Synthesis and properties of aromatic polyimides containing oxyalkylene linkages

1995 ◽  
Vol 7 (1) ◽  
pp. 23-40 ◽  
Author(s):  
Mark W Beltz ◽  
Frank W Harris
Keyword(s):  
Glass Transition ◽  
Organic Solvents ◽  
Ethyl Ether ◽  
Amic Acid ◽  
Pyromellitic Dianhydride ◽  
Melting Points ◽  
Aromatic Diamines ◽  
Thermal Methods ◽  
Glass Transition Temperatures ◽  
Aromatic Polyimides

A series of para-catenated aromatic diamines containing oxyalkylene linkages, i.e., i.2-bis(4-aminophenoxy)ethane, bis[2-(4-aminnophenoxy)ethyl]ether, 1,2-bis[24{4-aminio-phenoxy)ethoxyjethane and bis{2-[2A4-aminophenoxy)ethoxy]ethyllether were polymerized with 3,3',4.4'benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride. The poly(amic acid)s obtained were imidized by both chemical and thermal methods. It was postulated that the incorporation of the flexible linkages in the polyimides' backbones would result in solubility in organic solvents and moderate glass transition temperatures (Tg) that would allow the polymers to be melt processed. However, the polyimides were insoluble and highly crystalline with melting points (Tm) above 400"C. In an attempt to disrupt the polymers' symmetry. mixtures of the diamines and 1,3-bis(3-aminophenoxy)benzene were polymerized with BTDA. The resulting copolymers were insoluble and semrnicrystalline with Tm values near 310C. A polyimide with similar properties was obtained by polymerizing a disubstituted diamine, 2,2-diethyl-t,3-bis(4-aminophenoxy)propane, with BTDA. A soluble polymer that could be melt processed was prepared from BTDA and a meta-catenated diamine containing an oxyalkylene linkage, bis[2-(3-aminophenoxy)ethyl)ether. The polymer had a strong Tg near 156 'C and a weak Tm near 240C.

Preparation and Properties of Novel Aromatic Polyimides from 4,4′-Diamino-4″ -Hydroxytriphenylamine and Aromatic Tetracarboxylic Dianhydrides

2000 ◽  
Vol 12 (1) ◽  
pp. 197-203 ◽  
Author(s):  
Satoshi Akimoto ◽  
Mitsutoshi Jikei ◽  
Masa-aki Kakimoto
Keyword(s):  
Aqueous Solution ◽  
Weight Loss ◽  
Hydrogen Bonding ◽  
Glass Transition ◽  
Dimethyl Sulfoxide ◽  
Organic Solvents ◽  
Phthalic Anhydride ◽  
Glass Transition Temperatures ◽  
Aromatic Polyimides ◽  
Polymer Properties

Novel aromatic polyimides containing hydroxytriphenylamine units were prepared from 4,4′-diamino-4″-hydroxytriphenylamine 1 and various aromatic tetracarboxylic dianhydrides 2. The glass transition temperatures ( Tgs) of these polyimides were in the range of 274–388 °C and the 10% weight loss temperatures ( T d10s) were above 462 and 511 °C in air and nitrogen respectively. Polyimide 4f prepared from diamine 1 and 4,4′-hexafluoroisopropylidenebis(phthalic anhydride) (6FDA) was soluble not only in organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidone and dimethyl sulfoxide but also in tetramethylammonium hydroxide aqueous solution. Other resulting polyimides were not soluble in organic solvents. The resulting polyimides 4 possessed Tgs about 20–70 °C higher and poorer solubilities than the previously reported polyimides prepared from 4,4′-diaminotriphenylamine and various aromatic tetracarboxylic dianhydrides. These results indicated that polymer properties such as thermal behaviour and solubilities were influenced by the intermolecular interaction of hydrogen bonding due to hydroxy units.

