Siloxane Oligomers with Epoxy Pendant Groups

Siloxane Oligomers with Epoxy Pendant Groups

Omari Mukbaniani,2 Jimsher Aneli,2 Izabela Esartia,1,2 Tamar Tatrishvili,1,2 Eliza Markarashvili,1,2

Natia Jalagonia2

Summary: Hydrosilylation reaction of 2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasiloxane

with allyl glycidyl ether at 1:4.1 molar ratios of initial compounds in the presence of platinum

hydrochloric acid (0.1 M solution in THF), Karstedt’s catalyst (Pt2[(VinSiMe2)2O]3) and platinum on

the carbon have been studied and 2.4.6.8-tetrapropyl glycidyl-2.4.6.8-tetramethylcyclotetrasilox-

ane has been obtained. For hydrosilylation reaction order, rate constants and activation energy

have been determined in the presence of Karstedt’s catalyst. Ring–opening polymerization

reaction of D4R in the presence of catalytic amount of powder-like potassium hydroxide has been

carried out. Linear methylsiloxane oligomer with regular arrangement of propyl glycidyl groups in

the side chain has been obtained. The reaction of epoxy group containing compounds with

primary and secondary amines has been carried out and corresponding amino hydroxyl groups

containing compounds have been obtained. The synthesized organosiloxanes were studied by

FTIR, 1H, 13C and 29Si NMR spectroscopies. Comb-type oligomers were characterized by size-

exclusion chromatography, wide-angle X-ray methods. Via sol-gel processes of 2.4.6.8-tetrapropyl

glycidyl-2.4.6.8-tetramethylcycltetrasiloxane, ethylene diamine and tetraethoxysilane doped with

lithium trifluoromethylsulfonate (triflate) or lithium bis(trifluoromethylsulfonyl)imide solid

polymer electrolyte membranes have been obtained. The dependence of ionic conductivity as a

function of temperature and salt concentration has been studied. It is shown that the

conductivity of membrane containing 15 wt % of triflate type salt concentration is higher on the 3

orders than analogous containing the same amount of the salt lithium bis(trifluoromethylsul-

fonyl)imide. The difference is described in terms of ion mobilities in the polymer matrix.

Keywords: cross-linking; hydrosilylation; membranes; polymer electrolyte; polysiloxanes

Introduction

Polysiloxanes attract the widest interest among theinorganic backbone polymers. The reason lies inproperties of polysiloxanes such as strong heatresistance, elastomeric behavior, biocompatibility,thermal-, UV- and oxidative stabilities, low surfaceenergy, good weatherability, low melting points andglass transition temperatures, convenient rheologicalproperties and outstanding electrical properties.[1–3]

Epoxides are used in a wide range of fieldsincluding coatings, printed circuit boards, compo-sites, adhesives and civil engineering. In all casesepoxies bring adhesion, corrosion resistance,chemical and heat resistance and excellent me-chanical and physical properties to the system. Theproperties of organosilicon polymers depend on

the structure of macromolecular chains and on thenature of organic groups surrounding the siliconatom.[4] In comb-type copolymers there aredifferent sizes and nature organic substituentgroups bonded to the methylsiloxane hydrophobicmatrix. A wide range of variation of thesesubstituent groups is possible. Some siliconorganiccopolymers contain donor groups and exhibitcomplexing properties.[5–7]

The polysiloxanes with very low glass transitiontemperatures, Tg ¼ �123 �C for poly(dimethylsi-loxane) and extremely high free volumes andthermo-oxidative stability [8,9] are expected to begood hosts for Liþ transport when polar units areintroduced onto the polymer backbone.

A poly(methylhydroxysiloxane) (PMHS) ma-trix is commonly used for solid polymer electro-lytes based on organosilicon polymers. Vinyl-orhydroxyl-containing methylorganosiloxanes withdifferent donor groups in the side chain areobtained via hydrosilylation or dehydrocondensa-tion reactions of this matrix.

