N-异丙酸基马来酰亚胺的合成

以马来酸酐（MA）和氨基丙酸（Aln）为原料发生酰胺化反应生成N-异丙酸基马来酰胺酸（A—MA）,AMA再在催化剂三乙胺（Et,N）的作用下发生闭环脱水反应生成N-异丙酸基马来酰亚胺（AMI）单体。考察了溶剂、原料配比、催化剂用量、反应温度和反应时间对产品产率的影响。确定了最佳反应条件。并用GG47-FTS7000红外光谱仪、PE-2400有机元素分析仪对产品进行了检测。在最佳反应条件下,所得AMI的总产率达54．1％,纯度达98％,熔点100—101℃。     

PA封端型聚酰亚胺的合成与表征

以均苯四甲酸二酐(PMDA)和自制的1,3-双(4-氨基苯氧基)苯(TPER)在邻苯二甲酸酐(PA)封端的情况下溶液缩聚得到聚酰胺酸(PAA),通过溶液亚胺化和固相亚胺化相结合得到聚酰亚胺(PI).用傅立叶变换红外光谱仪、乌氏粘度计和热失重分析仪对PI进行了结构表征和性能测试,分析了封端剂加入量、亚胺化方式对PI性能的影响.结果表明,封端剂的加入可有效降低PI的粘度,两种亚胺化方式的结合可以降低PI的最终亚胺化温度,得到的PI热稳定性高.     

N—苯基马来酰亚胺的合成

以顺丁烯二酸酐和苯胺为原料,选择二步法合成了Ｎ－苯基马来酰亚胺,无需使用ＤＭＦ溶剂。用正交法优化了工艺条件,产品收率为９２％,质量分数为９７％,溶点８６．８￣８８．０℃。应用试验表明Ｎ－苯基马来酰亚胺是ＰＶＣ塑料有效的热稳定剂。     

N-苯基马来酰亚胺的合成研究

以苯胺和顺丁烯二酸酐为原料,以磷钨酸为催化剂、磷酸为脱水剂、对苯二酚为阻聚剂,两步法进行N-苯基马来酰亚胺合成.研究了原料配比、反应时间和催化剂用量等因素对产品收率的影响,采用正交实验方法确定了最佳工艺条件,使N-苯基马来酰亚胺的收率达到85%以上.     

一种新型马来酰亚胺的合成研究

研究了Ａｃ２Ｏ／Ｅｔ３Ｎ／ＮｉＳＯ４三元催化体系催化下Ｎ－己基马来酰亚胺的合成,考察了催化剂用量,反应温度,原料配比和反应时间对反应产率的影响,确定了最佳反应条件,所得Ｎ－己基马来酰亚胺产率达８４％,与传统酸催化法相比,该法具有反应条件温和,产率高等优点。     

合成N-苯基马来酰亚胺的研究

以马来酸酐和苯胺为原料合成N-苯基马来酰亚胺(N-PMI)的过程中，采用对甲苯磺酸和硫酸铜为催化剂，对羟基苯甲醚为阻聚剂，并采用甲苯／二甲基甲酰胺混合溶剂，有效提高了N-苯基马来酰亚胺的产率。加入金属铜盐催化剂后，N-苯基马来酰亚胺的纯度提高到99．4％左右。同时研究了反应物摩尔比、催化剂用量以及混合溶剂配比等因素对合成N-苯基马来酰亚胺的影响。     

韧性马来酰亚胺树脂的合成

文中介绍了三类新型的马来酰亚胶树脂——甲基取代双马来酰亚胺、环氧型双马来酰亚胺树脂及本征增韧型马来酰亚胶树脂。对其树脂、固化树脂及其复合材料的性能进行了详细的研究，得到了性能较佳的树脂体系。     

N-苯基马来酰亚胺的合成研究

以顺丁烯二酸酐和苯胺为原料、二甲苯和DMF的混合溶液作溶剂,采用两步法合成了N-苯基马来酰亚胺,产品用红外光谱和气相色谱进行了表征.确定了最佳工艺条件如下:n(苯胺)∶n(顺丁烯二酸酐)为1∶1.2;溶剂V(二甲苯)∶V(DMF)为20∶1; 胺化反应温度为40～50℃,环化反应温度为135℃;环化时间为2 h.在此条件下,产品收率达到90%、纯度达到98.15%.     