Synthesis and Properties of New Triphenylamine-Containing Aromatic Polyimides Based on N,N′-Bis(4-Aminophenyl)-N,N′-Diphenyl-4,4′-Biphenyldiamine

2003 ◽  
Vol 15 (3) ◽  
pp. 281-290 ◽  
Author(s):  
Yoshio Imai ◽  
Mina Ishida ◽  
Masa-Aki Kakimoto
Keyword(s):  
Weight Loss ◽  
Glass Transition ◽  
Tensile Properties ◽  
Organic Solvents ◽  
Ring Opening ◽  
Aromatic Diamine ◽  
Transition Temperatures ◽  
Glass Transition Temperatures ◽  
Aromatic Polyimides ◽  
Step Procedure

A new aromatic diamine monomer, N,N′-bis(4-aminophenyl)-N,N′-diphenyl-4,4′-biphenyldiamine, was first synthesized in two steps by the condensation of N,N′-diphenyl-4,4′-biphenyldiamine with 4-fluoronitrobenzene, followed by reduction. New triphenylamine-containing aromatic polyimides having inherent viscosities of 0.67-0.91 dl g−1 were synthesized from the aromatic diamine and various aromatic tetracarboxylic dianhydrides by the conventional two-step procedure that included ring-opening polyaddition giving precursor polyamic acids and subsequent thermal cyclodehydration. Most of the aromatic polyimides were soluble on heating in organic solvents such as dimethylacetamide, m-cresol, pyridine, and chloroform, and gave flexible and tough films with good tensile properties. The glass transition temperatures and 10% weight loss temperatures of the polyimides were in the range of 293-361 and 565-595 °C, respectively, in nitrogen.

Processable Poly(Keto-Imide)s Having Bulky Pendent Ether Groups

1998 ◽  
Vol 10 (1) ◽  
pp. 1-10 ◽  
Author(s):  
S Tamai ◽  
W Yamashita ◽  
A Yamaguchi
Keyword(s):  
Glass Transition ◽  
Thermal Properties ◽  
Melting Point ◽  
Ambient Temperature ◽  
Organic Solvents ◽  
Pyromellitic Dianhydride ◽  
Transition Temperatures ◽  
Glass Transition Temperatures ◽  
Chemical Structures ◽  
Tetracarboxylic Dianhydride

1, 3-Bis(3-aminobenzoyl)benzene (BAB), 1, 3-bis(3-amino-4-phenoxybenzoyl)benzene (BAPB) and 1, 3-bis(3-amino-4-biphenoxybenzoyl)benzene (BABB) were synthesized from 1, 3-bis(3-nitro-4-chlorobenzoyl)benzene. By using these three diamines and commercially available tetracarboxylic dianhydrides such as 3, 3′, 4, 4′-benzophenone tetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA), several kinds of poly(keto-imide)s were synthesized. Thermal properties and processability such as melt-flowability and solubility in organic solvents of the obtained poly(keto-imide)s were investigated by focusing on the chemical structures of their repeating structure units. Inherent viscosities of poly(keto-imide)s ranged from 0.54 to 0.75 dl g−1. These poly(keto-imide)s displayed glass transition temperatures ( Tg) between 219 and 256 °C, and only the poly(keto-imide) prepared from BAB and PMDA showed a melting point ( Tm)at 451 °C. Melt-flowabilities of these poly(keto-imide)s except for BAB/PMDA poly(keto-imide) were observed between 285 and 330 °C. The poly(keto-imide)s having bulky pendent ether groups were soluble in chloroform, 1, 1, 2-trichloroethane, N, N-dimethylacetamide and m-cresol at ambient temperature.

Organo-Soluble, Segmented Rigid-Rod Polyimides: Synthesis and Properties

1991 ◽  
Vol 227 ◽  
Author(s):  
F. W. Harris ◽  
S. L. C. Hsu ◽  
C. J. Lee ◽  
B. S. Lee ◽  
F. Arnold ◽  
...  
Keyword(s):  
Thin Films ◽  
Thermal Expansion ◽  
Glass Transition ◽  
Oxidative Stability ◽  
Organic Solvents ◽  
Dielectric Constants ◽  
Glass Transition Temperatures ◽  
Thermal Expansion Coefficients ◽  
Rigid Rod ◽  
Expansion Coefficients

ABSTRACTSeveral segmented, rigid-rod polyimides have been prepared that are soluble in organic solvents in their fully imidized form. The polymers were prepared from commercial dianhydrides and 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB). Their intrinsic viscosities ranged from 1.0 to 4.9 dL/g. Tough, colorless films could be cast from m-cresol solutions at 100°C. The polymers had glass transition temperatures (Tgs) above 275°C and displayed outstanding thermal and thermo-oxidative stability. Fibers were prepared from the 3,3′,4,4′-tetracarboxybiphenyl dianhydride (BPDA) based polymers that had moduli of 130 GPa and tensile strengths of 3.2 GPa. The thermal expansion coefficients and dielectric constants of thin films (20–25 μm) of the polymers were as low as −2.40×10−6 and 2.5, respectively.