1 Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave.1, 0179 Tbilisi, GeorgiaE-mail: [email protected]

2 Institute of Macromolecular Chemistry and Polymeric Materi-als, Iv. Javakhishvili Tbilisi State, Georgia

Macromol. Symp. 2013, 328, 25–37 DOI: 10.1002/masy.201350603 | 25

Copyright � 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com

This method of obtaining comb-type methyl-siloxane oligomers, however, is not recommendedbecause the reactions requires a long time,replacement of the silane hydrogens does notreach complete conversion, and various linkingsystems are obtained. Furthermore during reac-tion often branching and cross linking processestake place.

In accordance with scientific literature dataconnected with polyelectrolytes it is known thatthe dependence of conductivity s (s ¼ 1/r, wherer is specific volumetric resistance of materials) ofthese materials on the temperature in coordinateslogs–1/T may be described by two types ofequations: as a rule – either equation of Arrheniusor one known as Vogel-Tammann-Fulcher(VTF).[10] Applications of these dependences tothe real polyelectrolytes conductivity depends onthe character of design of microstructure andmobility of ions – charged particles transfer inthese materials.

In some investigations the dependence of thelogarithm of conductivity on the inverse tempera-ture shows a slight curvature and, accordingly, adeviation from strict Arrhenius dependence.These results may be described by the VTFequation:

s ¼ s0 � exp BT � TVF

� �

which is based on the migration mechanismdeveloped in.[11]

Experimental Part

2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasi-loxane (DH

4 ) (Aldrich), platinum hydrochloric acid(Aldrich), Karstedt’s catalyst (Pt2[(VinSi-Me2)2O]3) or platinum(0)-1,3-divinyl-1,1,3,3-tetra-methyldisiloxane complex (2% solution in xylene)(Aldrich), platinum hydrochloric acid (Aldrich),Pt/C (10%) (Aldrich), allyl acetoacetate (Aldrich),hexamethyldisiloxane (Aldrich) and vinyltriethox-ysilane were used as received. Lithium trifluor-omethylsulfonate (triflate) and lithium bis(trifluoromethylsulfonyl)imide were purchasedfrom (Aldrich). Toluene was dried over anddistilled from sodium under an atmosphere ofdry nitrogen. Tetrahydrofuran (THF) was driedover and distilled from K–Na alloy under anatmosphere of dry nitrogen. 0.1 M solution ofplatinum hydrochloric acid in THF was preparedand kept under nitrogen at low temperature.

Characterization

FTIR spectra were recorded on a Nicolet Nexus470 machine with MCTB detector. 1H, 13C NMRand 29Si NMR spectra were recorded on a VarianMercury 300VXNMR spectrometer, usingDMSOand CCl4 (or CDCl3) as the solvent and an internalstandard. Gel-permeation chromatographic inves-tigation was carried out with the use of WatersModel 6000A chromatograph with an R 401differential refractometer detector. The columnset comprised 103 and 104 Å Ultrastyragelcolumns. Sample concentration was approximate-ly 3% by weight in toluene and typical injectionvolume for the siloxane was 5 mL and the flow rate– was1.0 ml/min., calibration of the GPC withstyrene or polydimethylsiloxane standards.

Wide-angle X-ray analyses were performed ona Dron-2 (Burevestnik, Saint Petersburg, Russia)instrument. A-CuKa was measured without afilter; the angular velocity v of the motor wasabout 2�/min.

Hydrosilylation Reaction of DH4 with

Allyl glycidyl ether in the Presence ofPlatinum hydrochloric acid

DH4 (1.5000 g, 6.237 mmol) was transferred into a

50 ml flask under nitrogen using standard Schlenktechniques. High vacuum was applied to the flaskfor half an hour before the addition of allyl glycidylether (2.9014 g, 0.02619 mol). The mixture wasthen dissolved in 3 ml of toluene, and 0.1 Msolution of platinum hydrochloric acid in tetrahy-drofuran (5�9 · 10�5 g per 1.0 g of startingsubstance) was added and placed into an oil bath,which was previously set to 50 �C and reactioncontinued at 50 �C. The extend of reaction wascontrolled by decrease of intensity of active�Si-Hgroups. After disappearance of �Si-H groups0.1% activated carbon was added and refluxed for12 h for deactivation of catalysts.

