Printer Friendly

Synthesis, Characterization and Thermodynamic Properties of Two New 1,3-Dioxolane Containing Copolymers.

Byline: Zulfiye Ilter, Ilbey Oncu, M. Hamdi Karagoz, Selami Ercan and Ferhat Alhanli

Summary: This study, reports the synthesis and characterization of two new copolymers (poly[2-(p- chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate-co-styrene (PCPhDMA-co-St) and poly[2-(p-chlorophenyl)-1,3- dioxolane-4-yl] methyl acrylate-co-acrylonitrile (PCPhDMA-co-AN)). Copolymers were characterized by spectral (FT-IR, 1H - NMR) and thermal analysis (TGA, DSC). Their thermodynamic properties, such as the adsorption enthalpy, DHa, molar evaporation enthalpy, DHv, the sorption enthalpy, DH1s, sorption free energy, DG1s, sorption entropy, DS1s , the partial molar free energy, DG1[?], the partial molar heat of mixing, DH1[?], at infinite dilution were studied by inverse gas chromatography. Depending on specific retention volumes, V 0, of probes the w ht activity coefficients of solute probes at infinite dilution, 1[?], and Flory-Huggins interaction parameters, , between PCPhDMA-co-St and PCPhDMA-co-AN-solvents were investigated in the range of 413-453 K and 403-453 K, respectively.

Keywords: Polymer, Polymer Synthesis, Thermodynamic properties, Inverse Gas Chromatography, Solubility parameters

Introduction

Compounds containing dioxolane groups have great importance due to usage in negative electron-beam resistance, dry etching processes (because of their good resistance), and herbicides [1-5]. Rossi and coworkers [6] synthesized 1,3-dioxolane polymers for the purpose of bioconjugation reactions. In another study, polymers bearing 1,3-dioxolane at side chains are used as lithium ion conductors [7]. Radical addition polymerizations of 1,3- dioxolane with methacrylates and radical ring opening polymerizations of 1,3-dioxolane derivatives have also been published [8-10].

Condensation reactions of aldehydes or ketones with alcohols by catalyzing with acid gives 1,3-dioxolane derivatives with a smooth procedure [11-13]. We synthesized poly[2-(p-chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate-co-styrene (PCPhDMA-co-St) and poly[2- (p-chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate-co- acrylonitrile (PCPhDMA-co-AN) polymers by radical addition method. IR, 1H-NMR, and TGA were used for characterization of polymers. Also thermodynamic parameters of polymers were investigated by inverse gas chromatography (IGC), which is a widely used and accepted method for determining physicochemical properties [14, 15] of non-volatile materials such as polymers [16], liquid crystals [17], organic pollutants [18], pharmaceutical products [19, 20], and vegetable oils [21, 22].

The technique which is firstly investigated by Guillet and Smidsrod [23] can be used to identify various physicochemical properties of polymer systems such as interaction parameters of polymers with solvent, non-solvent and other polymers. Besides, the method is feasible to obtain solubility parameters, weight fraction coefficients, molar heat and free energy of mixing and sorption, crystallinity degree of semi-crystalline polymers, glass transition and melting points of polymers, decomposition temperatures of polymers, and surface energy of polymers [24, 25]. The inverse term of IGC points out that the interest in the IGC is the stationary phase unlike traditional gas chromatography. So the aim is to measure properties of stationary phase rather than the chromatographic separation process.

Volatile probes are run through the column at different temperatures by an inert gas and the retention times of probes which rely on interactions between the probes and stationary phase are directly measured. Thus IGC is a simple, fast, economical tool which provides valuable thermodynamic information of polymeric materials.

Thermodynamic interactions of poly[2-(p- chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate-co- styrene (PCKPhDMA-co-St) and poly[2-(p-chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate-co-acrylonitrile (PCKPhDMA-co-AN) with alcohols as polar and alkenes as nonpolar solvents were investigated between 50 to 180 degC degrees by IGC.

Experimental

Materials

Chemicals used for the synthesis; glycerin, p- chlorobenzaldehyde, p-toluene sulfonic acid, triethylamine, 2,2'-azobisisobutyronitrile (AIBN), anhydrous MgSO4, hydroquinone, 1,4-dioxane, and chemicals used for IGC studies; alcohols (ethanol, 1-propanol, 1-butanol) and hydrocarbons (n-hexane, n-heptane, n-octane and n- nonane) were purchased from Merc Chemical Co. as chromatographic grade. The coating material, chromosorb W (80-100 mesh) was supplied from Sigma Chemical Co.. To determine chemically different nature and polarity of polymers, four nonpolar (alkanes) and three polar (alcohols) probes were used in this study.

A Fourier transforms infrared spectrometer of Mattson 1000 with KBr pellets were used for IR spectra. 1H-13C-NMR spectra in CDCl3 solutions were obtained by a Gemini Varian 200 MHz spectrometer with tetramethylsilane as an internal reference. Thermal data and glass transition temperatures of PCPhDMA-co-St and PCPhDMA-co-AN were determined with a SHIMADZU DSC 50 instrument. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of copolymers were determined by Hawlet Packard GPC- Addon. Finally, a SHIMADZU GA-14A model gas chromatography equipped with dual flame ionization detector was used for IGC studies.