scholarly journals Studies of Formation Mechanism, Structure, and Properties of Network Copolymers Obtained by Cocuring of Rolivsan Thermosetting Resins with Aromatic Diamines

2019 ◽  
Vol 2019 ◽  
pp. 1-15
Author(s):  
B. A. Zaitsev ◽  
L. G. Kleptsova ◽  
I. D. Shvabskaya
Keyword(s):  
Glass Transition ◽  
High Temperature ◽  
Thermal Analyses ◽  
Polymer Network ◽  
Three Dimensional ◽  
Transition Temperatures ◽  
Structure And Properties ◽  
Aromatic Diamines ◽  
Thermosetting Resins ◽  
Glass Transition Temperatures

Rolivsan thermosetting resins (ROLs) demonstrate high glass-transition temperatures and excellent processability. In our work, high-temperature properties of ROLs were significantly improved using a novel technique for structural and chemical modification of microheterogeneous network polymers. This technique involves, among other procedures, cocuring of rolivsan resins with aromatic diamines (ADA). The most noticeable increase in storage moduli and glass transition temperatures (Tg) of these copolymers was achieved when ROLs were modified with 10-15 wt.% of ADA and the resulting blends were subjected to thermal treatment in air in the temperature range 180 to 320°C for several hours. FTIR, 13С NMR spectroscopy, and dynamic mechanical and thermal analyses were used for studying the structure and properties of the obtained products. It was demonstrated that the mechanism of formation of ROL-ADA copolymers includes the following high-temperature reactions: (i) three-dimensional radical copolymerization of unsaturated ROL components and (ii) cleavage of heat-sensitive methacrylate crosslinking units inside the polymer network. The second process is accompanied by formation of pending units of methacrylic acid and methacrylic anhydride, which participate in condensation reactions with ADA.

Novel allyl and propenyl monomers for modification of the bismaleimide resins, with excellent dielectric properties and high glass transition temperatures

2019 ◽  
Vol 32 (1) ◽  
pp. 116-126
Author(s):  
Chunyan Qu ◽  
Jiaying Chang ◽  
Changwei Liu ◽  
Dezhi Wang ◽  
Wanbao Xiao ◽  
...  
Keyword(s):  
Glass Transition ◽  
Bisphenol A ◽  
Dielectric Constants ◽  
Resonance Spectroscopy ◽  
Transition Temperatures ◽  
Melting Points ◽  
Scanning Calorimetry ◽  
Bismaleimide Resin ◽  
Glass Transition Temperatures ◽  
Bismaleimide Resins

Two new monomers were prepared by the reaction of 2-allylphenol and 4,4′-biphenyldicarbonyl chloride under different reaction conditions. The monomers were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The curing processes of N, N-4,4′-bismaleimidodiphenylmethyene with 4,4′-bis(2-allylphenyl) biphenyldicarbonylate (BABC) and 4,4′-bis(2-propenylphenyl benzoate) ether (BPBE) were studied by rheological analysis and differential scanning calorimetry. Melting points of two monomers, BABC and BPBE, are 64°C and 121°C, respectively. The ABMI [4,4′-bis(2-allylphenyl)biphenyl bismaleimide] and PBMI [4,4′-bis(2-propenylphenyl)biphenyl bismaleimide] resins showed exothermic peaks at 233°C and 204°C, respectively. The measured melting points are significantly lower than that of the traditional bismaleimide resin which is modified by allyl bisphenol A. Dynamic mechanical analysis of the materials showed glass transition temperatures of ABMI and PBMI to be in the range of 213–258°C and 302–339°C, respectively. Thermogravimetric analysis of the cured resins showed 5% weight loss for ABMI and PMBI at 437°C and 428°C, along with char residues of 35.6–39.5%, respectively, at 800°C under nitrogen atmosphere. Furthermore, dielectric constants of propenyl-modified resins were lower (2.46–3.10) with dissipation factors of 0.0034–0.0036, compared with those of allyl bisphenol A resins.