All volatile products were removed by rotaryevaporation and the polymeric compound wasprecipitated at least three times into pentane toremove side products. Finally, all volatiles wereremoved under vacuum and further evacuatedunder high vacuum for 24 h to isolate the colorlessviscous product I - DEp

4 , 4.1 g (95%).For compound I the calculated values in %:

C – 48.24, H – 8.11, Si – 16.12; M ¼ 697; forC28H56Si4O12 it was found values, %: C – 48.02,H – 7.98, Si – 16.25, M ¼ 685.

Macromol. Symp. 2013, 328, 25–3726 |

Copyright � 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ms-journal.de

The same hydrosilylation reactions in thepresence of Karstedt’s catalyst have been carriedout in the same manner.

Ring-Opening Copolymerization Reactionof D

Ep4 and Hexamethyldisiloxane

The 1.1365 g (1.4046 mmol) of compound I and0.0284 g (0.1756 mmol) hexamethyldisiloxanewere transferred into a 25 ml flask under drynitrogen. High vacuum was applied to the flask forhalf an hour. Then the compound was dissolved in1.8 ml dry toluene and 0.01% of total masspowdered potassium hydroxide was added. Themixture was degassed and placed in an oil bath,which was previously set to 60 �C, and polymer-ized under nitrogen for 25 h. After the reaction,7 ml of toluene were added to the mixture and theproduct was washed with water. The crude productwas stirred with MgSO4 for 6 h, filtered andevaporated, and the oligomer was precipitated atleast three times into pentane to remove sideproducts. Finally, all volatiles were removed undervacuum to isolate 1.0 g (86%) colorless viscousoligomers Dn

Ep (II). Co-polymerization reactionat different values m, respectively n, of thecomposition was carried out by the same method.

Addition of Benzyl amine to DEp4

In a three-necked flask equipped with a refluxcondenser and calcium chloride tube, droppingfunnel and mechanical stirrer the solution of1.0000 g (0.0014 mol) of compound I DEp

4 in 3 mlof toluene anhydrous solution and 0.6139 g(0.0057 mol) benzyl amine were refluxed underargon, until disappearance of epoxy resonancessignals at d ¼ 2.7 and d ¼ 3.1 ppm in the 1H NMRspectra. Then the solvent and excess amine wereremoved in vacuum at 80 �C to give 1.5 g (95%)the product III.

The addition of benzyl amine with oligomer II(DEp

n ) was carried out according to the above-mentioned method.

Addition of Diethyl amine to DEp4

The reaction was carried out in a three-neckedflask equipped with a reflux condenser and calciumchloride tube, dropping funnel and mechanicalstirrer. The solution of 1.0000 g (1.4345 mmol) of

compound I - DEp4 in 3 ml of toluene anhydrous

solution and 0.4220 g (5.7381 mmol) diethyl aminewere refluxed under argon, until disappearance ofepoxy resonances at d ¼ 2.7 and d ¼ 3.1 ppm inthe 1H NMR spectra. Then the solvent and excessamine were removed in vacuum at 80 �C to give1.3 g (96%) the product V.

The addition of diethyl amine with oligomer IIwas carried out according to the above-mentionedmethod.

The Reaction of Hydrogen Bromidewith Compound V

The reaction was carried out in a three-neckedflask equippedwith a reflux condenser and calciumchloride tube, dropping funnel and mechanicalstirrer. To the solution of 1.1000 g (1.1114 mmol)of compound V, 0.4512 g (5.570 mmol) diethylamino hydroxyl siloxane in 10 ml anhydrous toluenesolution 0.3145 g (3,89 mmol) (48%) hydrogenbromide was added in 3 ml water at 0 �C tempera-ture range. From water solution 1.44 g (93%)transparent vitreous product VII was received.

The reaction of compound VI with hydrogenbromide was carried out by the same method.

