Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies
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1 Moleules 2010, 15, ; doi: /moleules Artile PEN ACCESS moleules ISSN Synthesis nd Chrteriztion of rgnotin Contining Copolymers: Retivity Rtio Studies Slem S. Al-Deyb, Ali Mohsen Al-Hzmi nd Mohmed H. El-Newehy * Petrohemil Reserh Chir, Chemistry Deprtment, College of Siene, King Sud University, Riydh 11451, P.. Box 2455, Sudi Arbi; E-Mils: ssdeyb@ksu.edu.s (S.S.A.); petrohem@ksu.edu.s (A.M.A.) Author to whom orrespondene should be ddressed; E-Mil: mnewehy@hotmil.om (M.H.E.) Tel.: Reeived: 25 Jnury 2010; in revised form: 20 Februry 2010 / Aepted: 8 Mrh 2010 / Published: 12 Mrh 2010 Abstrt: rgnotin monomers ontining dibutyltin groups dibutyltin itronte (DBTC) s new monomer nd dibutyltin mlete (DBTM) were synthesized. Free rdil opolymeriztions of the orgnotin monomers with styrene (ST) nd butyl rylte (BA) were performed. The overll onversion ws kept low ( 15% wt/wt) for ll studied smples nd the opolymers omposition ws determined from tin nlysis using the Gillmn nd Rosenberg method. The retivity rtios were lulted from the opolymer omposition using the Finemn-Ross (FR) method. The synthesized monomers were hrterized by elementl nlysis, 1 H-, 13 C-NMR nd FTIR spetrosopy. Keywords: orgnotin monomers; itronte; mlete; styrene; butyl rylte; retivity rtio 1. Introdution Copolymeriztion is one of the most importnt mens to improve the performne of polymers. Copolymers re extensively used in industril proesses, beuse their physil properties, suh s elstiity, permebility, glss trnsition temperture (T g ) nd solvent diffusion kinetis n be vried within wide limits [1,2]. Knowledge of opolymer s omposition is n importnt ftor in the evlution of its utility [3,4]. Controlling the polymer property prmeters, suh s opolymer
2 Moleules 2010, omposition, opolymer sequene distribution nd moleulr weight verges, is of prtiulr importne in opolymeriztion proesses. This is beuse opolymer density nd visosity, whih re two of the most importnt property mesures used by polymer mnufturers, depend on these prmeters [5]. Retivity rtios re mong the most importnt prmeters for the omposition eqution of opolymers, whih n offer informtion suh s the reltive retivity of monomer pirs nd help estimte the opolymer omposition [3]. To lulte the polymeriztion rte or polymer produtivity nd opolymer omposition, monomer retivity rtios must be known. The method whih is used most often nowdys for estimting monomer retivity rtios is to perform low onversion opolymeriztion t vrious initil monomers feed ompositions. Subsequently, the opolymer omposition is determined for eh retion [5]. Retivity rtio vlues my be evluted by vrious proedures: liner proedures, nonliner proedures, nd other opolymer omposition equtions [6 9]. rgnotin derivtives of ompound ontining biotive lkyltin groups hve onsiderble interest s bioides [10]. rgnotin ompounds hve importnt pplitions in severl res nd hene they re mde industrilly on lrge sle [11]. The orgnotin