Synthesis of Copolymers

Synthesizes of monomer ([2-(4-Chlorophenyl)-1,3-dioxolane-4-yl] methyl acrylate: CPhDMA) and it's homopolymer (Poly(CPhDMA) were reported in our previous study in details [26]. Nevertheless, the synthetic reactions of monomers are shown in Scheme 1. Free radical polymerization of acrylonitrile (0.90 g) and styrene (1.34 g) with CPhDMA (5) was performed in a Schlenk flask using AIBN (0.10% percentage of total weight of monomer) as initiator in 1,4-dioxone (two times weight of monomer) at 60 degC for 24 hours. Copolymers were prepared in different percentage of CPhDMA and styrene (6) or acrylonitrile (7) monomers. The reactions of products those studied here are started with 50% percentage of styrene and 70% of acrylonitrile as initial amounts. The products were characterized by IR, and 1H-NMR techniques.

IGC Methodology

The thermodynamic calculations of polymers in IGC technique depend on terms of the elution behavior of ignescent solutes in chromatographic columns. Specific retention volume, (V0 ), is the key term for calculating thermodynamic parameters in IGC and these values are obtained directly from chromatographic parameters. V0 g is determined by relation:

(Equations)

where tp is the retention time of probe and tg is the retention time of methane, F is volumetric carrier gas flow rate, measured at room temperature, T is the column temperature (K), w is the mass of polymeric stationary phase, James- Martin correction factor, J is the factor that correct s the influence of the pressure drop throughout the column and Pi is inlet, P0 is outlet pressures.

As to IGC technique, the values of heats of vaporization and probes sorption enthalpy (DHa) adsorbed by the polymers can be computed according to equation (3) and (4), respectively [27].

(Equations)

The values of sorption parameters, the molar enthalpy, DH1 sorption, DS s) of probes absorbed by PCPhDMA-co-St and PCPhDMA-co-AN were calculated by Equations (5-7).

(Equations)

The weight fraction activity coefficient (1) of the solute at infinite dilution can be calculated from following relation [28].

(Equations)

where R is the gas constant, T is the column temperature, M1 is the molecular mass of the probe, P1 is the saturated vapor pressure of the probe at temperature T, and B11 is the second virial coefficient of the probe in the gaseous state and can be determine from Equation 15. V1, the molar volume of the solute is calculated by Equation 9. [29].

(Equation)

where Vc is the critical molar volume and r is the reduced density of the solute given as:

(Equation)

where zc and Tc are the critical compressibility factor and the critical temperature respectively. The values of zc and Tc are obtained from literature [30].

By obtaining the weight fraction activity coefficient, 1, the partial molar free energy, DG1 , and the average partial molar enthalpy, DH1 values can be calculated from following relations, respectively at infinite dilution [31-33].

(Equations)

Flory-Huggins Interaction Parameter

The Flory-Huggins parameter, (Eq.) shows the strength of interaction between PCPhDMA-co- St/PCPhDMA-co-AN and probe. At infinite dilution of different probes used in this study, the Flory-Huggins parameter is calculated by the following relation:

(Equations)

where and R are the specific volume of the polymer and the universal gas constant respectively. (Eq.) is the saturated vapor pressure which can be calculated from the Antonie equation shown below:

(Equation)

where t is the temperature (in degC) and A, B and C are constants [33]. The second virial coefficients B11 were computed using the following equation:

(Equation)

where Vc is the critical molar volume and Tc is the critical temperature of the solute and n is the number of carbon atoms in the solute.

Solubility Parameters

The solubility parameters of the probes, d1 can be calculated from Hildebrand-Scathard theories and also is a measure of the forces between molecules. d1 is calculated from the relation depicted below [34-36].

(Equations)

The Flory-Huggins interaction parameter is also used for defining solubility of a vapor or a liquid in polymers. Solubility parameter of the polymer, d2, can be computed by using this interaction parameter in the relation given below.

(Equation)

The solubility parameter of polymer d2 can be determined from both (2d2/RT) the slope and intercept ((Eq.) /RT) of the straight line [28] which obtained by plotting d1 versus the left side of Equation 18.

Instrumentation and Procedure

A flame ionization detector equipped with SHIMADZU GA-14A gas chromatograph and Shimadzu C-R6A model integrator used in the study. By following the procedure explained in our previously work [24], 80- 100 mesh size Chromosorb W handled with 1.3958 g PCPhDMA-co-St and 2.1223 g PCPhDMA-co-AN. 3 g of solid supporting material added to solution of polymers in 25 ml 1,4-dioxane and stirred. Then the solvent removed in a rotary evaporator by continuous stirring and slow evaporation under partial vacuum. The column was packed to gas chromatograph device and regenerated at a temperature over glass transition temperature by flowing carrier gas (N2) through column for 24 h prior to use. Hamilton syringes (1 uL) were used to inject probes into column. Three injections were performed at each measuring by volume of 0.2 uL. Shimadzu C-R6A model integrator was used to compute the retention times of probes. Methane was synthesized by reaction of sodium hydroxide with sodium acetate.

Results and Discussion

Characterization Studies of Synthesis

PCPhDMA-co-St and PCPhDMA-co-AN were synthesized by the reaction of [2-(4-chlorophenyl)-1,3- dioxolane-4-yl]methyl acrylate (CPhDMA) with styrene and acrylonitrile by free radical polymerization reaction. CPhDMA and co-polymers were characterized by FT-IR, and 1H-NMR spectral techniques The most important characteristic absorptions of CPhDMA are the stretching vibrations of C=C bond at 1640 cm-1 and stretching vibrations of C=O bond at 1727 cm-1. Comparing vibrations of monomer with PCPhDMA-co-St and PCPhDMA-co-AN shows that the band belongs to C=C stretching disappear in co-polymers spectrums. Besides, the band belong to C=O bond of monomer shifted from 1727 cm-1 to 1730 cm-1 in PCPhDMA-co-St and 1734 cm-1 for PCPhDMA-co-AN.