General Procedure for Preparation ofCross-Linked Polymer Electrolytes

1.0000 g (0.0014 mol) of compound I and 0.1721 g(0.0028 mmol) of ethylene diamines were dis-solved in 4 ml of dry THF and thoroughly mixedfor half an hour before the addition catalyticamount of acid (one drop of 0.1 N HCl solution inethyl alcohol) to initiate the cross-linking process.After stirring for another 3 h the required amountof lithium triflate from the previously preparedstock solution in THF was added to the mixtureand stirring continued for 1 h. The mixture wasthen poured into a Teflon mould with a diameterof 4 cm, and solvent was allowed to evaporateslowly overnight. Finally, the membrane was driedin an oven at 70 �C for 3 d and at 100 �C for 1 h.Homogeneous and transparent film with averagethickness of 200 mm were obtained in this way.These film were insoluble in all solvents, onlyswollen in THF.

Ac Impedance Measurements

The total ionic conductivity of samples wasdetermined by positioning an electrolyte disk

Macromol. Symp. 2013, 328, 25–37 | 27


between two 10 mm diameter brass electrodes.The electrode/electrolyte assembly was secured ina suitable constant volume support which allowedextremely reproducible measurements of conduc-tivity to be obtained between repeated heating-cooling cycles. The cell support was placed in anoven and the sample temperature was measuredby a thermocouple close to the electrolyte disk.The bulk conductivities of the electrolytes wereobtained during a heating cycle using the imped-ance technique (Impedance meter BM 507–TESLA for frequencies 50 Hz-500 kHz) over atemperature range between 20 and 100 �C.

Results and Discussion

In this work we present a new approach to thesynthesis of linear organosilicon oligomers withpropyl glycidyl side groups. The hydrosilylationreaction of DH

4 with allyl glycidyl ether was carriedout in the presence of platinum catalysts:(Pt2[(VinSiMe2)2O]3), platinum hydrochloricacid (0.1 M solution in THF) and platinum onthe carbon. The progress of the conversion ofactive �Si-H groups was followed by the disap-pearance of the �Si-H absorption at 2165 cm�1.Kinetic parameters of the hydrosilylation reactionshave been studied in dry toluene solution atC ¼ 0.1272 mol/l concentration. The hydrosilyla-tion reaction of DH

4 with allyl glycidyl etherproceeds according to the following Scheme 1:

Where at 50� (I), 40� (I1) and 30 �C (I2).The synthesized compound I - DEp

4 afterremoval of solvents is a colourless or light yellowliquid transparent product well soluble in commonorganic solvents.

In the FTIR spectra of DEp4 the absorption

bands at 850, 910 and 3483 cm�1 are characteristic

of epoxy groups, the absorption band at 1095 cm�1

corresponds to asymmetric valence oscillation of�Si-O-Si� bond in cyclotetrasiloxane fragment.The absorption bands in the range 2860–2931 cm�1, are typical for valence oscillations ofthe CH bonds in CH2 groups in ethylene bridges.Absorption bands at 1265 cm�1 are characteristicof �Si-Me bonds.

In 29Si NMR spectra of compound I there is adoublet centred d ¼ �19.73 and �19.80 ppmchemical shift indicating D (-R2SiO-) bonds inisomeric cyclotetrasiloxane fragment.

In the 1H NMR spectra of compound I(Figure 1) the singlet at d ¼ 0.05 ppm indicatesthe methyl protons of the silicon. The multipletcentred at d ¼ 0.5 ppm shows the protons of the�Si-CH2- fragment (anti-Markovnikov addition),the multiplet centred at d ¼ 1.0 ppm are themethyl protons in CH3-CH¼ fragments (Markov-nikov addition). The multiplets at d ¼ 1.5, 2.6, 3.0,3.25, 3.40 and 3.70 ppm are characteristic ofprotons in methylene and methin groups in-CH2- CH2-CH2O, -CH(O)CH2 (oxirane ring),CHOCH2 (oxirane ring), -CH2-CH2-CH2O andfor -O-CH2- CH(O)CH2 fragment accordingly.

