6 research outputs found
Effects of Spacer Length and Terminal Group on the Crystallization and Morphology of Biscarbamates: A Longer Spacer Does Not Reduce the Melting Temperature
The effects of alkyl side chain and
spacer lengths and the type
of terminal group on the morphology and crystallization of a homologous
series of biscarbamates (model compounds for polyurethanes) were investigated.
Biscarbamates were synthesized with alkyl side chains of various lengths
ranging from C<sub>4</sub> to C<sub>18</sub> and an alkyl spacer group
with 12 CH<sub>2</sub> units (C<sub>12</sub> spacer) between the two
hydrogen bonding motifs. The crystallization and morphological features
are compared with the previously studied biscarbamates with a C<sub>6</sub> spacer. As a token example, we also studied a biscarbamate
molecule in which the terminal methyl group was replaced by a phenyl
group. We stress four important conclusions of the study: (1) A number
of studies in the literature found that the longer alkyl spacers reduced
the thermal transition temperatures of the molecules, and such behavior
was attributed to an increase in the flexibility of the alkyl spacer.
However, the results of the present study are to the contrary. With
the biscarbamates studied here, the hydrogen-bonding groups on both
sides of the C<sub>12</sub> spacer act as “anchors”,
and the longer spacer does not reduce the melting temperatures compared
with those with the C<sub>6</sub> spacer. (2) The melt viscosity measurements
show shear-thinning behavior, which has been mostly observed with
polysaccharides and hydrogen-bonded polymers. (3) Avrami analysis
shows a two-stage crystallization, which is not commonly observed
in organic small molecule systems. (4) The phenyl end group does not
add another self-assembly code in terms of π-stacking but acts
as a defect. While formation of crystals was observed for biscarbamates
with short alkyl side chains with a C<sub>6</sub> spacer, an increase
in spacer length to C<sub>12</sub> induces spherulitic morphology.
Although the overall sizes of the spherulites are the same for both
spacers, the rate of spherulite growth was higher and the crystallization
rate was lower with the C<sub>12</sub> spacer compared with the C<sub>6</sub> spacer. In contrast with the biscarbamates containing C<sub>6</sub> spacer previously studied, we find that among the biscarbamates
with 12 CH<sub>2</sub> units in the spacer the C<sub>12</sub>–C<sub>12</sub> molecule shows the minimum spherulite size, spherulite growth
rate, and rate of crystallization. The infrared frequency shifts of
the N–H group due to hydrogen bonding were used to calculate
the N···O hydrogen-bonding distance and found to be
close to the value observed in the crystal structure of the biscarbamate
with a C<sub>6</sub> spacer and C<sub>10</sub> alkyl side chain
Synthesis and Properties of Bis(3,5-dimethyl-4-amino phenyl)-4′-methoxy phenyl Methane Based Polymerization of Monomeric Reactants Type Polyimide and Its Composites
Polymerization
of Monomeric Reactants (PMR) type of polyimide was prepared using
bisÂ(3,5-dimethyl-4-amino phenyl)-4′-methoxy phenyl methane
and characterized by elemental analysis, FT-IR, <sup>1</sup>H NMR,
and <sup>13</sup>C NMR spectral techniques. Differential scanning
calorimetry (DSC) analysis shows that melting and curing take place
in the temperature range of 215 to 230 °C and 265 to 315 °C
respectively. The uncured and cured prepolymer undergo two step (335
and 583 °C) and single step (537 °C) decomposition respectively.
The <i>T</i><sub>10%</sub> and char yield at 800 °C
were found to be 465 °C and 46 wt %, respectively. FT-IR and
thermogravimetric analysis (TGA) of the heat treated resin powder
and prepolymer reveal that imidization takes place in the temperature
range 250–275 °C and cross-linking occurs between 275
and 325 °C. The prepolymer was found to undergo photocross-linking.
The flexural strength, flexural modulus, and interlaminar shear strength
of carbon fiber (T300) reinforced BA4MPM-PMR type composite are 447
MPa, 34 GPa, and 42 MPa, respectively