moiety is tthed to the monomers nd opolymers vi - nd/or N- bonds [10 15]. Aryli opolymers with pendnt orgnotin moieties find widespred pplitions s ntifouling gents, [10,16] wood preservtives, [10] fungiides, pestiides, mosquito lrvides, [10,17] het nd light stbilizers in the mnufture of poly(vinyl hloride). [10] nd biologil tivities ginst vrious speies [10,18]. The present rtile investigtes the synthesis, nd struturl hrteriztion of opolymers of dibutyltin itronte (DBTC), nd dibutyltin mlete (DBTM), with styrene (ST) nd butyl rylte (BA) s well s the retivity rtios in the opolymeriztion. For this purpose, retivity rtios for the lssil opolymeriztion model were determined using the lineriztion methods of Finemnn Ross (FR method) [19]. 2. Results nd Disussion 2.1. Synthesis of rgnotin Monomers rgnotin monomers, (I) nd (II), were prepred by the retion of dibutyltin oxide (DBT) with mlei nhydride or itroni nhydride in equimoleulr rtio s shown in Shemes 1 nd 2. Sheme 1. Synthesis of dibutyl mlete (DTBM, I). Dibutyltin oxide (DBT) + Mlei nhydride Benzene Reflux Dibutyltin mlete (DBTM) ( I )
3 Moleules 2010, Sheme 2. Synthesis of dibutyltin itronte (DBTC, II) Dibutyltin oxide (DBT) + Citroni nhydride Benzene Reflux Dibutyltin itronte (DBTC) (II) The strutures were eluidted by elementl nlysis, FTIR, 1 H nd 13 C-NMR spetrosopy. In ddition, the purity of the prepred monomers ws heked by Thin Lyer Chromtogrphy (TLC) using ethyl ette/ylohexne (2:1). Generlly, elementl mironlyses, s shown in Tble 1, re in good greement with the lulted vlues. Tble 1. Elementl mironlysis of synthesized monomers I nd II. Monomer Dibutyltin Mlete (DBTM, I) Cl. Found %C %H % %C %H %* I II * ws estimted using the Gilmn nd Rosenberg method [20]. The FT-IR spetrum of dibutyltin mlete (DBTM, I) showed hrteristi peks t: 2,854, 2,868, 2,926, nd 2,958 m -1 ssigned to C-H strething (-CH 2 CH 2 CH 2 CH 3, nd -CH=CH-), 1,615 m -1 ssigned to C= strething nd 1,582 m -1 ssigned to C=C strething. The 1 H-NMR spetrum (CDCl 3 ) showed peks t δ 0.86 (triplet, -CH 2 CH 2 CH 2 CH 3 ), δ (multiplet, - CH 2 CH 2 CH 2 CH 3 ), δ 1.65 (multiplet, -CH 2 CH 2 CH 2 CH 3 ), δ 1.74 (triplet, -CH 2 CH 2 CH 2 CH 3 ), δ 6.22 (singlet, -CH=CH-). The 13 C-NMR spetrum (CDCl 3 ) showed peks t δ 13.60, 25.79, 26.54, (-CH 2 CH 2 CH 2 CH 3 ), δ (-CH=CH-), δ (-C=) Dibutyltin Citronte (DBTC, II) The FT-IR spetrum of dibutyltin itroonte (DBTC, II) showed peks t: 2,857, 2,868, 2,927, nd 2,956 m -1 ssigned to C-H strething (-CH 2 CH 2 CH 2 CH 3, & -CH=CH-), 1,610 nd 1,667 m -1 ssigned to C= strething, 1,561 m -1 ssigned to C=C strething. The 1 H-NMR spetrum showed peks t δ 0.80 (triplet, -CH 2 CH 2 CH 2 CH 3 ), δ 1.26 (multiplet, -CH 2 CH 2 CH 2 CH 3 ), δ 1.59 (multiplet, -CH 2 CH 2 CH 2 CH 3 ), δ 1.61 (triplet, -CH 2 CH 2 CH 2 CH 3 ), δ 1.96 (singlet, -CH=C-CH 3 ), δ 5.77 (singlet, -CH=C-CH 3 ). The 13 C-NMR spetrum showed peks t δ 13.59, 25.46, 26.62, (- CH 2 CH 2 CH 2 CH 3 ), δ (-CH=C-CH 3 ), δ (-CH=C-CH 3 ), δ (-CH=C-CH 3 ), δ (- CH=CCH 3 -C=), δ (-C-CH=C-CH 3 ).