The characteristic stretching bond of CN could be seen at 2260 cm-1. The 1H - NMR spectrum of monomer depicts, signals at d=3.7-4.3 ppm of -CH2-CH- CH2, d=5,5-5.7 ppm of O2CH, 5.5-6.4 ppm =CH2, and 7.3- 7.7 ppm of aromatic hydrogens peaks. PCPhDMA-co-St and PCPhDMA-co-AN 1H - NMR peaks defined as 1.2-2.5, 1.6-2.5 ppm for CH2CH, 3.2-4.4, 3.4-4.3 ppm for - OCH2-CHO-CH2O-, 5.4-5.6, 5.2-5.5 ppm for O2CH and 6.5-7.6, 7.2-7.4 ppm for aromatic hydrogens respectively.

We also determined the Mn, Mw average molecular weights and PDI values of copolymers by GPC. The values of Mn, Mw, and PDI for PCPhDMA-co-St and PCPhDMA-co-AN are obtained as 556250 g/mol, 2620000 g/mol, 4.71, 8340 g/mol, 15600 g/mol and 1.873, respectively.

Thermal Analysis of Copolymers

The thermal analysis of polymers were performed at 10 degC min-1 under nitrogen gas flow by TGA and curves of thermographs of the copolymers are depicted in Fig 1 according to percent of included monomer units. Thermal properties of two samples of PCPhDMA-co-St and four samples of PCPhDMA-co-AN were studied with TGA. The residue at 480degC for PCPhDMA-co-St and PCPhDMA-co- AN increases by the increasing the percentage of styrene and acrylonitrile monomers in copolymers.

Decomposition of copolymers with increasing temperature is depicted in Table-1. Grand and Grassie [37] denoted that depolymerization process of poly-(methacrylic ester)s is the starting point of thermal degradation of those polymers, and a nucleophilic addition reaction of nitrile groups starts the thermal degradation of polyacrylonitrile [38]. A cyclisation of an expanded conjugated structure takes place after nucleophilic attack to a nitrile [39]. CPhDMA units restrict the intermolecular cyclization between nitrile groups. So the increasing unit numbers of CPhDMA decrease the amount of residue [40-42].

Table-1: The decomposition temperatures and percentage weight loss obtained from TGA curves of PCPhDMA-co-St and PCPhDMA-co-AN according to rising temperature

Copolymers###Decomposition###Weight###Decomposition###Residue

###starting###Loss###ending###(%)

###T (degC)###T (degC)

###PCPhDMA-co-St

###%20 %50 %70

###a###303###320 380 405###440###8

###b###308###330 375 400###435###12

###PCPhDMA-co-AN

###a###310###400 -###-###490###69

###b###304###335 380###-###480###33

###c###306###340 385 440###440###25

###d###307###380 380 410###450###14

The Tg temperatures of copolymers were investigated by DSC. Tg values are calculated 90 degC for PCPhDMA-co-St and 82 degC PCPhDMA-co-AN.

Thermodynamic Properties by Inverse Gas Chromatography

Thermodynamic properties of seven solvents were determined from 323 to 453 K by IGC where PCPhDMA-co-St and PCPhDMA-co-AN were used as stationary phases. The specific retention volumes, Vg were calculated according to Equation (1) and the values of PCPhDMA-co-St and PCPhDMA-co-AN-probes are given in Table-2 and 3, respectively.

It seems that Vg values vary depending on the physical and chemical structures of probes. The values of all probes were found to decrease by increasing temperature as stated by Chen and coworker [43].

The Vg values of probes with PCPhDMA-co-St are higher than with PCPhDMA-co-AN. The greater retention volume of probes in PCPhDMA-co-St compared to PCPhDMA-co-AN might be attributed to larger surface of the styrene residues, which provide better interaction sites for probes and hence cause larger retention times in the column. The larger retention times observed for alcohols compared to with hydrocarbons in the both polymers may be ascribed to the possible hydrogen bonds. The graphics of 1/T versus lnVg0 which are determined from retention volumes of probes are important for observing temperature of glass transition state and polymer-solvent interactions.

The Tg values for PCPhDMA-co-St and PCPhDMA-co-AN were found to be around 363 K and 353 K respectively.

DHa and DH1 s values of PCPhDMA-co-St and PCPhDMA-co-AN were calculated from equation 4 and 5, respectively by plotting 1/T versus lnV 0.

Table-4 and 5 shows experimentally observed values of adsorption enthalpy, DHa, the molar sorption enthalpy, DH1 s, molar sorption free energy, DG1 s, and molar sorption entropy, DS1 s, respectively for PCPhDMA-co-St and PCPhDMA-co- AN polymer-probe systems. Sorption properties are calculated between 363-393 K temperatures for both polymer-probe systems where adsorption enthalpy, DHa, is calculated between 323-363 K for PCPhDMA-co-St and 323-353 K for PCPhDMA-co-AN-probe systems.

The endothermic adsorption enthalpy, DHa, values mean that probes do not interact with polymers in the range of adsorption temperatures. The calculated values of DH1 s, DG1s, and DS s according to Equations 5-7 are shown in Table 4 and 5 respectively for PCPhDMA-co-St and PCPhDMA-co-AN polymer-probe systems. The positive values of DH1 , DG1 , and the negative values of DS1 are compatible with previously published works about dioxolane ring containing polymer-probe systems [24, 43-45]. The exothermic molar sorption enthalpy and the negativity of molar sorption entropy are indicative of endothermic molar sorption free energy.