二层法双面挠性覆铜板用热塑性聚酰亚胺的合成与应用研究

选用合适的单体芳香二酐二苯甲酮四酸二酐（BTDA）、2,2’-双[4-（3,4-二羧基苯氧基）苯基]丙烷四羧酸二酐（BPADA）和芳香二胺3,3′,5,5′-四甲基-4,4′-二氨基二苯甲烷（AMD）、4,4′-二氨基二苯甲烷（MDA）、4,4′-二氨基二苯醚（ODA）,3,4＇-二氨基二苯醚（3,4＇-ODA）根据不同配比反应得到聚酰胺酸,用乙酸酐／三乙胺经化学亚胺化得到热塑性聚酰亚胺（TPI）,将其用N-甲基吡咯烷酮（NMP）溶解配成一定固含量的胶液,涂覆铜箔烘干溶剂得到二层挠性覆铜板（2L—FCCL）,然后将2L—FCCL高温压合制备双面挠性覆铜板,其剥离强度较高。     

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4′-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 × 10⁻⁶ to 0.80 × 10⁻⁶ cm²/s at room temperature, which was much lower than that of Nafion (2 × 10⁻⁶ cm²/s). The copolymers were thermally stable up to 340 °C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.     

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。     

Synthesis and characterization of novel fluorinated polyimides derived from bis[4-(4′-aminophenoxy)phenyl]-3,5-bis(trifluoromethyl)phenyl phosphine oxide

A novel fluorinated aromatic diamine, bis[4-(4′-aminophenoxy)phenyl]-3,5-bis(trifluoromethyl)phenyl phosphine oxide, was synthesized. A series of new fluorinated polyimides containing phosphine oxide was prepared from the novel diamine with various commercially available aromatic dianhydrides. All the fluorinated polyimides show high glass transition temperatures, excellent thermal stability, and good solubility in common organic solvents.     

Synthesis and characterization of novel polyimides derived from 1,1-bis[4-(4′-aminophenoxy)phenyl]-1- [3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane

A novel fluorinated aromatic diamine monomer, 1,1-bis[4-(4′-aminophenoxy)phenyl]-1-[3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane(9FTPBA), was synthesized by coupling 3′,5′-bis(trifluoromethyl)-2,2,2-trifluoroacetophenone with 4-nitrophenyl phenyl ether under the catalysis of trifluoromethanesulfonic acid, followed reduced by reductive iron and hydrochloric acid. A series of new fluorine-containing polyimides having inherent viscosities of 0.96-1.23 dl/g was synthesized from the novel diamine with various commercially available aromatic dianhydrides using a standard two-stage process with thermal imidization and chemical imidization of poly(amic acid) films. All the fluorinated polyimides were soluble in many polar organic solvents such as NMP, DMAc, DMF, and m-cresol, as well as some of low boiling point organic solvents such as chloroform and acetone. The polymer films have good thermal stability with the glass transition temperature of 223-225 °C, the temperature at 5% weight loss of 535-568 °C in nitrogen, and have outstanding mechanical properties with the tensile strengths of 68-89 MPa, initial moduli of 2.14-2.19 GPa, and elongations at breakage of 3.2-10.5%.     

Synthesis and properties of novel side-chain-sulfonated polyimides from bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone

A novel side-chain-sulfonated aromatic diamine of bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone (BAPSBPS) was synthesized. Sulfonated copolyimides were synthesized by random and sequenced block copolymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, BAPSBPS and nonsulfonated diamine. They displayed good solubility in common aprotic solvents and high desulfonation temperature of 350 °C, suggesting the high stability of sulfonic acid groups. The reduced viscosity was in the range of 0.4-1.8 dl/g at 0.5 g/dl and 35 °C. Flexible and tough membranes with reasonably high mechanical strength were prepared. They showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity (σ), taking their lower ion exchanging capacity (IEC) into account. For example, the membrane with IEC of 1.54 mequiv/g showed σ values of 81 and 11 mS/cm in water and 70% RH, respectively, at 60 °C.     