4 Moleules 2010, Copolymeriztion Method Copolymeriztion of DBTM or DBTC with styrene (ST) nd butyl rylte (BA) ws done in solution using benzoyl peroxide s inititor vi the free rdil tehnique (Shemes 3 nd 4). Sheme 3. Copolymeriztion of DBTM with ST nd BA. Styrene (ST) x y Dibutyltin mlete (DBTM) ( I ) 1% BP Benzene Butyl rylte (BA) Poly((DBTM-o-ST) ( III ) x y Poly((DBTM-o-BA) ( IV ) Sheme 4. Copolymeriztion of DBTC with ST nd BA. Styrene (ST) x y Dibutyltin itronte (DBTC) ( II ) 1% BP Benzene Butyl rylte (BA) Poly((DBTC-o-ST) ( V ) x y Poly((DBTC-o-BA) ( VI ) Copolymeriztion ws done t 70 ºC in benzene with totl onentrtion of 2 mol/l t different time intervls. The formed opolymer ws preipitted in n exess mount (20 fold), of the orresponding solvent, nd ws purified by wshing with exess preipittion solvent or by repreipittion from benzene, hloroform, or etone, depending on the type of opolymer. All
5 Moleules 2010, smples were dried in n oven under vuum t ºC. Different opolymers with different rtios were prepred nd the perentge of tin ws determined in eh smple [20] (Tble 2). Tble 2. Tin perentge of opolymers (III-VI) with different rtios. Copolymer Rtio % III IV b V VI d 80/ / / / / DBTM/ST; b DBTM/BA; DBTC/ST; d DBTC/BA 2.3. verll Conversion nd Struturl Chrteriztion The im of the opolymeriztion ws to study the opolymeriztion behvior of the monomers DBTM nd DBTC, with ST nd BA. The overll onversion of monomers to poly(dbtm-o-st) (III), poly(dbtm-o-ba) (IV), poly(dbtc-o-st) (V) nd poly(dbtc-o-ba) (VI), fter 2 h, ws found to be 4.09, 34.01%, 4.52 nd 24.93%, respetively. After 8 h, the overll onversion of monomers to (III), (IV), (V) nd (VI) ws found to be 13.89, 36.8%, nd 38.40%, respetively. So the opolymeriztion of DBTM or DBTC with BA showed the highest overll onversion, ompred to ST. Bsed on the perentge of tin (Tble 3), the opolymer omposition showed tht the ontent of DBTM in (III) is higher thn in (IV) nd the opolymer omposition showed tht the ontent of DBTC in (V) is lower thn in (VI) fter 4 h [21]. Copolymer ode Tble 3. Copolymers omposition fter 4 h. % Moles of DBTM DBTC ST BA III IV V VI Copolymer Composition. F The struturl hrteriztions of (III), (IV), (V) nd (VI) were done by FTIR nd 1 H-NMR spetrosopy. The FTIR spetrum of (III), (IV), (V) nd (VI) with overll onversion fter 8 hrs of 13.89, 36.80, nd 38.40%, respetively, ws hrterized by the dispperne of C=C strething bnds t 1,582 nd 1,610 1,640 m -1 of DBTM or DBTC with ST or BA, respetively whih onfirm the formtion of the opolymer. Generlly, the FTIR spetrum showed peks t 1,452, 1,492, 1,583, nd 1,601 m -1 ssigned to C=C strething of the romti ring of ST [8]. The FTIR spetrum lso showed peks t 3,024, 3,058, nd 3,080 m -1 ssigned to C-H strething of the romti ring, nd peks t 2,848, 2872, 2931, 2,914, nd 2957m -1 ssigned to liphti C-H strething. n the other hnd, the FTIR showed hrteristi peks t 1,605 nd 1,736 m -1 ssigned to C= strething of DBTM nd BA, respetively.
6 Moleules 2010, The 1 H-NMR spetrum of (III) nd (IV) ws hrterized by the dispperne of peks t δ ppm (-CH=CH- nd CH 2 =CH-) or (-CH=CCH 3 - nd CH 2 =CH-) of DBTM or DBTC with ST or BA, respetively, whih onfirm the formtion of the opolymer. The 1 H-NMR spetrum of (III) ws hrterized by the pperne of peks t δ ppm (-CH 2 CH 2 CH 2 CH 3, -CH 2 -CPh-, nd -CH-CH-), nd t δ ppm (H rom ). The 1 H-NMR spetrum of (IV) ws hrterized by the pperne of peks t δ ppm (-CH 2 CH 2 CH 2 CH 3, -CCH 2 CH 2 CH 2 CH 3, -CH-CHC-) nd t δ 4.03 ppm (-CH-CH-, -CH- CHC-). The 1 H-NMR spetrum of (V) ws hrterized by the pperne of peks t δ ppm (-CH 2 CH 2 CH 2 CH 3, -CH 