Table-2. Differing specific retention volumes, (V g (cm /g), of alchols and alkanes by temperature using PCPhDMA- co-St as stationary phase

T(K)/Probe EtOH 1-Propanol 1-Butanol Hexane###Heptane Octane Nonane

323###60.75###66.18###92.09###54.48###59.88###73.89 110.13

333###54.37###57.32###70.10###53.72###52.41###63.38 82.22

343###50.96###53.57###61.70###49.27###49.73###55.25 69.37

353###47.26###49.42###54.18###44.24###45.82###50.87 58.65

363###43.36###45.40###50.95###42.82###42.82###46.62 52.17

373###42.25###44.42###48.88###40.08###39.69###44.42 48.75

383###41.29###44.54###47.92###40.57###39.37###40.69 44.66

393###38.18###39.50###44.93###39.46###37.98###40.48 42.08

403###35.00###38.51###40.48###35.31###34.28###36.45 38.72

413###36.64###36.50###40.12###34.74###33.56###35.42 37.58

423###33.52###33.89###38.35###33.42###31.47###33.89 35.75

433###31.11###32.12###35.14###32.63###30.87###32.54 34.92

443###31.11###32.12###35.14###31.70###30.61###31.28 32.20

453###27.91###28.87###31.36###28.39###28.87###29.67 31.44

Table 3. Differing specific retention volumes, (V0g (cm3/g), of alchols and alkanes by temperature using PCPhDMA-co-AN as stationary phase

T(K)/Probe###EtOH 1-Propanol 1-Butanol Hexane Heptane Octane Nonane

###323###38,26###42,05###55,38###36,42 38,03###47,56 71,23

###333###33,89###37,33###45,18###32,60 35,50###41,53 55,83

###343###31,18###33,30###38,25###30,27 32,80###35,93 44,81

###353###30,15###31,19###32,69###28,65 30,34###32,78 38,33

###363###28,47###30,20###31,57###28,38 30,11###31,47 35,29

###373###27,18###28,64###30,35###26,67 27,70###29,67 32,33

###383###26,63###26,47###28,98###26,79 26,87###27,52 29,54

###393###25,44###25,74###28,45###25,36 24,76###25,66 26,87

###403###24,00###25,29###27,35###23,93 23,72###24,72 25,71

###413###23,18###24,86###24,92###25,93 22,51###23,51 24,45

###423###22,44###23,65###24,79###22,12 21,86###22,31 22,69

###433###22,04###22,70###24,16###22,34 21,43###21,92 22,89

###443###20,74###22,06###22,86###21,66 20,40###20,80 21,77

###453###19,99###20,70###21,29###19,45 19,13###19,78 20,10

Exothermic molar sorption enthalpy, (Eq.) alcohols and n-alkanes increases as the numbers of groups increase except for 1-butanol. Enhancing the chain lengths of alcohols may provide data to determine effects of increasing -CH2 groups on enthalpy change, which is the sorption process depending on interaction between the probe-polymer systems. The different numbers of -CH2 means different chemical nature and thus adding -CH2 group to probes is expected to make molar sorption enthalpies more exothermic. The results hint that the individual -CH2 groups have a significant interaction with PCPhDMA-co-St and PCPhDMA-co-AN regardless of the chemical natures of probes. The close values of enthalpy changes for alcohols and alkanes might suggest that there are dispersive forces between probes and polymers rather than dipole-dipole interactions.

Table-4: The partial molar sorption free energies, DG1s (kcal/mol), the partial molar sorption enthalpy, DH1s (kcal/mol), adsorption enthalpy DHa (kcal/mol) and sorption entropy, DS1s (kcal/mol) of PCPhDMA-co-St with selected alchols and alkanes systems

###DG1s###DH1s###DHa###DS1s

###(kcal/mol)

Probe/T(K)###363###373###383###393###363-393###323-363###363###373###383###393

###Ethanol###1.74###1.81###1.88###1.99###-1.14###7.00###-7.94###-7.91###-7.87###-7.95

1-Propanol###1.52###1.58###1.62###1.75###-1.16###6.92###-7.37###-7.33###-7.25###-7.41

1-Butanol###1.28###1.35###1.40###1.49###-1.12###6.27###-6.63###-6.63###-6.59###-6.64

###Hexane###1.30###1.39###1.41###1.47###-0.67###4.01###-5.42###-5.50###-5.43###-5.44

###Heptane###1.19###1.28###1.32###1.38###-1.05###5.44###-6.17###-6.24###-6.19###-6.19

###Octane###1.04###1.10###1.20###1.23###-1.45###5.71###-6.86###-6.84###-6.92###-6.83

###Nonane###0.87###0.95###1.04###1.11###-2.08###5.61###-8.12###-8.10###-8.13###-8.11

Table 5. The partial molar sorption free energies, DG1s (kcal/mol), the partial molar sorption enthalpy, DH1s (kcal/mol), adsorption enthalpy DHa (kcal/mol) and sorption entropy, DS1s (kcal/mol) of PCPhDMA-co-AN with selected alchols and alkanes systems

###DG1s###DH1s###DHa###DS1s

###(kcal/mol)

Probe/T(K)###363###373###383###393 363-393 323-353###363###373###383###393

###Ethanol###2.05###2.14###2.21###2.30 -1.02###7.32###-8.44###-8.46###-8.42###-8.45

1-Propanol###1.81###1.90###2.01###2.09 -1.59###7.94###-9.36###-9.35###-9.40###-9.35

1-Butanol###1.63###1.70###1.78###1.84 -1.02###6.40###-7.29###-7.30###-7.32###-7.29

###Hexane###1.60###1.69###1.73###1.82 -0.94###4.89###-7.00###-7.06###-6.98###-7.03

###Heptane###1.45###1.55###1.61###1.72 -1.75###6.59###-8.80###-8.84###-8.77###-8.82

