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APPLICATION OF CAPRATE ALIPHATIC ESTER AS BIO-PLASTICIZER AND BIO-ADDITIVE IN PLASTICS

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Abstract

The aim of the present study is to investigate the application of caprate aliphatic esters as co-plasticizers and biodegradable additives in polyvinyl chloride. i-Bu caprate was used in different proportions. The applicability of a mixture of esters as bio-plasticizers and bio-additives in polyvinyl chloride was studied. The influence of the ester on the glass transition temperature Tg of polyvinyl chloride at the selected ratios was determined by the method of differential-scanning calorimetry. It was found that with increasing its amount Tg of the polymer decreases, ie. the flexibility of macromolecules increases which is a prerequisite for higher deformability. This supports the conclusion that the ester mixture has a plasticizing effect.
II-289
International Scientific ConferenceUNITECH 2022 Gabrovo
INTERNATIONAL SCIENTIFIC CONFERENCE
18-19 November 2022, GABROVO
APPLICATION OF CAPRATE ALIPHATIC ESTER
AS BIO-PLASTICIZER AND BIO-ADDITIVE IN PLASTICS
Dragomir Vasilev1, Nadezhda Petkova2, Milka Atanasova1, Panteley Denev2
1 Technical University of Gabrovo
2 University of Food Technologies, Plovdiv
Abstract
The aim of the present study is to investigate the application of caprate aliphatic esters as co-plasticizers and
biodegradable additives in polyvinyl chloride. i-Bu caprate was used in different proportions. The applicability of a
mixture of esters as bio-plasticizers and bio-additives in polyvinyl chloride was studied. The influence of the ester on
the glass transition temperature Tg of polyvinyl chloride at the selected ratios was determined by the method of
differential-scanning calorimetry. It was found that with increasing its amount Tg of the polymer decreases, ie. the
flexibility of macromolecules increases which is a prerequisite for higher deformability. This supports the conclusion
that the ester mixture has a plasticizing effect.
Keywords: keywords, keywords, keywords, keywords, keywords, keywords, keywords.
INTRODUCTION
During plasticization, the ability of the
polymer to large highly elastic deformations is
improved [1]. The addition of plasticizers in
polymer composite materials leads to a reduction
in energy costs during their processing, the
duration of preparation of the mixtures. The
participation of plasticizers facilitates the
dispersion of the components of the polymer
compositions and the formation of the products.
There are major theories explaining the
changes in the polymer during plasticization, all
of which explain the effect of the plasticizer on
the interaction of its molecules with the polymer
at the molecular and supramolecular level,
which is determined by the compatibility
between the polymer and the plasticizer. An
indicator of this is the lowering of the glass
transition temperature of the polymer Tg, which
is largely determined by the chemical composition,
the structure of the molecule and the amount of
plasticizer [2].
Of the esters of aliphatic acids, stearates and
oleates are the most widely used, especially for
compositions with plasticity at low temperatures.
The search for possibilities to replace the classic
plasticizers with non-toxic and biodegradable
products leads to researching the possibilities of
using aliphatic esters of higher fatty acids or esters
of mono-, di- and polysaccharides. [3, 4]
Glycerol, sorbitol and urea have been found
to be used as hydrophilic plasticizers in
biodegradable starch films. [5, 6]
A similar study was conducted to determine
the influence of sucrose and invert sugar on the
mechanical properties, hydrophilicity of starch
films. The mechanical properties of sucrose,
oleic acid, sorbitol and mannitol as plasticizers
for gelatin films were investigated. [7-10]
Yin and co-authors investigated the
application of three glucose esters, in
comparison with glucose pentaacetate and
sucrooctaacetate, as bioplasticizers for polyvinyl
chloride. [9]
The purpose of the study is to investigate the
influence of i-Bu caprate when incorporated
into polyvinyl chloride polymers to evaluate the
possibilities of its application as a plasticizer.
MATERIALS AND METHODS
Preparing the samples
For the purposes of the experiment,
commercial polyvinyl chloride was used,
without dyes, stabilizers and fillers. i-Bu caprate
obtained by the method described by Vasilev
and co-authors [11] was used as a polyvinyl
chloride plasticizer. The experimental studies
were carried out with samples in the form of
2022
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International Scientific ConferenceUNITECH 2022 Gabrovo
polymer films prepared by solution casting in
tetrahydrofuran. The weighed amount of
polyvinyl chloride is placed in a beaker and 100
cm3 of tetrahydrofuran is added to it. The mixture
is heated in a water bath at 40oC until the
complete dissolution of the polyvinyl chloride,
after which the selected plasticizer is added . The
resulting solution was homogenized for 2 h,
then poured into a Petri dish and left at room
temperature until the solvent completely evaporated.
The film was dried at room temperature in a
vacuum dryer. [9]
Investigation of the plasticizing effect -
differential scanning calorimetry
The thermal properties of the obtained films
were investigated by differential scanning
calorimetry (DSC). The measurements were
carried out on a scanning calorimeter DSC 204
F1 Phoenix (NETZSCH Gerätebau gmbh) in an
argon environment, with a heat flow rate of 20
cm 3 /min at the following temperature regimes:
Heating from 20°C to 200°C at a rate of 10
K/min (first scan);
Isothermal mode at 200°C for 3 min;
Cooling in liquid nitrogen from 200°С to
50°С, with a cooling rate of 10 K/min;
Isothermal mode at 50°C for 5 min;
Heating from –50°C to 200°C at a rate of
10 K/min (second scan);
The weight of a single sample of each sample
is 2.5-4.2 g.
