CONDENS AT ION MORGAMC RXZAT iORS POLY ME ‘ ‘1 ‘ ‘1'- .o .- I" a F. .. J .2 0 fl .2 5-; A. J . EAST LANSEI‘JG, MICHIGAN WAC? WC mmum muons by Build G. 631w Sum: imam coma: MW bun mod Ind tin tent.» tin migmnt of tin :30: peak; in thc infrared mam i‘m 241:5» for thus compounds tum bun nude. The stability of th- Si-O—Sn lining. in the“ cmpounda as studied by infrared migycic. lo rur- nngmntofSi-O-Si bowiladSn-O-Snbmmfoutdtooecur in. Iixtm of Whitman!“ tad bia(tri--n~butyitin) unid- undar tilt mum conditions cuploycd. 1h- poiycondcnution auction 5: diaodiun aimniwxonu with dibutyitin dichiaridc and diphmyitin dichloridc in n uthnoi— ‘ twi-tolum nixtun m bun ltudicd. A point” containing tin titanium lining. —0~Si-O-Sn~ lining. did not turn. I. link!!! or product: an obtain-d which unsuited into two traction, on of which contains n SmSi uto- ntio gram thin m and tho cunt n Snasi nun ratio has thin om. Son: apocuintious :bout tbs structun of tin Meta hum bun nude. IEOimAUIC ”WHO! POLYMIZATIOHS 3‘! mm a. Gum ATHESIS Submittcd to nichimn Stat. University in putial fulti Hunt of tho requirements for the dcgru at EASTER OF SCIEICE Departs-eat of m1 stry 1963 MOMENTS '11:: tumor viehee to mess hie mention to Dr. J. B. Kineinger for hie gulchnce end cooperetim during the course or this investigation. Appacietian in also extended to the United States Air Force vhoee "lurch great provided pertiei fimciel nuisance. ii TABLE OF CONTE‘XIS IOnmmmOQOO.‘OIOIOCCOOOOO II. A. B. C. D. E. F. G. III. A. B. C. I). IV. SW WWOGOODOOODQeQOOeOOI mtimofReectente . . . . . . . . 1. Sodium Triphewlsihmhtc . . 2. Di sodium Diphcmrlni Minut- 30 Wmtin Mona”?! e C I‘ l 6 e Prep-retina of Simple Stannosiimm SOIMt Purification e e e e e o Wiml.......... Poly-er Pup-ration Molecular Weight Determination InfmedSpectre....... mammmm........ Sign): sumeilmume Wound InfmfldSpIcm....... Stebiiity Studies Poly-Ir rotation W Stildi.. e UDOOOOOOO W....... WPHMXA........ APPENDIXB........ iii 0 O C O 9 O 0 .~ 0 Compounds .0... Fomtionmd 00-0.... ‘0 WG-44 ‘4 0-0 10 10 11 12 13 17 21 243 29 30 32 M TABLE I . III. IV. V. LIST 01“ TABLES Reaction Conditions and Material minnce for the Various P01”? PPWtim e e e o e e e e o e e e Stameeilmm Compound- Przpered in This Study . . .- Infru'ed Absorption Bands in CS, at Wands mundmmi.SWeeeeeeeeeeeeeeee Fuetiomtion But: for the 251((341‘Ja)2-(n—C.;H,)t'5nC12 Cmdemtimmtt....o...¢....... Analytic! an In: Duty! and Phenyl Promete . . . . iv PAGE 12 15 21 23 LIST OF FIGURES new: _ was 1. Infrared Spectrum of ¢3sic1 in Cuban Dieuli'ide . . . . 33 a. warm 5mm of man in Clrbon Dilulfldt . . . . 3h 3. mm Spactm of mam, in Carbon ammo. . . . . 35 h. Infrared Sputum of $531054, in when meanw- . . . 36 5. mm Speetrun of (£13510),sz¢, in Cuban ammu- .. 37 6. Inn-urea 5mm of (9'3SnO).Si¢3 in (ht-boa Noumea . 38 1. Infrared Spectrum of Butyi Built Product in m:- . . . . . 39 8. 1m Spectrum at Gatlmiubie Pnctien in KB: . . to 9. Inland Spectra: of ml‘~SOIUbIC “action in Cuban mmu‘“eeeteeeeeeceeeeeeeeeeee hi 10.1nmudmotibwimikl’rodnetinm Dimlfldd eeeeeeeeeeeeeeeeeeeeeee 1memdmv1WM‘nm eeeeee ‘63 12} aluminum Ml mime Game for fissiosnd, “(“33“,)lslyteeeeee'eeeeeeeeeeeeee '45 u. mama-u M mm omen tor( lanai, “MMIWteeeeeeeeefiefieeeeee ‘16 fi; I . INTRODUCTION A widespread mad he vaunted itself in recent years for new uterine poueeeing extraordinary resistance to chenicel and thermal hurattion. Particularly, there ie an increasing intereet in the prep~ eretion or high-teaperatwe poly.” for application in high velocity aircraft, rockete, etc. ,‘lhe polyeilaganee are mm; the net that-ally etable poly-ere, nintaining their urticular physio“ prepertiee over a wide renge of teqaraturee («70’ to 250° or even 300%) (1). However, theee polyaei'e have liaitatione; their use et very high mum. being reetrioted hemae of a tendency to undergo rearrenaelent to tone cyclic etructuree of ice loleculer weight. The atehility of the Si-O—Si linkage largely deterainee the re- eietanee or the slum pob'nare te therml «mum. lodifying