###Octane###1.32###1.40###1.49###1.59 -1.95###6.55###-9.00###-8.97###-8.98###-8.99

###Nonane###1.15###1.25###1.35###1.46 -2.57###6.28###-10.27###-10.25###-10.25###-10.27

The weight fraction activity coefficient, [?], and Flory-Huggins interaction parameter are important for x 1 2 [?] defining solvent-polymer interactions. 1 and parameters could be calculated from equations 8 and 13, respectively (Table 6, 7). These values were calculated from 413 to 453 K for PCPhDMA-co-St and from 403 to 453 K for PCPhDMA-co-AN polymer-probe systems (Fig. 2,3). [?] values decrease as temperature increase. The weight fraction activity coefficient values are important at infinite dilution. There is a rule for determining solubility of polymer-solute systems. According to this rule probes are good solvent for values of 1 <5, moderate for 5< 1 10 [46]. Besides, there is a similar rule for values. For good solvents the values of are <0.5 while moderate solvents have a value of 0.5< <1 and poor solvents have greater values than 1 [47].

It should be noted that good solubility means that there are favorable interactions between molecules. In this case selected alcohols and alkanes are good solvents for PCPhDMA-co-St with exception of nonane at the 413 and 423 K temperatures. For the PCPhDMA-co-AN polymer ethanol, 1-propanol, hexane, heptane are good solvents while 1-butanol, octane and nonane could be solvent only at high temperatures. Table-6 shows that nonane is a solvent for polymer only at 453 K according to 1 values. The results indicate that ascending in the number of carbon decreases the solubility of the polymers and rising temperature enhances their solubility.

The current study has also produced data to determine the partial molar free energy of mixing, DG1, and partial molar heats of mixing, DH1 at infinite dilution of the solutes and polymer-probes systems from Equations 11 and 12 respectively. The results are shown at Table 8 and 9 for PCPhDMA-co-St and for PCPhDMA-co-AN, respectively. All of these parameters appear to be temperature dependent. DG1 values decrease with increasing temperature. The DH1[?] values of polymer-probe systems are calculated from the slopes of 1/T (K-1) versus Ln [?] (Fig. 2,3). The DH [?] values of PCPhDMA-co-St and PCPhDMA-co-AN-probe systems are changed from 5.26 to 8.53 kcal mol-1 and from 5.42 to 8.77 kcal mol-1. Molar evaporation enthalpy, DHv, values are calculated from Equation 3 and 17 and shown in Tables 8 and 9. As seen in the Tables 8 and 9 DHv values are changed from 5.92 to 9.89 kcal mol-1 for PCPhDMA-co-St and from 6.37 to 10.45 kcal mol-1.

Table-6: The weight fraction activity coefficients, [?] and Flory-Huggins interaction parameters, kh12 , of PCPhDMA- co-St with selected alcohols and alkenes systems.

###1 [?]###x 12 [?]

Probe/T(K)###413###423###433###443###453###413###423###433###443###453

Ethanol###1.84###1.45###1.16###0.95###0.84###-0.80###-1.04###-1.26###-1.46###-1.58

1-Propanol###2.52###2.06###1.58###1.31###1.15###-0.47###-0.68###-0.95###-1.14###-1.27

1-Butanol###3.61###2.80###2.22###1.77###1.54###-0.10###-0.36###-0.59###-0.82###-0.96

Hexane###1.24###1.06###0.90###0.77###0.73###-1.29###-1.45###-1.61###-1.76###-1.81

Heptane###2.28###1.94###1.60###1.32###1.16###-0.67###-0.83###-1.02###-1.21###-1.34

Octane###3.79###3.09###2.55###2.12###1.81###-0.15###-0.36###-0.56###-0.74###-0.90

Nonane###6.32###5.05###3.99###3.39###2.75###0.34###0.12###-0.12###-0.29###-0.50

Table-7: The weight fraction activity coefficients, 1[?] and Flory-Huggins interaction parameters, kh12[?], of PCPhDMA-co-AN with selected alcohols and alkenes systems.

###1 [?]###x 12 [?]

Probe/T(K) 403###413###423###433###443###453###403###413###423###433###443###453

###Ethanol 3.52###2.74###2.17###1.71###1.43###1.17###-0.14###-0.40###-0.64###-0.87###-1.05###-1.24

1-Propanol 4.89###3.71###2.95###2.37###1.9###1.6###0.20###-0.09###-0.32###-0.54###-0.76###-0.93

1-Butanol 7.29###5.81###4.33###3.35###2.71###2.27###0.61###0.38###0.08###-0.18###-0.39###-0.57

###Hexane###2.22###1.66###1.6###1.31###1.13###1.06###-0.71###-0.99###-1.03###-1.23###-1.38###-1.44

###Heptane 4.08###3.39###2.8###2.31###1.99###1.75###-0.08###-0.27###-0.46###-0.66###-0.81###-0.93

###Octane###7.07###5.71###4.7###3.78###3.19###2.71###0.48###0.26###0.06###-0.16###-0.33###-0.49

###Nonane###12.34###9.71###7.95###6.09###5.01###4.3###1.02###0.77###0.57###0.30###0.10###-0.05

Table-8: The partial molar free energies of mixing, DG1[?] (kcal/mol) and the partial molar enthalpy of mixing DH1[?] (kcal/mol), molar evaporation enthalpy, DHv (kcal/mol) of PCPhDMA-co-St with selected some alcohols and alkenes systems.