2 -C-C-, nd -CH-CHCH 3 -), nd t δ ppm (H rom ). The 1 H-NMR spetrum of (VI) ws hrterized by the pperne of peks t δ ppm (-CH 2 CH 2 CH 2 CH 3, -CCH 2 CH 2 CH 2 CH 3, -CH-CHC-, -CH-CHCH 3 -) nd t δ 4.01 ppm (-CH- CHCH 3 -, -CH-CHC-) Retivity Rtio Determintion Poly(DBTM-o-ST) (III) Poly(DBTM-o-ST) (III) ws prepred using different rtios of DBTM nd ST with BP s inititor nd the polymeriztion ws stopped t n overll onversion 15 wt/wt%. The opolymer ws preipitted in exess methnol. The perentge of tin ws lulted ording to the Gilmn nd Rosenberg method [20], nd subsequently the opolymer omposition (f) ws determined s shown in (Tble 4). The monomers retivity rtios nd the ontent of the retion mixture nd the opolymer ws lulted ording to the FR method [22 24] (Tble 5). The FR prmeters for DBTM nd ST (Tble 6) were lulted by plotting the reltion between F(f-1)/f nd F 2 /f. From the vlues of the experimentl retivity rtio, r 1 (k 11 /k 12 ) is smller thn r 2 (k 22 /k 21 ), it is evident tht monomer DBTM (r 1 = 0.099) is less retive towrds the ddition of its units ompred to the ddition of ST units. n the other hnd, the route of ST (r 2 = ) is more retive towrds the ddition of its units ompred to the ddition of DBTM units. As r 1 r 2 < 1, so the opolymer tends to rndom distribution of its monomer units [15] Poly(DBTM-o-BA) (IV) Poly(DBTM-o-BA) (IV) ws prepred using different rtios of DBTM nd BA with BP s inititor nd the polymeriztion ws stopped t n overll onversion 15 wt/wt%. The opolymer ws preipitted in exess methnol nd ws purified by repreipittion in hloroform. The perentge of tin ws lulted ording to the Gilmn nd Rosenberg method [20], nd subsequently the opolymer omposition (f) ws determined s shown in Tble 7. The monomers retivity rtios nd the ontent of the retion mixture nd the opolymer ws lulted ording to FR method [12 14] (Tble 8). The FR prmeters for DBTM nd BA (Tble 6) were lulted by plotting the reltion between F(f-1)/f nd F 2 /f. From the vlues of the experimentl retivity rtio, r 1 (k 11 /k 12 ) is smller thn r 2 (k 22 /k 21 ), it is evident tht monomer DBTM (r 1 = ) is less retive towrds the ddition of its units ompred to the ddition of BA units. n the other hnd, the route of BA (r 2 = ) is more
7 Moleules 2010, retive towrds the ddition of its units ompred to the ddition of DBTM units. As r 1 < 1 nd r 2 > 1, so the opolymer will ontin bloks of BA with low rndom units of DBTM due to the high retivity of BA with its high retivity rtio ompred to DBTM [25]. Moreover, s r 1 r 2 < 1, so the opolymer tends to rndom distribution of its monomer units. Tble 4. The prmeters of poly(dbtm-o-st) (III) omposition. Copolymer Rtio % M 1 F b m 1 f d Conversion (wt/wt%) e 20/ / / / / Mole frtion of DBTM in retion mixture; b Molr rtio of DBTM to ST in retion mixture; Mole frtion of DBTM in opolymer; d Molr rtio of DBTM to ST in opolymer; e verll onversion. Tble 5. The monomer retivity rtios nd the FR prmeters of poly(dbtm-o-st) (III). Copolymer Rtio Monomer Rtio F = M 1 /M 2 M-Unit Rtio in Copolymer Prmeters of FR Eq. F 2 /f F/f(f-1) 20/ / / / / Tble 6. Experimentl retivity rtios ording to the FR method. Copolymer r 1 (k 11 /k 12 ) r 2 (k 21 /k 22 ) b r 1 r 2 III IV V VI Retivity Rtio of DBTM or DBTC; b Retivity Rtio of vinyl monomers (ST nd BA) Poly(DBTC-o-ST) (V) Poly(DBTC-o-ST) (V) ws prepred using different rtios of DBTC nd ST using BP s inititor nd the opolymeriztion ws stopped t overll onversion 15 wt/wt%. The opolymer ws preipitted in exess methnol. The perentge of tin ws lulted ording to the Gilmn nd Rosenberg method [20], nd subsequently the opolymer omposition (f) ws determined (Tble 9). The monomers retivity rtios nd the ontent of the retion mixture nd the opolymer ws lulted ording to FR method [22 24] (Tble 10). The FR prmeters for DBTC nd ST (Tble 6) were lulted by plotting the reltion between F(f-1)/f nd F 2 /f. From the vlues of the experimentl retivity rtio, r 1 (k 11 /k 12 ) is smller thn r 2 (k 22 /k 21 ), it is evident tht the monomer ST prefers the ddition of its units ompred to the ddition of DBTC
