| Summary: | 碩士 === 大同工學院 === 化學工程研究所 === 87 === ABSTRACT
Four series of new aromatic poly(amide-imide)s were synthesized from 3,3’,4,4’-diphenylsulfone tetracarboxylic dianhydride (DSDA) and four aromatic diamines (4,4’-ODA, 4,4’-MDA, TPE-R, BAPP) with various aromatic dicarboxylic acids. First, the imide-containing diamines (Ⅰ, Ⅱ, Ⅲ, Ⅳ) were prepared in a dipolar aprotic solvents by the ring-opening addition of diamine to DSDA to form amic acid-diamines, followed by cyclodehydration by means of toluene-water azeotropic distillation. After analyses, these diamine monomers were a mixture of diimide-diamines (Ⅰ’,Ⅱ’, Ⅲ’, Ⅳ’), tetraimide-diamines (Ⅰ’’,Ⅱ’’, Ⅲ’’, Ⅳ’’) and residual diamines. Different ratios of these diamine monomers were obtained under different reaction conditions.
PART Ⅰ
Composition ratio of these monomers (Ⅰ) analyzed by 1H-NMR spectrum was 24:38:38 of Ⅰ’:Ⅰ’’:4,4’-ODA. The eight PAIs (Ⅰ-PAIa~h ) were synthesized by direct polycondensation of this mixture diamine monomer (Ⅰ) and various aromatic dicarboxylic acids using triphenyl phosphite (TPP) and pyridine (Py) as condensing agents in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of these Ⅰ-PAIa~h were in the range of 0.82~1.56 dL/g. Most Ⅰ-PAI series were soluble in polar solvents such as NMP, N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO), and even in less polar solvents like m-cresol and pyridine. They had the better solubility as compared with corresponding Ⅰ-PI and Ⅰ-PA series, which have similar structures. Ⅰ-PAI films cast from polymer solutions had tensile strengths of 102~119 MPa, elongations at break of 7~12 %, and initial moduli of 2.33~2.99 GPa. The glass transition temperatures (Tgs) of Ⅰ-PAI series by DSC were in the range of 293~317 ℃. Except for Ⅰ-PAIb and Ⅰ-PAIf, Ⅰ-PAI series showed Tg values higher than Ⅰ-PI (Tg = 301℃) and Ⅰ-PA series (Tg = 232~307℃). Their 10 % weight loss temperatures by TGA were recorded in the range of 493~529 ℃ in nitrogen and 503~531 ℃ in the air atmosphere, and most Ⅰ-PAI series were also between corresponding Ⅰ-PI and Ⅰ-PA series.
PART Ⅱ
Composition ratio of these monomers (Ⅱ) analyzed by 1H-NMR spectrum was 28:36:36 of Ⅱ’:Ⅱ’’:4,4’-MDA. The eight PAIs (Ⅱ-PAIa~h ) were synthesized by direct polycondensation of this mixture diamine monomer (Ⅱ) and various aromatic dicarboxylic acids using triphenyl phosphite (TPP) and pyridine (Py) as condensing agents in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of these Ⅱ-PAIa~h were in the range of 0.91~1.54 dL/g. All Ⅱ-PAI series were soluble in polar solvents such as NMP and N,N-dimethylacetamide (DMAc), and they had the better solubility as compared with corresponding Ⅱ-PI andⅡ-PA series, which have similar structures. Ⅱ-PAI films cast from polymer solutions had tensile strengths of 80~95 MPa, elongations at break of 8~14 %, and initial moduli of 1.86~2.08 GPa. The glass transition temperatures (Tgs) of Ⅱ-PAI series by DSC were in the range of 249~316 ℃, and PAIs (Ⅱ-PAIc, f, g, h) showed Tg values lower than corresponding Ⅱ-PI (Tg = 314 ℃) and Ⅱ-PA series (Tgs of Ⅱ-PAc, f, g, h ranged from 290~299 ℃). Their 10 % weight loss temperatures by TGA were recorded in the range of 493~508 ℃ in nitrogen and 488~528 ℃ in the air atmosphere, and were also between corresponding Ⅱ-PI and Ⅱ-PA series.
PART Ⅲ
Composition ratio of these monomers (Ⅲ) analyzed by 1H-NMR spectrum was 38:31:31 of Ⅲ’:Ⅲ’’:TPE-R. The eight PAIs (Ⅲ-PAIa~h ) were synthesized by direct polycondensation of this mixture diamine monomer (Ⅲ) and various aromatic dicarboxylic acids using triphenyl phosphite (TPP) and pyridine (Py) as condensing agents in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of these Ⅲ-PAIa~h were in the range of 0.72~1.19 dL/g. All Ⅲ-PAI series could dissolved in polar solvents such as NMP and N,N-dimethylacetamide (DMAc), and they had the better solubility as compared with corresponding Ⅲ-PI and PAs (Ⅲ-PAa~h) those with similar structures. Ⅲ-PAI films cast from polymer solutions had tensile strengths of 92~99 MPa, elongations at break of 6~14 %, and initial moduli of 1.95~2.28 GPa. The glass transition temperatures (Tgs) of Ⅲ-PAI series by DSC ranged from 240~257 ℃. In comparison with Tgs of Ⅲ-PAI series, Ⅲ-PA series and Ⅲ-PI, Ⅲ-PI had the highest Tg value (256 ℃), and Ⅲ-PAIa, b, f showed Tg values between Ⅲ-PI and Ⅲ-PAa, b, f, but Tg values of Ⅲ-PAIc, g,, h were lower both. The 10 % weight loss temperatures of Ⅲ-PAI series by TGA were recorded in the range of 493~529 ℃ in nitrogen and 503~531 ℃ in the air atmosphere, and every values were between corresponding Ⅲ-PI and Ⅲ-PA series.
PART Ⅳ
Composition ratio of these monomers (Ⅳ) analyzed by 1H-NMR spectrum was 80:10:10 of Ⅳ’/Ⅳ’’/ BAPP. The eight PAIs (Ⅳ-PAIa~h ) were synthesized by the direct polycondensation of this mixture diamine monomer (Ⅳ) and various aromatic dicarboxylic acids using triphenyl phosphite (TPP) and pyridine (Py) as condensing agents in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of these Ⅳ-PAIa~h ranged from of 0.83~1.27 dL/g. All Ⅳ-PAI series exhibited the excellent solubility, and they had the better solubility as compared with corresponding Ⅳ-PI and Ⅳ-PA series those with similar structures. Ⅳ-PAI films cast from polymer solutions had tensile strengths of 68~81 MPa, elongations at break of 14~23 %, and initial moduli of 1.82~2.45 GPa. The glass transition temperatures (Tgs) of Ⅳ-PAI series by DSC ranged from 241~256 ℃, and were between Ⅳ-PI (Tg ＝ 263 ℃) and Ⅳ-PA series (Tgs ＝ 227~254 ℃). Ⅳ-PAI series had good thermal stability, and their 10 % weight loss temperatures by TGA were recorded in the range of 511~518 ℃ in nitrogen and 494~511 ℃ in the air atmosphere. And their T10 values in the air were between corresponding Ⅳ-PI and Ⅳ-PA series, but these in nitrogen were higher than both.
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