###DG1###DH1[?]###DHv*###DHv**

Probe/T(K)###413###423###433###443###453

Ethanol###0.50###0.31###0.13 -0.04###-0.16###7.76###8.89###9.26

1-Propanol###0.76###0.61###0.39 0.24###0.13###7.87###9.03###9.48

1-Butanol###1.05###0.87###0.69 0.50###0.39###8.53###9.65###10.21

Hexane###0.18###0.05###-0.09 -0.23###-0.28###5.26###5.92###6.81

Heptane###0.67###0.56###0.41 0.25###0.13###6.27###7.32###7.66

Octane###1.09###0.95###0.80 0.66###0.53###6.93###8.38###8.53

Nonane###1.51###1.36###1.19 1.07###0.91###7.82###9.89###9.38

Table 9. The partial molar free energies of mixing, DG1[?] (kcal/mol) and the partial molar enthalpy of mixing DH1[?] (kcal/mol), molar evaporation enthalpy, DHv (kcal/mol) of PCPhDMA-co-AN with selected some alcohols and alkenes systems

###DG1###DH1[?]###DHv*###DHv**

Probe/T(K)###403###413###423 433###443###453

Ethanol###1.01###0.83###0.65 0.46###0.31###0.14###7.97###8.98###9.28

1-Propanol###1.27###1.08###0.91 0.74###0.57###0.43###8.32###9.91###9.54

1-Butanol###1.59###1.44###1.23 1.04###0.88###0.74###8.77###9.79 10.28

Hexane###0.64###0.42###0.39 0.23###0.11###0.06###5.42###6.37###6.83

Heptane###1.13###1.00###0.86 0.72###0.6###0.50###6.30###8.05###7.69

Octane###1.57###1.43###1.3 1.14###1.02###0.90###7.09###9.04###8.57

In the Equation 18, the solubility parameter of a polymer, d2, can be determined by plotting d1 versus (d 2/RT)-((Eq.)/V ) (Fig. 4-5). The slope of this plot gives 2d2/RT while the intercept gives ( /RT). The values of solubility parameter of PCPhDMA-co-St are in the range of 7.3-7.9 (cal cm-3)0.5 from slope and 6.55-7.47 (cal cm-3)0.5 from intercept where same values for PCPhDMA-co-AN are in the range of 7.1-7.7 (cal cm-3)0.5 from slope and 6.51-7.52 (cal cm-3)0.5 from intercept (Table-10).

Table-10. The solubility parameters, d2 (cal/cm3)0.5 of PCPhDMA-co-St and PCPhDMA-co-AN between 413-453 and 403-453, respectively.

###T(K)###Slope Intercept###Cal. From slope,d2###Cal. From intercept, d2###r

###413###0.0193 -0.0681###7.919089###7.475625###0.9777

###423###0.0187 -0.0635###7.858684###7.305602###0.9742

PCPhDMA-###433###0.0181 -0.0590###7.786358###7.124738###0.9697

co-St###443###0.0173 -0.0534###7.614085###6.856010###0.9462

###453###0.0164 -0.0477###7.380910###6.552503###0.9362

###403###0.0192 -0.0706###7.687306###7.518891###0.9823

PCPhDMA-co-###413###0.0185 -0.0657###7.590837###7.342715###0.9778

###AN###423###0.0180 -0.0621###7.564509###7.224618###0.9765

###433###0.0174 -0.0572###7.485228###7.015214###0.9722

###443###0.0165 -0.0515###7.261988###6.732935###0.9508

###453###0.0159 -0.0471###7.155882###6.511162###0.9398

Conclusions

PCPhDMA-co-St and PCPhDMA-co-AN polymers were synthesized by free radical polymerization and characterized by FT-IR, and 1H-NMR spectral techniques. The monomer peaks, C=C bond in FT-IR and vinyl hydrogens in 1H-NMR spectra disappeared in polymers spectra. On the other hand, degradation of polymers was investigated by TGA where Tg and Mn, Mw values were obtained from DSC curves and GPC, respectively.

Besides the inverse gas chromatography is a simple, fast and economical technique for providing valuable thermodynamic and physical chemistry information of the polymeric materials. This technique was successfully applied to PCPhDMA-co-St and PCPhDMA- co-AN polymer-probe systems to determine their thermodynamic properties. In the study, the adsorption enthalpy, molar evaporation enthalpy, sorption enthalpy, sorption free energy, sorption entropy, Flory-Huggins interaction parameters, partial molar free energy of mixing, weight fraction activity coefficients, solubility parameter of polymer, and the partial molar heats of mixing at infinite dilution were also determined.

Supporting Information

Spectrums of 1H - NMR and FT-IR of monomer and copolymers, spectrums of average molecular weights, and plots of solubility parameters.

Acknowledgment

This project has been supported by Firat University Scientific Research Projects Unit (FUBAP) with number of 744.

References

1. H. Kamogawa, S. Okabe and M. Nanasawa, Synthesis of Polymerizable Acetals. I. Vinylbenzaldehyde Acetals with Perfume Alcohols, Bull Chem Soc Jpn., 49, 1917 (1976).

2. H. Kamogawa, Y. Haramoto and M. Nanasawa, Syntheses of Polymerizable Acetals. II. Readily Hydrolyzable Acetals from Citronellol and Vitamins, Bull Chem Soc Jpn, 52, 846 (1979).

3. E. Schacht, G. Desmarets and T. St. Pierre, Polymeric pesticides, 3. Synthesis and Characterization of Polyacetals Prepared from a,o-diols and 2,6- dichlorobenzaldehyde, Makromol. Chem., 179, 543 (1978).

4. E. Schacht, G. Desmarets and Y. Bogaert, Polymeric Pesticides, 4. Synthesis of Polyamides and a Polyester containing 2,6-dichlorobenzaldehyde, Makromol. Chem., 179, 837 (1978).