Synthesis and Characterization of Polyimides Derived From Cyano-Containing 1,4-Bis(4-aminophenoxy)benzene Monomers

Summary A series of three new cyano-containing diamines based upon 1,4-bis(4-aminophenoxy)benzene was synthesized and polymerized with six different dianhydrides to yield 18 different polyimides. Due to the high dipole moment of the cyano group, it was believed that these polymers would display differing degrees of electroactivity depending upon the degree and position of cyano substitution. The type of dianhydride bridging group and length are also factors that affect the electroactivity of polyimides. Polyimides based upon 1,4-bis(4-aminophenoxy)benzene were used as reference materials by which the respective cyano-containing analogs were compared. As the degree of cyano group substitution increased, the glass transition temperature increased. As cyano substitution increased, the polymer chain flexibility decreased due to hindered rotation about the phenyl-ether-phenyl linkages in the diamine portion of the polymer. The tensile moduli ranged from 2.97 to 4.57 GPa and ultimate tensile strengths from 79 to 156 MPa, which are typical values of aromatic polyimides.     

Synthesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benzene

A new fluorinated diamine monomer, [1,4-bis(4-amino-3-trifluoromethylphenoxy)benzene (2)], and a known isomeric analog 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (3) were synthesized. A series of organosoluble polyimides Ia–d and IIa were prepared from the diamines (2, 3) and dianhydrides (a–d) by a high-temperature one-step method. The effects of the trifluoromethyl substituents on the properties of polyimides were evaluated through the study of their soluble, thermal, optical, and gas permeability properties. Polyimides (Ia–d) had glass transition temperatures between 229 and 279 °C, and the temperatures at 5% weight loss ranged from 510 to 533 °C under nitrogen. These polyimides could be cast into flexible and tough membranes from DMAc solutions. The membranes had tensile strengths in the range of 137–169 MPa, tensile modulus in the range of 1.6–2.2 GPa and elongations at break from 11% to 14%. The polyimide Ia with trifluoromethyl groups ortho to the imide nitrogen exhibited enhanced gas permeability, solubility, transparency, and thermal stability compared with the isomeric polyimide IIa with the CF₃ group meta to the imide nitrogen. Thus, the effect of substituents in the ortho-positions of nitrogen on properties was greater than the effect of substituents in the meta-positions.     

Synthesis and Characterization of Polyamides Derived From Cyano-Containing 1,4-Bis(4-aminophenoxy)benzene Monomers

Summary A series of potentially electroactive aromatic-aliphatic polyamides based upon 3,6-bis(2-cyano-4-aminophenoxy)phthalonitrile (1) was synthesized in N,N-dimethylacetamide to yield polymers with intrinsic viscosities of 0.66-1.04 dL/g. One polyamide was synthesized using 1,4-bis(2-cyano-4-aminophenoxy)benzene (2) to compare to 1. There appears to be an odd-even effect of methylene spacer length upon the mechanical properties and glass transition temperature, with an even number of methylene groups yielding the larger values. Thermogravimetric analysis in air and nitrogen showed that these polymers had similar 5% weight losses in both atmospheres, which indicated that oxygen is not involved in the initial degradation of these polymers.     

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。     

2,2’-双[4-(4-氨基苯氧基)苯基]丙烷的制备方法

介绍了以2,2’-双(4-羟基苯基)丙烷、对氯硝基苯,碱金属碳酸盐或碱金属氢氧化物为原料,在合适的溶剂中合成2,2’-双[4-(4-硝基苯氧基)苯基]丙烷,再经不同还原方法制备2,2’-双[4-(4-氨基苯氧基)苯基]丙烷。并从反应工艺条件、产品收率、产物纯度、是否适合规模化生产等方面阐述了制备2,2’-双[4-(4-氨基苯氧基)苯基]丙烷方法的优缺点。通过比较、分析指出了2,2’-双[4-(4-氨基苯氧基)苯基]丙烷的研究和发展方向。