The signals at d¼-1.07 ppm in 13CNMR spectraof compound I are characteristic of carbon inmethyl groups d ¼ 12.52, 22.56, 42.94, 49.77, 70.83,72.76 ppm represent the carbon in �Si-CH2-,-CH2-CH2-CH2O-, -CH(O)CH2 (oxirane ring),CHOCH2 (oxirane ring), -CH2-CH2-CH2O- andfor O-CH2-CH(O)CH2- fragment accordingly(Figure 2).

During hydrosilylation reaction of DH4 with

allyl glycidyl ether in dry toluene solution(C¼ 0.1272 mole/l), activation energies and rateconstants have been determined for hydrosilyla-tion reactions of DH

4 with allyl glycidyl ether in thepresence of Karstedt’s catalyst.

Scheme 1.

Hydrosilylation reaction of DH4 with allyl glycidyl ether.

Macromol. Symp. 2013, 328, 25–3728 |


In Figure 3 the changes of the concentration ofactive �Si-H groups with time during hydro-silylation reactions of DH

4 with allyl glycidyl etherin the presence of Karstedt’s catalysts is presented.From Figure 3 it is evident that all active �Si-Hgroups participate in hydrosilylation reaction.

As it is seen from Figure 3 hydrosilylatioinreaction of DH

4 with allyl glycidyl ether in thepresence of platinium hydrochloric acid proceedswith the same rate as in the presence of Karstedt’scatalyst. With an increase of temperature thereaction rate rises. Figure 4 demonstrates thedependence of the inverse concentration of �Si-H

groups on time during hydrosilylation reaction ofDH

4 with allyl glycidyl ether at various temper-atures. The reaction curves shows that the hydro-silylation reaction at initial stages is of a secondorder. The reaction rate constants of hydrideaddition reactions of DH

4 with allyl glycidyl ether atvarious temperatures were determined: k30 �C¼ 0.9657, k40 �C ¼ 1.1917 and k50 �C ¼ 1.4826mol · l�1 · min�1.

From the dependence of the logarithm of rateconstants on the reciprocal temperature theactivation energy of hydrosilylation reaction wascalculated (E ¼ 17.9 kJ/mol).

Figure 1.1H NMR spectra of compound I.

Figure 2.13C NMR spectra of compound I.

Macromol. Symp. 2013, 328, 25–37 | 29


The ring opening co-oligomerization reactionproduct I was carried out using potassium hydrox-ide and terminated with hexamethyldisiloxane (atvarious ratio of initial compounds) in dilutesolution of dry toluene and inert atmosphere.

In the presence of powdered anhydrouspotassium hydroxide 0.01% of the total massand at temperatures 60–70 �C, oligomerizationreactions follow Scheme 2:

Where at (n:m): 4:0.8 molar ratios, 60 �C – II, at4:0.5 molar ratios, 60 �C – II1 and at 4:0.4 molarratios, 60 �C – II2.

It was established that ring-opening oligomeri-zation in the presence of potassium hydroxideproceeds during 48–64 h. The optimal condition ofoligomerization reaction has been determined andit was established that the oligomerization

Figure 3.

Time-dependence of the concentration of active �Si-H groups reaction time during hydrosilylation reactions of DH4

with allyl glycidyl ether in the presence of Karstedt’s catalysts at 50 �C (1), 40 �C (2), 30 �C (3) and platinum hydrochloric acid at

30 �C (4).

Figure 4.

Dependence of reciprocal concentration of �Si-H groups on

the time during hydrosilylation reaction of DH4 with allyl

glycidyl ether in toluene solution in the presence of Karstdet’s

catalyst at 30 �C (B), 40 �C (C) and 50 �C (D).

Scheme 2.

Ring-opening oligomerization of D4R in the presence of potassium hydroxide.

Macromol. Symp. 2013, 328, 25–3730 |


reactions proceeds better in solution than in meltcondition, in temperature range 60–70 �C. Theobtained oligomers with oxirane rings in the sidechain are liquid, colorless (or light yellow)transparent products, well soluble in ordinaryorganic solvents with hsp ¼ 0.06–0.08. Structureand compositions of the obtained oligomers wereestablished on the basis of elemental analysis,FTIR and 1H, 13C and 29Si NMR spectral data.Some properties of linear epoxides are presentedin Table 1.