5. K. Oguchi, K. Sanui and N. Ogata, Relationship between Electron Sensitivity and Chemical Structures of Polymers as Electron Beam Resist. VII: Electron Sensitivity of Vinyl Polymers Containing Pendant 1,3- Dioxolan Groups, Polym Eng Sci., 30, 449 (1990).

6. N. A. A. Rossi, Y. Zou, M. D. Scott and J. N. Kizhakkedathu, RAFT Synthesis of Acrylic Copolymers Containing Poly(ethyleneglycol) and Dioxolane Functional Groups: Toward Well-Defined Aldehyde Containing Copolymers for Bioconjugation, Macromolecules, 41, 5272 (2008).

7. J. Britz, W. H. Meyer and G. Wegner, Blends of Poly(meth)acrylates with 2-Oxo-(1,3)dioxolane Side Chains and Lithium Salts as Lithium Ion Conductors. Macromolecules, 40, 7558 (2007).

8. S. Morariu, E. C. Buruiana and B. C. Simionescu, Free-Radical Ring-Opening Polymerization of 2-(o- chlorophenyl)-4-methylene-1,3-dioxolane. Polymer Bullettin January, 30, 1, 7 (1993).

9. T. Koizumi and H. Yutaka, Synthesis and Photodegradation of Polyacrylonitrile Having Ketone Group Obtained from Radical Copolymerization of 2,2-Diphenyl-4-Methylene-1,3-dioxolane with Acrylonitrile. J. of Poly. Sci.:Part A:Polym. Chem., 32, 3193 (1994).

10. P. Park, T. Y. Kozawa and T. Endo, Cationic Ring- Opening Polymerization of 2-isopropenyl-4- methylene-1,3-dioxolane. J. Polym Sci Part A: Polym Chem., 31, 1141 (1993).

11. C. Y. Pan and Z. Wu, Preparation and Polymerization of 2-phenyl-4-methylene-1,3-dioxolane, J Polym Sci Part C: Polym Lett., 25, 243 (1987).

12. J. C. Soutif, S. L. Ouchatar, D. Courret and J.-C. Brosse, Polymeres Porteurs De Derives Du Glycerol, 5. Derives de la progesterone, Makromol. Chem., 187, 561 (1986).

13. M. Coskun, Z. Ilter, E. Ozdemir, K. Demirelli and M. Ahmedzade, Synthesis, Characterization and Thermal Degradation of Poly [(2-Phenyl-1,3-Dioxolane-4- yl)Methylmethacrylate]. Polymer Degradation and Stability, 60, 185 (1998).

14. O. F. von Meien, E. C. Biscaia Jr and R. Nobrega, Polymer-Solute Diffusion and Equilibrium Parameters by Inverse Gas Chromatography. AIChE Journal, 43, 2932 (1997).

15. A. Voelkel, B. Strzemiecka, K. Adamska and K. Milczewska, Inverse Gas Chromatography as a Source of Physiochemical Data. Journal of Chromatography A, 1216, 1551 (2009).

16. G. DiPaola-Baranyi, Estimation of Polymer Solubility Parameters by Inverse Gas Chromatography, Macromolecules, 15, 622 (1982).

17. S. M. Pestov, V. A. Molotchkov and R. A. Lidine, Solubility of Liquid Crystals in Organic Solvents, Thermochim. Acta, 236, 131 (1994).

18. A. Voelkel and T. J. Kopczynski, Inverse Gas Chromatography in the Examination of Organic Compounds: Polarity and Solubility Parameters of Isoquinoline Derivatives, Chromatogr. A, 795, 349 (1998).

19. O. Planinsek and G. Buckton, Inverse Gas Chromatography: Considerations about Appropriate Use for Amorphous and Crystalline Powders, J. Pharm. Sci., 92, 1286 (2003).

20. M. Shyamala, S. Ranjan and J. V. C. Sharma, Pharmaceutical Applications of Inverse Gas Chromatography, International Journal of Pharma Sciences, 3, 201 (2013).

21. J. W. King and G. R. List, A Solution Thermodynamic Study of Soybean Oil/Solvent Systems by Inverse Gas Chromatography, J. Am. Oil Chem. Soc., 67, 424 (1990).

22. K. Srinivas, T. M. Potts and J. W. King, Characterization of Solvent Properties of Methyl Soyate by Inverse Gas Chromatography and Solubility Parameters, Green Chem., 11, 1581 (2009).

23. O. Smidsrod and J. E. Guillet, Study of Polymer- Solute Interactions by Gas Chromatography, Macromolecules, 2, 272, (1969).

24. Z. Ilter, I. Kaya and S. Ercan, Thermodynamic Properties of Poly(2-[3-(6-tetralino)-3-methyl-1- cyclobutyl]-2-hydroxy ethyl methacrylate) and Poly[2- (3-mesityl-3-methyl-1-cyclobutyl)-2-oxoethyl methacrylate). Journal of Macromolecular Science, Part A Pure and Applied Chemistry, 44, 21 (2007).

25. K. Milczewska and A. Voelkel, Characterization of the Interactions in Polymer-Filler Systems by Inverse Gas Chromatography. Journal of Chromatography A, 969, 255 (2002).

26. Z. Ilter, F. Alhanli, F. Dogan and I. Kaya, Synthesis and Characterization of an Acrylate Polymer Containing Chlorine-1,3-dioxolane Groups in Side Chains. Chinese Journal of Polymer Science, 30, 642 (2012).

27. C. Uriarte, M. J. Fdez Berridi, J. M. Elorza and J. J. Iruin, Determination of the Interaction Parameter g by Inverse Gas Chromatography: an Additional Experimental Test of the Classic Lattice Model, Polymer, 30, 1493 (1989).