Synthesis and properties of novel polyimides containing 2,6-benzobisoxazole units

e-Polymers ◽  
2009 ◽  
Vol 9 (1) ◽  
Author(s):  
Xiangli Meng ◽  
Yudong Huang ◽  
Zushun Lv ◽  
Hong Yu
Keyword(s):  
Thermal Stability ◽  
Weight Loss ◽  
Amic Acid ◽  
Aprotic Solvents ◽  
Polyimide Films ◽  
Excellent Thermal Stability ◽  
Glass Transition Temperatures ◽  
Aromatic Polyimides ◽  
H Nmr ◽  
Structures And Properties

AbstractThe diamine monomer, 2,6-bis(p-aminophenyl)-benzo-[1,2-d; 5,4-d’] bisoxazole was successfully synthesized. Three aromatic polyimides (PI) based on 2,6-bis(p-aminophenyl)-benzo-[1,2-d; 5,4-d’] bisoxazole were prepared via a conventional two-stage procedure with a variety of dianhydrides. Their structures and properties were characterized by FTIR, 1H NMR, TG, DSC and XRD. The intermediate poly(amic-acid)s (PAA) had inherent viscosities of 1.18-1.70 dL/g and could be thermally converted into lightly yellow polyimide films. The resulted polyimides showed excellent thermal stability, and the glass transition temperatures (Tg) of all polymers were above 280 oC, and the 5% weight loss temperatures of polymers were about 550 oC in N2. The solubility of these polyimides in various solvents was evaluated. They were all insoluble in conventional polar aprotic solvents.

Preparation of aromatic polyamides from newly separated optically pure phenylindanedicarboxylic acid and their application to enantioseparation

1994 ◽  
Vol 6 (4) ◽  
pp. 415-421 ◽  
Author(s):  
Atsushi Morikawa ◽  
Masa-Aki Kakimoto ◽  
Yoshio Imai
Keyword(s):  
Glass Transition ◽  
Stationary Phase ◽  
Optically Active ◽  
Aromatic Diamines ◽  
Glass Transition Temperatures ◽  
Aromatic Polyamides ◽  
Pure Alcohol ◽  
Optically Pure ◽  
Hydrolysis Of ◽  
Pure Isomer

An optically pure isomer of 1,l,3.-trimethyl-3-phenylindane-4',5-dicarboxylic acid (PIDA) was obtained by introduction of racemric PIDA to a diester of the optically pure alcohol. D-(-)-pantolactone, followed by hydrolysis of the separated stereoisomer of the diester. Optically active aromatic polyamides (aramids) were synthesized by the reaction of the optically pure PIDA with various aromatic diamines. The specific rotations of these aramids ranged from + 284 to +4416. The aramids were soluble in organic solvents such as N,N-dimethylacetamide, pyridine and m-cresol. These materials had glass transition temperatures over 290 'C, and did not decompose below 380 C. The solubility and thermal behaviour were almost the same as those of the racemic aramids. The optically active aramids were examined as a stationary phase for chromatographic enantioseparation. When the aramid derived from p-phenylenediamine was used for this purpose, the stereoisomers of l-phenylethylamine could be easily separated.

Aromatic Poly(ether imide oxadiazole)s

1992 ◽  
Vol 4 (2) ◽  
pp. 73-80 ◽  
Author(s):  
F. W. Mercer
Keyword(s):  
Thermal Stability ◽  
Glass Transition ◽  
Aprotic Solvent ◽  
Dielectric Constants ◽  
Aromatic Diamines ◽  
Glass Transition Temperatures ◽  
Good Thermal Stability ◽  
Polar Aprotic Solvent ◽  
Carbonate Reaction ◽  
Poly Imide

Two oxadiazole containing aromatic diamines were synthesized. The diamines were prepared by reaction of aminophenols with 2,5-bis(4-fluorophenyl)-4l3,4-oxadiazole in a polar aprotic solvent in the presence of potassium carbonate. Reaction of the resulting 2,5-bis(4-(aminophenoxy)phenyl)-1,3,4-oxadiazoles with dianhydrides gave a series of polymeric amic acids. Thermal treatment yielded poly(imide ether oxadazole) films which displayed good thermal stability, flexibility, and glass transition temperatures ranging from 241 to 344C. The dielectric constants of the films were characterized as a function of relative humidity.

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