8 Moleules 2010, units. As r 1 < 1 nd r 2 > 1, so the opolymer will ontin bloks of ST with low rndom units of DBTC due to the high retivity of ST with its high retivity rtio ompred to DBTC [25]. Finlly, when r 1 < 1, the opolymeriztion is preferred nd when r 2 > 1, ST will tend to homopolymeriztions. Tble 7. The prmeters of poly(dbtm-o-ba) (IV) omposition. Copolymer Rtio % M 1 F b m 1 F d Conversion (wt/wt%) f 20/ / / / / Mole frtion of DBTM in retion mixture; b Molr rtio of DBTM to BA in retion mixture; Mole frtion of DBTM in opolymer; d Molr rtio of DBTM to BA in opolymer; f verll onversion. Tble 8. The monomers retivity rtios nd the FR prmeters of poly(dbtm-o-ba) (IV). Copolymer Rtio Monomer Rtio F = M 1 /M 2 M-Unit Rtio in Copolymer Prmeters of FR Eq. F 2 /f F/f(f-1) 20/ / / / / Tble 9. The prmeters of poly(dbtc-o-st) (V) omposition. Copolymer Rtio % M 1 F b m 1 F d Conversion (wt/wt%) e 20/ / / / / Mole frtion of DBTC in retion mixture; b Molr rtio of DBTC to ST in retion mixture; Mole frtion of DBTC in opolymer; d Molr rtio of DBTC to ST in opolymer; e verll onversion Poly(DBTC-o-BA) (VI) Poly(DBTC-o-BA) (VI) ws prepred using different rtios of DBTC nd BA using BP s inititor nd the polymeriztion ws stopped t overll onversion 15 wt/wt%. The opolymer ws preipitted in exess methnol nd ws purified by repreipittion from etone. The perentge of Tin ws lulted ording to Gilmn nd Rosenberg method [20], nd subsequently the opolymer omposition (f) ws determined s shown in (Tble 11). The monomers retivity rtios nd the
9 Moleules 2010, ontent of the retion mixture nd the opolymer ws lulted ording to FR method [22 24] (Tble 12). The FR prmeters for DBTC nd BA (Tble 6) were lulted by plotting the reltion between F(f-1)/f nd F 2 /f. From the vlues of the experimentl retivity rtio, r 1 (k 11 /k 12 ) is smller thn r 2 (k 22 /k 21 ), it is evident tht monomer DBTC (r 1 = ) is less retive towrds the ddition of its units ompred to the ddition of BA units. n the other hnd, the route of BA (r 2 = ) is more retive towrds the ddition of its units ompred to the ddition of DBTC units. As r 1 < 1 nd r 2 > 1, so the opolymer will ontin bloks of BA with low rndom units of DBTC due to the high retivity of BA with its high retivity rtio ompred to DBTC [25]. Moreover, when r 1 < 1, the opolymeriztion is preferred nd when r 2 > 1, BA will tend to homopolymeriztion. Tble 10. The monomers retivity rtios nd the FR prmeters of poly(dbtc-o-st) (V). Copolymer Rtio Monomer Rtio F = M 1 /M 2 M-Unit Rtio in Copolymer Prmeters of FR Eq. F 2 /f F/f(f-1) 20/ / / / / Tble 11. The prmeters of poly(dbtc-o-ba) (VI) omposition. Copolymer Rtio % M 1 F b m 1 f d Conversion (wt/wt%) e 20/ / / / / Mole frtion of DBTC in retion mixture; b Molr rtio of DBTC to BA in retion mixture; Mole frtion of DBTC in opolymer; d Molr rtio of DBTC to BA in opolymer; f verll onversion. Tble 12. The monomer retivity rtios nd the FR prmeters of poly(dbtc-o-ba) (VI). Copolymer Rtio Monomer Rtio M-Unit Rtio Prmeters of FR Eq. F = M1/M2 in Copolymer F2/f F/f(f-1) 20/ / / / /