28. G. J. Price, J. E. Guillet and J. H. Purnell, Measurement of Solubility Parameters by Gas-Liquid Chromatography, J. Chromatography A, 369, 273 (1986).

29. R. C. Reid and T. K. Sherwood, The Properties of Gases and Liquids, 2nd Ed.; McGraw Hill, New York, (1966).

30. R. C. Reid, J. M. Prausnit and T. K. Sherwood, The Properties of Gases and Liquids, 3rd Ed.; McGraw- Hill Book Comp., New York, (1977).

31. J. M. Braun and J. E. Guillet, Determination of Crystallinity by Gas Chromatography. Effect of Curvilinearity of Retention Diagrams, Macromolecules, 10, 101 (1977).

32. G. DiPaola-Baranyi and J. E. Guillet, Estimation of Polymer Solubility Parameters by Gas Chromatography, Macromolecules, 11, 228 (1978).

33. M. Galin and L. Maslinco, Gas-Liquid Chromatography Study of poly(vinylidene fluoride)- Solvent Interactions. Correlation Analysis of the Partial Molar Enthalpy of Mixing with Probe Polarity, Macromolecules, 18, 2192 (1985).

34. I. Kaya, Z. Ilter and D. Senol, Thermodynamic Interactions and Characterization of poly(glycidyl methacrylate-co-methyl, ethyl, butyl)methacrylate by Inverse Gas Chromatography. Polymer, 24, 6455 (2002).

35. A. Dasgupta, E. R. Santee and H. J. Harwood, Arylsulfone Derivatives of Polystyrene. J. Macromol. Sci.-Chem., 23, 87 (1986).

36. I. Kaya, K. Demirelli and M. Coskun, 3,4- dichlorobenzyl methacrylate and ethyl methacrylate system: Monomer Reactivity Ratios and Determination of Thermodynamic Properties at Infinite Dilution by Using Inverse Gas Chromatography. Polymer, 42, 5181 (2001).

37. D. H. Grant and N. Grassie, The Thermal Decomposition of poly(t-butyl methacrylate), Polymer, 1, 445 (1960).

38. N. Grassie and I. C. McNeill, Thermal Degradation of Polymethacrylonitrile. Part V. The Mechanism of the Initiation Step in Coloration Reactions, J. Polym. Sci., 39, 211 (1959).

39. R. T. Conley and J. F. Biernon, Examination of the Oxidative Degradation of Polyacrylonitrile Using Infrared Spectroscopy, J. Appl. Polym. Sci., 7, 1757 (1963).

40. H. S. Fochler, J. R. Money, L. E. Ball, R. D. Bayer and J. G. Graselli, Infrared and NMR Spectroscopic Studies of the Thermal Degradation of Polyacrylonitrile, Spectrochim Acta A, 41, 271 (1985).

41. J. J. Rafalco, Fourier-Transform Infrared Studies of the Thermal Degradation of Isotopically Labeled Polyacrylonitriles, J Polym Sci Polym Phys Ed, 22, 1211 (1984).

42. T. Usami, T. Itoh, H. Othani and S. Tsuge, Structural Study of Polyacrylonitrile Fibers During Oxidative Thermal Degradation by Pyrolysis-Gas Chromatography, Solid-State Carbon-13 NMR, and Fourier-Transform Infrared Spectroscopy, Macromolecules, 23, 2460 (1990).

43. Y. Chen, Q. Wang, Z. Zhang and J. Tang, Determination of the Solubility Parameter of Ionic Liquid 1-Hexyl-3-methylimidazolium Hexafluorophosphate by Inverse Gas Chromatography. Ind. Eng. Chem. Res., 51, 15293 (2012).

44. Z. Ilter, I. Kaya and A. Acikses, Determination of Thermodynamic Properties of poly[(2-phenyl-1,3- dioxolane-4-yl) Metyl Methacrylate] by Inverse Gas Chromatography. Journal of Polymer Engineering, 22, 1, 45 (2002).

45. Z. Ilter, I. Kaya and A. Acikses, Determination of poly[(2-phenyl-1,3- dioxolane-4-yl) methyl methacrylate-co-glycidyl methacrylate)]-probe Interactions by Inverse Gas Chromatography. Polymer-Plastics Technology Engineering, 43, 229 (2004).

46. J. E. Guillet, J. H. Purnel, Advances in Analytical Chemistry and In Strumentation, in: Gas Chromatography, Wiley, New York, (1973).

47. J. Klein and H. E. Jeberien, Chainlength Dependence of Thermodynamic Properties of poly(ethylene glycol). Macromol. Chem. and Phys., 181, 1237 (1980).
COPYRIGHT 2016 Asianet-Pakistan
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2016 Gale, Cengage Learning. All rights reserved.

Article Details
Printer friendly Cite/link Email Feedback
Author:Ilter, Zulfiye; Oncu, Ilbey; Karagoz, M. Hamdi; Ercan, Selami; Alhanli, Ferhat
Publication:Journal of the Chemical Society of Pakistan
Article Type:Report
Date:Aug 31, 2016
Words:6895
Previous Article:Synthesis and Enzyme Inhibitory Studies of Some New N-Alkylated/Aralkylated N-(4-Ethoxyphenyl)-2,3-dihydrobenzo-[1,4]-dioxin-6-sulfonamides.
Next Article:Global Trends of Electrodialysis Research during 1991-2014: a Bibliometric Analysis.
Topics:

Terms of use | Privacy policy | Copyright © 2021 Farlex, Inc. | Feedback | For webmasters