。合成的聚酰胺酸和聚酰亚胺都具有一定的荧光性能，聚酰亚胺具有一定的磁性。