10 Moleules 2010, Experimentl 3.1. Mterils Dibutyltin (IV) oxide ws purhsed from Sigm-Aldrih. Citroni nhydride nd styrene (ST) were purhsed from Fluk. Mlei nhydride 99% nd benzoyl peroxide (BP) were purhsed from BDH. Butyl rylte nd 2, 2 -zobisisobutyronitrile (AIBN) were purhsed from Riedel-de-Hen. All solvents were purhsed from BDH nd were used s reeived Chrteriztion 1 H- nd 13 C-NMR Spetr were reorded on Jeol (400 MHz) instrument. FTIR Spetr were reorded on Perkin Elmer 883. Elementl nlyses were performed t Perkin Elmer Series II CHN/ Anlyzer Thin-lyer hromtogrphy (TLC) ws performed using the sending tehnique with sili gel 60F 254 preoted luminum sheets Synthesis of rgnotin Monomers Synthesis of Dibutyltin Mlete (DBTM, I) In 500 ml round bottom flsk, mlei nhydride (4.90 g, 50.0 mmol) ws dded to dibutyltin oxide (12.44 g, 50.0 mmol) in dry benzene (170 ml). The mixture ws heted under gentle reflux for 9 h. The formed preipitte ws removed by filtrtion, nd the solvent ws totlly evported on rotvpor to give n oily residue. The oily residue ws dissolved in diethyl ether (100 ml) under gentle heting with stirring. The solution ws filtered nd the filtrte ws onentrted to one third its volume on rotvpor. The solution ws ooled to room temperture nd then ws kept in freezer (-10 ºC) for 72 h to give white preipitte. The formed preipitte ws filtered, rerystllized from diethyl ether [26] nd ws dried under vuum t 40 ºC for 24 h to give g, 58.8% yield nd m.p ºC. The produt I ws hrterized by elementl nlysis (Tble 1), FTIR nd 1 H- nd 13 C NMR spetrosopy Synthesis of Dibutyltin Citronte (DBTC, II) The dibutyltin itronte (DBTC, II) ws prepred s desribed erlier for DBTM (I) using the following quntities nd onditions: dibutyltin oxide (12.44 g, 50.0 mmol), itroni nhydride (5.60 g, 50.0 mmol) in dry benzene (170 ml) for 10 hrs. The produt II ws rerystllized from n- hexne nd ws dried under vuum t 40 ºC for 24 h to give 9.10 g, 50.4% yield nd m.p ºC. The produt II ws hrterized by elementl nlysis (Tble 1), FTIR nd 1 H- nd 13 C- NMR spetrosopy Generl Proedure for Copolymeriztion Copolymeriztions were rried out in three nek round bottomed flsk. Copolymeriztion ws done in solution by dissolving benzoyl peroxide (BP) (1% mol) in 2 ml of the orresponding solvent, nd then the lulted molr quntities of the monomers were dded. The retion mixture
11 Moleules 2010, ws bubbled with nitrogen to expel oxygen. Copolymeriztion ws done t 70 ºC for the desired period of time. The formed opolymer ws preipitted in exess mount (20 fold), of the orresponding solvent. All smples were dried in oven under vuum t ºC. For retivity rtio determintion, the opolymeriztion ws stopped t overll onversion below 15% wt/wt [25] from the totl weight of both monomers by hnging the time of polymeriztion verll Conversion The overll onversion in opolymeriztion [25,27,28] of monomers DBTM nd DBTC with ST nd BA ws studied by tking fixed number of moles (20 mmol), nd omposition of 20% mol of monomer DBTM or DBTC nd 80% mol of ST nd BA, in benzene with totl onentrtion of 2 mol/l t different time intervls. The overll onversion by weight (wt/wt%) ws determined using Eqution (1): verll onversion by weight (wt/wt%) 3.6. Retivity Rtios Determintion weight of the opolymer = X 100 (1) Totl weight of strted monomers For retivity rtio determintion, opolymeriztions were performed with different initil feed rtios while mintining the monomer onversion below 15%. The Finemn Ross (FR) method ws employed. The inititor onentrtion ws kept t 1% reltive to the totl monomers onentrtion in benzene. Monomer retivity rtios n be lulted from the experimentl results depending on the opolymer omposition. Copolymer omposition n be expressed s