the electronic amour of the band would improve tin thernl “abil- ity. thy, a note ionic polymer with e higher theme! etnbil— ity ehould remit by providing e m pour band with the replacement oreomottheSi-Ounite inthepolyaer chainvithR-O, wheraiirepre— eente a metal, nu electrepoeitive then eilieon. Since the sw—si mi... in pom, pom containing um link~ age w he expected to diepley e higher degree of tharni etability. Miamg'l‘iret eyntheeieed poiyergam—etmeilme by the co-tvdroi» yeie of dietivldichloroetemne with dinethyl~ or dietlwl-dichioro~ ailene and also with mixtures of diethvldiohloroeilane and phenyltri-A chloroeilnna tollmd by further domination of the products (2). Gian-like producte are toned iv the following echeaea l . R C RfiiCl. . (gamma fig?» {0421‘}- 0 ~— $311;- 0 - R e 61H, where n, as deterained rm fractiomtion data, varies from i to it. We teetlte in the tendon integrstion of tin into the polymeric sil- mne chain. Mia end coworkers prepared polyorganostannosilmnee by the condenntion of «gratin oxides with silanols (3,10 R o R3310 0 ”SHOW!“ %én—O+S:>i-O R e ' n It was {mad that this reection proceeded with or without e solvent end the polyur products were obteined es brittle resins raving molec- ulerweighta varying within the limits 1000—5000. Polycrgenostemoailme with an alternating Si--O-Sn~0 etructure can in principle be for-ad by two methods, one of which is the slkoxide- ecyloucide motion, where it in possible to we either acetoocytin der- ivativee end alhooqysilanes, or ecetmcysilanes and smoxytin compounds. Imam“): inbi‘Mh _..._., 2n 0 :1 0 WW .. .. - - ~e ‘ 3 3130(sz . skim“). i i' Another useful nethod is the relction of organotin chlorides with alkali metal silemlatee. . R - R' ' ' . ' 825ml: . R351 (We); “9 . 5n " O " SI " 0 ’ maCL I R. 3 O'Brien prepared polymeric mterials by the motion of dib-dtyltin dieoetate with e dielivl or s dieryl dielkoocysilene end by the reaction of dibutyltin dinethoxide with e dislkyldiacetmqrsilane (5). home» ing the teirpereture or the motion caused the polymric enteriels to change from s clear saber liquid et 160°C. to e waxy solid at 220°C. However, the polymeric nterinls were not crnncteriecd beyond noting their physical appearance and it is rnknown whether polyners with the alternating Si-O-Sn-O linkage were forced. Kocnig end Hutchinson reported the preparation of e low molecular weight polymer by the motion or disodiun diphernrlsilanedioleto with dipherorltin dichloride in dimne (a). The (Hammer, was prepared by the reaction of sodium metal with (HDzSMI and used in $91. A precipitate, which formed after the resction nixture was rerlzoced for one hour and allowed to stand for severel days, wee ieoleted by til- tretion end teund to be e mixture of 8061111! chloride end an unidentified solid. An oily nteriai of low eoleculer weight was isolated from the dioncene filtrete end contained 20.88% Sn end 7.16% Si. However, these vslues ere in poor screenent with the theoretical values for s in. eilcon-tin unruly-Ir (211.16 Sn and 5.77:: Si) so it is domino that . s regularly elternating polyur was formed. 'ihies synthesized severel stannosiloxone polymrs by in 2.53:3. condensation of (3,10),st with (n«C,-,H9)25nClz (6). The polymers were found to have low molecular weight and the fractionation of the poly- Iers into e methanoleeoluhle and methanol insoluble fraction indicated undesirable side resctione had occurred in the polycondcnsotion process. ‘ihies elso synthesised simple stormoeiloxane compozmds by the re» action of meow, in benzene with organotin chlorides. Under the mild h reaction conditions employed quantitative yields were obtained and no side rcactiona were obeorved. Results of Ihdeo' investigations indi- cated that the reaction of'pure (Bao)23i¢g'with RzSnClz in an aprotic solvent should.yield otannooiloxane polymere having a regular alternat— ing (Si-O~Sn-O) structure. He postulated that if cyclic compounds are formed, it should.be pooeible to isolate and identity these and that She-Si or Sn-O—Sn