In the FTIR spectra of oligomer II one can seethat the absorption bands at 864, 910 and3471 cm�1 characteristic of oxirane rings ispreserved, the absorption band at 1095 cm�1

corresponds to asymmetric valence oscillation ofthe�Si-O-Si� fragment. In 29Si NMR spectrum ofthe oligomer II the signals with chemical shifts atd ¼ �19.72 and �21.99 ppm characterizing for

linear siloxane bonds and 10.1 ppm for Me3SiOare observed.

On Figure 5 the 1H NMR spectrum of oligomerII is presented. In the spectrum one can observethe same signals as in 1H NMR spectrum ofcompound I. In the 1HNMR spectrum of oligomerII the singlet signals for methyl protons intrimethylsiloxy group with chemical shift d¼0.05ppm, for methyl group at d¼0.01 ppm areobserved. The multiplets at d¼0.49; 1.0; 1.50;3.0, 3.30, 3.4, 3.70; 2.5, 2.7; 2.38, 2.63 ppm arecharacteristic of protons in -C6H2-, CH3-CH¼(Markovnikov addition), -C5H2-, C3H2, -C4H2,-C2H and -C1H2 groups, accordingly.

In the 13C NMR spectrum of oligomer IIFigure 6 one can observe the signals with chemicalshifts at �1.01 ppm (C7); 12.44 ppm (C6);22.53 ppm (C5); 72.76 ppm (C4); 70.84 ppm(C3); 49.84 ppm (C2) and 42.93 ppm (C1).

Table 1.Some physical-chemical characterization of cyclic and linear epoxy compounds

# Yield, % Reaction Temperature, �C Molar ratio, n:m M Epoxy�, % hsp��

n m Found Calculated Found Calculated

I 95 50 1 4.2 685 697 24.68 24.71 –I1 95 40 1 4.2 – – 24.62 24.71 –I2 93 30 1 4.2 – – 24.64 24.71 –II 86 60 4 0.8 3710 3642 23.58 23.61 0.08II1 85 60 4 0.5 – 5730 23.96 24.01 0.07II2 82 60 4 0.4 7300 7122 24.00 24.15 0.06

�Epoxy groups were determined according to the literature data.[12]�� In 1% toluene solution at 25 �C.

Figure 5.1H NMR spectra of oligomer II.

Macromol. Symp. 2013, 328, 25–37 | 31


GPC analysis of oligomers has been carried outand it was shown that oligomer II and II1 havemonomodal molecular weight distribution. Theoligomers are characterized with a low value ofdispersity. The dispersity of oligomers is aboutD ¼ 1,1–1.2 and the average molecular masses arein the range of Mn ¼ 3:710� 7:30� 103 andMw ¼ 4:081� 8:760� 103. Epoxy group contain-ing compounds I and II reacted with primary andsecondary amines. The reactions were carried outin 10% solution of dry toluene. The reactionmixture was heated up to the boiling point of

toluene for 12 h. The completion of the reactionwas confirmed on the basis of 1H NMR spectra bythe disappearance of the resonance signalscharacteristic of epoxy groups at d ¼ 2.7 andd ¼ 3.1 ppm in the 1H NMR spectra. The ring-opening reaction of epoxy group of DEp

4 andcompound II (Dn

Ep) with primary benzyl amineproceeds according to the following Scheme 3:

Where: in case of DEp4 (III), �DEp

n � (IV).The same reactions of DEp

4 and linear com-pound II (DEp

n ) with diethyl amine proceedsaccording to the following Scheme 4:

Figure 6.13C NMR spectra of oligomer II.

Scheme 3.

Ring-opening reaction of epoxy group with benzyl amine.

Scheme 4.

Ring-opening reaction of epoxy group with diethyl amine.

Macromol. Symp. 2013, 328, 25–3732 |


Where: in case of DEp4 (V), �DEp

n � (VI).The composition of liquid tertiary amino

hydroxyl siloxanes cyclic (III, V) and linear (IV,VI) structure was established by means ofelementary analysis, by finding of molecularmasses by FTIR and NMR spectra data (seeTable 2).