following; f 1 = m 1 /m 2 nd f 2 = m 2 /m 1 Where m 1 & m 2 re the mole frtions of DBTM or DBTC nd vinyl monomer in the opolymer, respetively, nd f 1 & f 2 re its molr rtios in the opolymer. Moreover, the feed omposition of the retion mixture is known in dvne, so feed omposition ws used in the lultions of the retivity rtios nd n be expressed s follows: F 1 = M 1 /M 2 nd F 2 = M 2 /M 1 where M 1 & M 2 re the mole frtions of DBTM or DBTC nd vinyl monomer in the retion mixture, respetively, nd F 1 & F 2 re its Molr rtios in the feed omposition. In this reserh, the lultions were bsed on the tin ontent in the opolymer omposition [29]. The Finemn Ross (FR) [30] method is bsed on the use of opolymer omposition nd the ontent of the polymeriztion mixture. Bsed on the lultions of the opolymer omposition nd feed omposition nd ording to eqution (2): F(f-1) f r F 2 = 1 - r 2 (2) f
12 Moleules 2010, A plot of (F 2 /f) on X-xis vs {F/f(f-1)} on Y-xis gve stright line, the interept is r 2 nd the slope is r Conlusions The orgnotin monomers dibutyltin itronte (DBTC) s new monomer, nd dibutyltin mlete (DBTM), were synthesized. The orgnotin monomers were opolymerized with styrene (ST) nd butyl rylte (BA) using free rdil tehnique. The overll onversion ws kept low ( 15% wt/wt) for ll studied smples nd the opolymers omposition ws determined from tin nlysis. From the vlues of the experimentl retivity rtio, r 1 (k 11 /k 12 ) is smller thn r 2 (k 22 /k 21 ), it is evident tht poly(dbtmo-st) (III), poly(dbtm-o-ba) (IV) tend to rndom distribution of its monomer units s r 1 r 2 < 1. For poly(dbtc-o-st) (V), r 1 < 1 nd r 2 > 1, so the opolymer will ontin bloks of ST with low rndom units of DBTC due to the high retivity of ST with its high retivity rtio ompred to DBTC. For poly(dbtc-o-ba) (VI), r 1 < 1 nd r 2 > 1, so the opolymer will ontin bloks of BA with low rndom units of DBTC due to the high retivity of BA with its high retivity rtio ompred to DBTC. Referenes 1. Liu, G.; Zhng, L.; Wng, Y.; Zho, P. Studies on binry opolymeriztion nd glss trnsition tempertures of methyl methrylte with ethyl methrylte nd n-butyl methrylte. J. Appl. Polym. Si. 2009, 114, Sby-Dubreuil, A.C.; Guerrier, B.; Allin, C. Glss trnsition indued by solvent desorption for sttistil MMA/nBMA opolymers-influene of opolymer omposition. Polymer 2001, 42, Erol, I.; Sen,.; Dedelioglu, A.; Cifi, C. Synthesis nd hrteriztion of novel fluorineontining methrylte opolymers: Retivity rtios, therml properties, nd ntimirobil tivity. J. Appl. Polym. Si. 2009, 114, Hou, C.; Liu, J.; Ji, C.; Ying, L.; Sun, H.; Wng, C. Monomer pprent retivity rtios for rylonitrile/methyl vinyl ketone opolymeriztion system. J. Appl. Polym. Si. 2006, 102, Hbibi, A.; Frhni, E.V.; Semsrzdeh, M.A.; Sdghini, K. Monomer retivity rtios for luryl methrylte-isobutyl methrylte in bulk free rdil opolymeriztion. Polym. Int. 2003, 52, Hou, C.; Ji, C.; Ying, L. Monomer pprent retivity rtios for rylonitrile/mmonium itonte rdil opolymeriztion systems. J. Appl. Polym. Si. 2007, 103, Miller, A.; Szfko, J.; Tursk, E. Retivity rtios for rylonitrile-vinyl hloroette opolymeriztion systems. J. Polym. Si. 1977, 15, Bjj, P.; Sen, K.; Hjir, B.S. Solution polymeriztion of rylonitrile with vinyl ids in dimethylformmide. J. Appl. Polym. Si. 1996, 59, Soykn, C.; Coskun, M.; Ahmedzde, M. Synthesis nd hrteriztion of phenyl methrylte - rylonitrile opolymers nd determintion of monomer retivity rtios. Polym. Int. 2000, 49,