The glass transition temperature Tg was
determined in the second scan as the inflection
point of the thermogram. The processing was
done with PROTEUS specialized software for
DSC 204 F1
RESULTS AND DISCUSSION
The plasticization of polymers is based on
increasing the flexibility of macromolecules and
supramolecular structures, under the action of
the plasticizer, which depends on its
compatibility with the polymer. The parameter
related to the change in flexibility of the
structural elements that can be used to evaluate
the compatibility and the plasticizing effect is
the glass transition temperature.
The glass transition temperature was
determined in the second scan as the inflection
point of the thermogram. The processing was
done with PROTEUS specialized software for
DSC 204 F1.
The results of the DSC analysis of the studied
samples are presented in Table 1 and Fig. 1.
Table 1. Tg data depending on the content of i-Bu caprate
Content of i-Bu caprate in the
studied sample, %
The glass transition
temperature (Tg),
o
C
0
80.5
10
75.8
20
68.1
40
56.7
60
53.5
80,5
75,8
68,1
56,7 53,5
0
10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70
Tg, оC
i-Bu caprate, %
Fig. IV.13. Variation of Tg depending on the content of i-Bu caprate in the sample
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International Scientific ConferenceUNITECH 2022 Gabrovo
The obtained results show the presence of
only one inflection point (one glass transition
temperature) in the thermograms of the studied -
films, which indicates good miscibility between
i-Bu caprate and PVC. The glass transition
temperatures of the studied samples depending
on the content of i-Bu caprate are presented in
Fig. 1. There is a significant decrease in Tg with
increasing content of i-Bu caprate, which is a
confirmation of its plasticizing effect on PVC.
As the content of i-Bu caprate increases, a sharp
decrease in the glass transition temperature is
observed, and at 40 and 60% the difference in
Tg is minimal.
CONCLUSION
The applicability of sonochemistry synthesized
i-Bu caprate as a bio-plasticizer and/or
biodegradable filler in polyvinyl chloride mixtures
was investigated. Using the DSC method, the
effect of ester on the glass transition temperature
of PVC at contents of 0-60% was determined. It
was found that as its amount increases, the Tg of
the polymer decreases, i.e. the flexibility of
macromolecules increases, which is a prerequisite
for higher deformability.
The results obtained at this stage of the
research show that sonochemistry synthesized
i-Bu caprate is applicable as a bio-plasticizer
and/or biodegradable filler in polyvinyl chloride
mixtures in contents up to 40%. Further research
is needed to establish the mechanism of action of
the ester at higher concentrations, with a view to
expanding its application.
Acknowledgement: This research was
financially supported by Fund Science Contract
No 2202С, Technical University of Gabrovo,
Gabrovo, Bulgaria
REFERENCE
[1]. George Wypych, Handbook of plasticizers,
ChemTec Publishing, 2004
[2]. Wilkes, Ch., Ch. Daniels, J. Summers, PVC
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[3]. Tishkova, J., V. Ch.-Bagdassarian, T.
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[4]. Baker, I., R. Willing, D. Furlong, F. Grieser, C.
Drummond, Sugar Fatty Acid Ester Surfactants:
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[5]. Galdeano MC, Grossmann MVE, Mali S,
Bello-Perez LA, Garcia MA, Zamudio-Flores
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oat starch. Mater Sci Eng C 2009, 29 (2), 492-8.
[6]. Galdeano MC, Mali S, G. MVE, Yamashita F,
García MA. Effects of plasticizers on the
properties of oat starch films. Mater Sci Eng C
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[7]. Veiga-Santos P, Oliveira LM, Cereda MP,
Scamparini ARP. Sucrose and inverted sugar as
plasticizer. Effect on cassava starch–gelatin
film mechanical properties, hydrophilicity and
water activity. Food Chem 2007, 103(2):25562.
[8]. Yang X Cao N, Fu Y. Effects of various
plasticizers on mechanical and water vapor
barrier properties of gelatin films. Food
Hydrocol 2009;23(3):729–35.
[9]. Yin, B., N. Atsenggari, Xi Yang, M.
Hakkarainen, Glucose esters as biobased PVC
plasticizers, European Polymer Journal 58 (2014) 3440.
[10]. Jia P., et al. al. Properties of polyvinyl
chloride incorporated with a novel soybean oil
based secondary plasticizer containing a flame
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[11]. Vassilev, D., N. Petkova, P. Denev,
Application of sonochemistry for the synthesis
of capric
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19
Международна научна конференция “УНИТЕХ’21 Габрово
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5Technical University of Gabrovo, 4 H. Dimitar Str., 5300 Gabrovo, Bulgaria
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Dragomir Vasilev1, Nadezhda Petkova2, Panteley Denev2
1Technical University of Gabrovo, Bulgaria
2University of Food Technologies, Plovdiv, Bulgaria
20
Международна научна конференция “УНИТЕХ’21 Габрово
APPLICATION OF CAPRATE ALIPHATIC ESTER AS BIO-PLASTICIZER AND BIO-
ADDITIVE IN PLASTICS ....................................................................................................... 289
Dragomir Vasilev1, Nadezhda Petkova2, Milka Atanasova1, Panteley Denev2
1Technical University of Gabrovo, Bulgaria
2University of Food Technologies, Plovdiv, Bulgaria
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2Dept. of Physics, Trakya University, 22030, Edirne Turkey
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