ABSTRACT:The simultaneous polymerization and processing under high pressure was carried out by using a piston-cylinder type hot pressing apparatus. Before the polymer synthesis, the Michael addition of aniline to N-phenylmaleimide was performed under high pressure as a model reaction, giving N,N'-diphenylaspartimide. The Michael-type polyaddition of 4,4'-methylenedianiline to 4,4'-bismaleimidodiphenylmethane under 150-820MPa at 180-300°C for 20-40h afforded the linear polyaminoimide having inherent viscosities in the range of 0.2-0.8dlg-1 . When the polymerization was carried out at higher temperature, the closslinked polymer was produced. The polymerization under higher pressure required higher temperature. The closslinked polymer synthesized under high pressure was very hard resin with Vickers hardness of 330-360 MPa and high modulus ( > 1.5 GPa), compared with the polymer obtained under ordinary pressure.KEY WORDS High Pressure Polymerization / Polyaminoimide / MichaelType Polyaddition / Bismaleimide / Polyaminoimide resins derived from aromatic bismaleimides and aromatic diamines are known as a class of high temperature thermosetting addition-type polyimides, and used widely as matrices for composite in electronics and aerospace industries. 1 -3 The advantage is that they contain reactive maleimide groups, which are thermally polymerizable without the elimination of volatile by-products that cause voids in highly closslinked polymeric materials.In the field of synthetic polymer chemistry, the reactive hot pressing technique has been developed for many years. 4 • 5 The concept of this technique is to simultaneously synthesize and mold intractable polymeric materials directly from solid monomers, and the technique was applied to the polymerizationprocessing of high temperature aromatic polymers. The application of high pressure to Michael addition reactions has been demonstrated to be extremely effective means due to both kinetic and thermodynamic backgrounds. 6 • 7 We already reported the application of high pressure to the cycloaddition polymerization of p-cyanobenzonitrile N-oxide and found that the solid state polymerization at room temperature giving poly-1,2,4-oxaziazole was accelerated under high pressure. 8 The present investigation was undertaken to explore high pressure polymerization and simultaneous processing for the polyaminoimide by the Michael-type polyaddition of 4,4' -bismaleimidodiphenylmethane (BMI) to 4,4'-methylenedianiline (MDI) without use of both solvent and catalyst [eq l].
New phenolic hydroxyl-pendant aromatic polyimides were synthesized with the N-silylated diamine method in two steps: the ring-opening polyaddition of tetrakis(trimethylsilyl)-substituted 4,4Ј-diamino-3,3Ј-dihydroxybiphenyl to various aromatic tetracarboxylic dianhydrides, giving trimethylsiloxy-pendant poly(amic acid) trimethylsilyl esters, and thermal imidization. The hydroxyl-bearing polyimides were amorphous but insoluble in organic solvents. They had glass-transition temperatures greater than 370°C and temperatures of 10% weight loss greater than 415°C in nitrogen. The hydroxyl-pendant polypyromellitimide film had a high tensile strength and a high modulus of 310 MPa and 10 GPa, respectively.
The sulfur analog of spiroorthocarbonate (SOC) capable of
undergoing tandem double ring-opening polymerization
(dibenzo[3,4;10,11]-1,6,8,13-tetrathiaspiro[6.6]tridecane,
4) was synthesized, and
its polymerization behavior was studied. Some properties of the
polymers obtained and the volume change
on polymerization of 4 were also examined. The
synthesis of 4 was performed by the
acid-catalyzed
ester-exchange reaction of tetrakis(methylthio)methane with
o-xylenedithiol and was obtained in 98%
yield. The structure of 4 was determined by the
spectral and elemental analysis data. Cationic
polymerization of 4 with latent thermal initiator benzyl
tetrahydrothiophenium hexafluoroantimonate
in nitrobenzene proceeded efficiently at more than 150 °C to give the
corresponding poly(thioether−trithiocarbonate) 5. The polymer structure was
determined by the spectral data and further confirmed
by the structures of the decomposition products formed by the reductive
cleavage of the trithiocarbonate
bond of 5 with LiAlH4. The mechanism of the
polymerization was postulated from the results obtained.
Thermal properties of 5 such as
T
g and T
m were examined
and compared with those of its oxygen analog
(13). The volume change was studied in the
polymerizations of 4 and its oxygen analog (2),
during which
5.2 and 6.7% volume expansions were observed,
respectively.
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