In COSY (homonuclear) NMR spectra oflinear siloxanes with amino hydroxyl side groups(Figure 7) one can observe resonance signals withchemical shift 0.1–0.15 ppm for methyl protons at

silicon in 7 position for III and IV and fortrimethylsiloxy end group for oligomer IV. Thereare observed the multiplet resonance signals withthe centre of chemical shifts d ¼ 0.5, 1.5, 2.2, 2.9–3.6 ppm for protons in methylene group, andsignal for hydroxyl group at 3.9 ppm.

In COSY NMR spectra of compound V(Figure 8) one can observe singlet signals formethyl protons at silicon with chemical shiftd0.1 ppm, resonance m-signals with centre ofchemical shifts d0.5, 1.5 and 3.4 corresponds to

Table 2.Some physical-chemical characterization of cyclic and linear compounds

# Yield, % hsp� M�� d1, A Elementary composition, %

NCalc NExp

III 95 – 11241150

– 4.98 4.83

IV 94 0.10 57825800

7.12 4.84 4.70

V 96 – 9881024

– 5.67 5.41

VI 95 0.11 5102� 7.09 5.49 5.22

VII 93 – 13121300

– 4.27 4.11

VIII 94 0.11 6722� 7.14 4.17 4.09

�Molecular masses have been determined via ebullioscopic method (in numerator calculated values andin denominator found values).�� In 1% toluene solution at 25 �C.

Figure 7.

Homonuclear COSY NMR spectra of oligomer IV.

Macromol. Symp. 2013, 328, 25–37 | 33


methylene protons at 6, 5 and 4 position. Tripletsignal at d1.0 ppm corresponds to methyl pro-tons in ethyl group.

For the obtained organosiloxanes wide angle X-ray investigation have been carried out. It wasshown that oligomers are represented as single-phase amorphous systems with value of interchaindistances d1 in the range – 7.09–7.14 Å.

For the purpose of synthesis of organosiliconquaternary ammonium salts the reaction ofhydrogen bromide with amino hydroxyl organo-siloxanes has been investigated. The reaction wascarried out in the dilute dry toluene solution, at0 �C temperature to prevent the break of �Si-O-Si� backbone. Equimolar amounts of hydrogen

bromide reacted with amino hydroxyl compounds(V, VI) with formation of quaternary ammoniumsalts according to the following Scheme 5:

Where: in case of D4Am

– R ¼ R’ ¼ C2H5

(VII), -DnAm - R ¼ R’ ¼ C2H5 (VIII).

The obtained salts are glass type, transparentcolorless products, well soluble in water. Bydetermination of molecular masses it was shownthat, during formation of quaternary ammoniumsalts under the given conditions, scission of thesiloxane backbone does not takes place. In 1HNMRspectra of compoundsVII andVIII (Figure 9and 10) one can see resonance singlet signals formethyl protons of the CH3-groups at silicon atomd0.1–0.13 ppm, multiplet signals for protons in

Figure 8.

Homonuclear COSY NMR spectra of oligomer V.

Scheme 5.

The reaction of hydrogen bromide with amino hydroxyl compounds (V, VI).

Macromol. Symp. 2013, 328, 25–3734 |


methylene groups with chemical shifts at d 0.5,1.3–1.7, 3.2 and 3.6 ppm (6-1position and inNCH2CH3 group). The comparison of chemicalshifts for N-CH2 - groups in tertiary andquaternary amino hydroxyl siloxanes shows asignificant shift in low field for quaternarycompounds.

To obtain membrane the reaction of compoundI with ethylene diamine was investigated and solidtransparent yellow film IX has been obtained.

Via sol-gel processes of compound I, ethylenediamine with tetraethoxysilane doped with lithiumsalts: lithium-trifluoromethylsulfonate (triflate) -S1 or lithium bis(trifluoromethylsulfonyl)imide -S2, polymer electrolyte membranes have beenobtained according to the Scheme 6:

The dependence of ionic conductivity s of thepolyelectrolyte membranes as a function oftemperature and salt concentration in polymericmatrix was investigated.