13 Moleules 2010, Al-Muikel, N.S.; Al-Dib, S.S.; Al-Slmh, A.A.; Zid, A.M.A. Synthesis nd hrteriztion of novel orgnotin monomers nd opolymers nd their ntibteril tivity. J. Appl. Polym. Si. 2000, 77, Rehmn, S-ur.; Shhid, K.; Ali, S.; Mzhr, M.; Bdshh, A.; Eng, G.; Song, X.; Ryzkowski, J. Synthesis, spetrosopi hrteriztion, nd in vitro biologil tivity of orgnotin(iv) omplexes of (E)-3-(4-methoxyphenyl)-2-phenyl-2-propenoi id. Heter. Chem. 2005, 16, Grg, B.K.; Corredor, J.; Subrmnin, R.V. Copolymeriztion of Tri-n-butyltin Arylte nd Trin-butyltin Methrylte Monomers with Vinyl Monomers Contining Funtionl Groups. J. Mromol. Si. Prt A: Pure Appl. Chem. 1977, 11, Al-Dib, S.S. Synthesis of novel orgnotin opolymers. J. Chem. Res. 1986, (S), Gin, C.; Gin, V. Synthesis nd hrteriztion of novel orgnotin rboxylte mleimide monomers nd polymers. express Polym. Lett. 2009, 3, Twfik, S.Y.; Messih, N.N.; El-Hmouly, S.H. Effet of substitution on the retivity of some new p-phenylrylmide derivtives with orgnotin monomers. J. Polym. Si. 1993, 31, Ghnem, N.A.; Messih, N.N.; Abd-Elmlek, M.M.; Ikldious, N.E.; Shbn, A.F. J. Cot. Teh. 1981, 53, Shbn, A.F.; Hilmym, N.H.; Wkid, A.M.; El-Moniry,.M.; Mohmmed, A.A. Strutureperformne reltionships in orgnotin merptide stbilizers. Pure Appl. Chem. 1981, 53, Eng, G.; Tierney, E.J.; Bellm, J.M.; Brinkmn, F.E. Correltion of moleulr totl surfe re with orgnotin toxiity for biologil nd physiohemil pplitions Appl. rgnomet. Chem. 1988, 2, Finemnn, M.; Ross, S.D. Liner method for determining monomer retivity rtios in opolymeriztion. J. Polym. Si. 1950, 5, Gilmn, H.; Rosenberg, D. Retion of Triphenyltin Hydride with Methyllithium. J. Am. Chem. So. 1953, 75, Shbn, A.F.; Arief, M.M.; Mhmoud, A.A.; Messih, N.N. rgnotin polymers. XI. Rdil opolymeriztion retions of di-(tri-n-butyltin) itonte with 2-hloroethyl rylte n-butyl rylte nd llyl methrylte. At Polym. 1987, 38, Pekel, N.; Shiner, N.; Guven,.; Rzev, Z.M.. Synthesis nd hrteriztion of N- vinylimidzole ethyl methrylte opolymers nd determintion of monomer retivity rtios. Eur. Polym. J. 2001, 37, Minor, Y.; Tdokoro, T.; Susuki, Y. Rdil opolymeriztion of rotonyl ompounds with styrene. J. Polym. Si. Prt A-1: Polym. Chem. 1967, 5, din, G. Priniples of Polymeriztion, 4th ed.; John Willy & Sons In.: New York, NY, USA, 2004; pp Koton, M.M.; Kiselev, T.M.; Florinskii, F.S. The effet of hemil struture on the bility of unsturted orgnometlli ompounds to undergo polymeriztion. J. Polym. Si. 1961, 52, Kreisel, M.; Grbtski, U.; Dvid, H.K. Copolymeriztion of styrene. I. Copolymeriztion with styrene derivtives ontining nitrile groups in the side-hin. J. Polym. Si. 1964, 2,
14 Moleules 2010, Ghnem, N.A.; Messih, N.N.; Ikldious, N.E.; Shbn, A.F. rgnotin polymers. IV. Binry nd ternry opolymeriztions of tributyltin rylte nd methrylte with styrene, llyl methrylte, butyl methrylte, butyl rylte, nd rylonitrile. J. Appl. Polym. Si. 1981, 26, Al-Dib, S.S.; Suh, H.K.; Mrk, J.E.; Zimmer, H. Rdil opolymeriztion of 3-tri-nbutylstnnylstyrene with severl vinyl monomers. J. Polym. Si. 1990, 28, Shbn, A.F.; Arief, M.M.; Mhmoud, A.A.; Messih, N.N. rgnotin polymers: 10. Copolymeriztion prmeters for di-(tri-n-butyltin) itonte with methyl rylte, ethyl rylte, N-vinyl pyrrolidone nd rylonitrile. Polymer 1987, 28, Stnely, R.S.; Dnnin, J.; Tsou, K.S. Copolymeriztion of p-triphenyltinstyrene nd p- triphenylledstyrene with styrene or vinyltoluene. J. Polym. Si. Prt A: Gen. Pp. 1965, 3, Smple Avilbility: Smples of the ompounds re vilble from uthors by the uthors; liensee Moleulr Diversity Preservtion Interntionl, Bsel, Switzerlnd. This rtile is n open-ess rtile distributed under the terms nd onditions of the Cretive Commons Attribution liense (
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