Characterization of Acetone-Solution Casting Film of PMMA

Front. Chem.
China (2006) 1: 45–47

DOI 10.1007/s11458-005-0007-4
RESEARCH ARTICLE
Xue Feng, Fu Weiwen, Cheng Rongshi
Characterization of Acetone-Solution Casting Film of PMMA
# Higher Education Press and Springer-Verlag 2006
Abstract Acetone solution-casting films of poly(methyl- of polymer. Some researches on this subject have been done
methacrylate) were analyzed by differential scanning calorim- [15,16] recently. Since the alternative vibration field
etry and pyrolysis gas chromatography-mass spectroscopy seriously affects the polymer melt, we can expect that a
under natural evaporation and ultrasonic vibration, respec- similar effect may also occur in the film formation when
tively. Analytical results indicate that both the condensed casting a polymer solution as an external field [17,18]. The
structure of the polymer and the residue solvent in the films aim of the present work is to study the effect of the externally
vary in different film-forming conditions and that the residue- applied ultrasonic field on the nascent films obtained by
solvated acetone in films prepared under natural evapora- casting a poly(methylmethacrylate) (PMMA) solution.
tion is 12 times greater than that under ultrasonic vibration.
Keywords solution casting, poly(methylmethacrylate), 2 Experimental

ultrasonic, condensed structure, characterization
2.1 Materials
1 Introduction Poly(methylmethacrylate) was prepared by free-radical

polymerization, with acetone and ethanol as analytical-
Extrusion of the thermoplastic polymer melts by providing grade reagents.
electromechanical vibration led Qu to invent the electro-
magnetic dynamic extruder and injector. These novel
polymer processing machines have significant advantages, 2.2 Sample preparation and characterization
such as low energy consumption, lower processing tem-
perature, and diminished die swelling. Hence, it is possible The prepared PMMA was dissolved in acetone, filtered,
to get final products with superior physical properties when precipitated by the addition of ethanol, and then dried. A
compared with those of conventional single-screw extruder 1% acetone solution of the purified PMMA sample was
or injector [1–7]. Previous research mainly focused on the prepared and divided into two equal parts, A and B, and
rheological behaviors of the polymer during dynamic pro- placed in two glass dishes of the same dimensions. Solution
cessing and on the mechanical properties of the final prod- A was evaporated under natural conditions, while solution
ucts [8 –14]. Relatively, little attention had been paid to the B was evaporated using ultrasonic vibration. Both were put
structural changes of polymers when placed in other phys- in the same ventilated case. After the solvents in the tubes
ical fields such as mechanical vibration. The influences of were almost volatilized, the condensed film was placed in a
the extra field on the structure and properties of polymers dryer for 30 min at 70°C, and place the sample on standby
come under the category of the effects of the metastable state in a desiccator.
The samples were studied by differential scanning
Translated from Journal of South China University of Technology calorimetry (DSC; MDSC 2910, TA Instruments, USA)
(Natural Science Edition), 2005, 33(3) (in Chinese) using the following procedure. They were scanned from 30
to 200°C at a heating rate of 20°C/min, kept isothermally at
Xue Feng (*), Fu Weiwen, Cheng Rongshi (*) 200°C for 5 min, cooled to 30°C at the same cooling rate,
College of Materials, South China University of Technology,
Guangzhou 510640, China and then kept at 30°C for 1 min. Scanning was continued at
E-mail: [email protected] the same temperature programming for five cycles.
The samples were also studied by pyrolysis gas
Cheng Rongshi chromatography-mass spectroscopy (PyGC-MS; JHP-3S
College of Chemistry and Chemical Engineering,
Nanjing University, Courier Pyrolysis Analyzer, Japan Analysis Industry; HP
Nanjing 210093, China GC 5973-MS 6890, Agilent Instrument Co., USA ) and
E-mail: [email protected] pyrolyzed at 590°C for 10 s.
46
Fig. 3 Enlarged DSC curve of PMMA film (second to fifth heating)

Fig. 1 DSC curve of PMMA film (first heating)
shown in Fig. 4. This figure illustrates that the Tg of the cast

3 Results and discussion film under natural conditions (sample A) is higher than that
of the ultrasonic cast film (sample B). The Tg of both
The initial DSC heating curves represent the behavior of the samples increases with the order of scan number, but the
nascent films. Samples A and B display distinct differences, extent of variation in sample B is greater than that in sample
as shown in Fig. 1. A wide exothermic peak at about 100°C A; it approaches that of sample A only after the fifth cycle of
is seen in sample A, which appears like a glass transition or scanning. This implies that the structural difference of the
as a pair of adjacent endothermic and exothermic peaks. In nascent films prepared under different conditions may
sample B, neither an endothermic nor an exothermic peak is gradually vanish in the course of cyclic heat treatment in
observed, nor is glass transition. DSC measurements.
As the nascent film via first scan is heated to the melting There are two possible reasons why the nascent films of
state and then cooled down to low temperatures, the con- the samples have such a great difference when the first DSC
densed structure of the polymer is spontaneously reas- scan is performed. The first is that the structure of the
sembled. The reassembling course may be followed by condensed state of the polymers under ultrasonic vibration
successive DSC scan curves. The second to fifth DSC changes. The second is that the residue solvent present in
heating curves are shown in Fig. 2. Both samples A and B the nascent films formed under varied conditions may be
showed similar behavior, with a distinct glass transition different. In the course of film formation by casting a poly-
region at around 120°C. This fact indicates that after heat mer solution under externally applied ultrasonic vibration,
treatment by the first scan, differences in the structural the polymer chain may be rearranged because of the force
characteristics of the nascent films are almost eliminated. field to form a more uniform structure similar to the struc-
However, if we study the enlarged portion of the glass ture of the melt. Hence, in the first DSC scanning of the
transition region, as shown in Fig. 3, a nonnegligible differ- nascent film, no glass transition region could be observed.
ence still exists between the samples. We recorded the However, for successive scans, the cohesive entanglements
temperatures at both the onset and inflection points of rebuild spontaneously in the glass state as the temperature is
various scan curves as the glass transition temperatures (Tg) lowered in the melt. Therefore, we may infer that the main
of the polymer. A plot of Tg vs the order of scan number is
Fig. 2 DSC curve of PMMA film (second to fifth heating) Fig. 4 Relationship between scan number and Tg
47
evaporation is 12 times greater than that in films prepared

under ultrasonic vibration.
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Front. Chem.

China (2006) 1: 45–47

Xue Feng, Fu Weiwen, Cheng Rongshi

Characterization of Acetone-Solution Casting Film of PMMA

# Higher Education Press and Springer-Verlag 2006

Keywords solution casting, poly(methylmethacrylate), 2 Experimental

1 Introduction Poly(methylmethacrylate) was prepared by free-radical

Fig. 3 Enlarged DSC curve of PMMA film (second to fifth heating)

shown in Fig. 4. This figure illustrates that the Tg of the cast

evaporation is 12 times greater than that in films prepared

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