In Figure 11 Arrhenius plots of the dependenceof electrical conductivity of polymer electrolytemembranes containing the salts S1 and S2 withdifferent contents are presented. Analysis of thecurves of Figure 11 leads to opinion that first of allthey are described satisfactorily by the equationanalogical to well known Vogel-Tammann-Fulcher (VTF) that describes the temperaturedependence of the bulk viscosity. The curves showan increasing conductivity with increasing saltconcentration and temperature. Assuming that theelectrolyte concentration (¼salt concentration) isequal to the electrolyte activity, it could be

Figure 9.

Homonuclear COSY NMR spectra of compound VII.

Figure 10.1H NMR spectra of oligomer VIII.

Macromol. Symp. 2013, 328, 25–37 | 35


expected that the conductivity increases withincreasing concentration.

The diversity of values of the conductivity forthe membranes containing 5 and 15 wt% of salt S1at 30 �C differ from one another up to three ordersof magnitude (Table 3). This effect can beexplained by an effective involvement of the saltconstituents in the charge transfer due to a goodsolubility and dissociation of the salt in thepolymer matrix and a high ion mobility.

Membranes containing salt S2 show a similarconcentration dependence of the conductivity onthe salt concentration. The mobility of the S2–ions,however, is lower compared with the mobility ofthe S1–ions and the conductivity of the membranescontaining S2 consequently is also lower.

The values of the conductivities for thesemembranes are presented in the Table 3.

Comparison of the polyelectrolyte membranesfrom oligomers with epoxy groups in the side chainwith analogous membranes described by otherauthors [7–11] shows that the transport of electricalcharges in our membranes is constrained atrelative low temperatures by a rather densenetwork structure.

Conclusion

New epoxy containing organocyclotetrasiloxanehave been synthesized via hydrosilylation reactionof tetrahydrotetramethylcyclotetrasiloxane withallyl glycidyl ether in the presence of platinumcatalysts. By ring-opening reactions of epoxygroups with primary and secondary aminescorresponding amino hydroxyl derivatives havebeen obtained. Via sol-gel processes of aminohydroxyl compounds doped with lithium trifluor-omethylsulfonate (triflate) or lithium bis

Scheme 6.

Synthesis of solid polymer electrolyte membranes.

2,8 2,9 3,0 3,1 3,2 3,3 3,4

-12

-11

-10

-9

-8

-7

-6

B C D E F G

lgσ

, S/c

m

1000/T,1/K

Figure 11.

Arrhenius plot of the dependence of electrical conductivity of

polymer electrolyte membranes containing salt S1 with

concentrations 5 (F), 10 (G) 15 wt% (C) and salt S2 with

concentrations 5 (B), 15 (E), 20 wt% (D).

Table 3.Conductivity of polymer elecytrolyte membranes on the basis of polymer P containing the salts S1 and S2.

No Salt Content of salt, wt % s (30 �C), S/cm s(90 �C), S/cm1 S1 5 4.1 � 10�10 1.3 � 10�7

2 S1 10 6.4 � 10�10 3.1 � 10�7

3 S1 15 2.0 � 10�7 1.6 � 10�6

4 S2 5 1.6 � 10�11 7.9 � 10�10

5 S2 15 5.2 � 10�11 4.1 � 10�9

6 S2 20 1.6 � 10�10 3.2 � 10�8

Macromol. Symp. 2013, 328, 25–3736 |


(trifluoromethylsulfonyl)imide solid polymer elec-trolyte membranes have been obtained.

The dependence of the conductivity obeys theformula of Vogel, Tammann and Fulcher (VTF).Some membranes containing the Li-triflat salt arecharacterized by a significantly higher conductivitythan those containing lithium bis(trifluoromethyl-sulfonyl)imide with the same concentrationsbecause of the relatively higher mobility of thetriflat anions compared to the bis(trifluoromethyl-sulfonyl)imide anions.

Acknowledgment: The financial support of the GeorgianNational Science Foundation Grant #STCU 5055 isgratefully acknowledged.

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