bonds ehould not be formed by various aide reactions under normal reaction conditions if'pure reactante are employed. Few reports concerning the eyntheeie end stability of aiaple orgonostannoeilomane compounds can be fonnd in the literature. Siaple alkyi stannosiloxenee were first reported'hy Thtlock and Rochow who lyntheaized bie-(trimthyleiloxy)~dinethyltin, tin (n) triuuiyieii- anolate and tin (IV) trinethyloilanolate hy the reaction of'eodiua.or potassium trinethyloiienolete‘with.HezSnCiz, SnClz and SnCl. (1). However, wry little analytical data and physical contents were given in the dbecription of these compounds. mm end Hutchinson (h) mtmsizeci (¢33io),si~.(ai3), by the re- actiOn of triphefiyleillnol with dinethyltin oxide end Papetti end Foot (3) eyntheeiaed dasiosnd, by the reaction of ¢35nC1 with gsnm. In both cases tin and lilioon analyses were in good agreement with the calculated wines. Oiiawnre, gt .e_l_ synthesized compo. ndo corresponding to the for» vies He;$i0(SnR20) 151303, masic-csniizosno:5 and m33i0(sm),sme3 by covet-omit of the eppropriate aliiyl tin and ailicon chloride: (9). Tin, carbon.and hydrogen.percentages wore in good agreement with the calculated values end convincing evidence for the distannoxane struc* ture of the commda HefiiNSnRzO) 281%; was the fact that the 5 caves-emu at haste! um cmfiwsmp gm tn. an product. How-- m, mgxosmpsm, new to uJSiOSih; m hfimsnaphsuh, on manna w: 11.35103») .51», ace-pom um- «an: am, .- indium bola: nugmsmhsm. wagimsm),asm, . (n-n) hfiimufi, minute‘w to yrs-nu in. «amnion mum and my 010 amnion muma mo in tho m at um. Sch-1mm: mi Schaddt mums-ad mwumim, 2m- ttinuvinilw-iiuuvnm and air-tritium.“ Minimum by the auction or lithium triuthyhiilnohu in Mi solution via: an Wm: tin chins-Mu (10). mwuumonm M my: m1 «ability but bis-triuwmmmnwxm been» pond u M. and an um. mm to (on ”Whitman” and diuihyipom. 1‘ (C33) 33101‘30(G3)1 “O x(di;)§imi(013)3 O [(aa)‘wl‘ that Illult audition uihuiuwuiimuvntm marge" m1 amnion yioiding mwmmm Ind poiynric ntivipolyltm which mu contain- trinthyiliicmy my. “hand to tin. miehio rm an M his~(tripinw1tin)uidc in mm with m amma or urban mum, th- mm is qm‘ntitttinly n- pw by sulfur, yielding pun his-(triplmltin)mlfldn lad «than comma. and/«- aux-hon ammo (u). smut tin mic command: having um-Wui or anal—hydrazine bonds 0.180 undergo this motion with carbon diauiridn to yield mind“, m: umiogouo 6 silicon «mounds do not sxchsngs oxygen for sulfur in this suction. m. purposs or this study us: to synthesize sdditiaui sigh Mistsmosilmns mounds sad strut; the stability e: um: She—~51: lining”. Tbs ewemistic inn-Ind tbsorptions tm‘ it. m1- silicon, Ml-tin Ind Iii-04:1 were to be determinsd and ussd to study tbs products of tbs suction of (XaOhSIth with RzSnm, using high” puss metsnts. II . WMPflv‘TAL A. Preparation of React-ants 1.05% II: M by cleaving waphcrvM-ieiionm with stoi- éhimic Wt. 91 Iodiun hydroxide (12,13). fissiosigi; + zone}! : man-31¢, + H30 The reaction is forced to the product side by removal of the later from the reaction. In e typical preparation, 1.57 g. of sodium hydroxide (0.0168 mole) was pulverized in en inert etnospiwre boot and dissolved in 20 mi. of estiunol._ A stoichiometric mint oi‘ gsmsida (12.51 9., 0.0231; male) was then sand to this solution vith 10 ml. of isopropenoli no slurry m ~Utll t. ”I 1y“ mature end 1'5 811. of toluene were added. Abmt 15 I1. oi‘ solvent were slwiy removed over e period of one hour vie e Dean—Stark trap before 10 acre :1. of isopropenoi were edded to the reaction fixture. This concentration and addition procedure was repeated m1 tines 1until I clear or elightiy hszy solution formed. Then S mi. of isopropsnoi end 5 ml. of toluene were udded and 15 more :1. of soiventvere once again reaoved from the motion mixture. A 5 :1. portion of toluene we: once again added and the reuniting viscous solution was concentrated another 10 n1. before being allowed to cool to room tmersturs. After overnight crystsliiation, tho HaOSifi; crystels were removed by {i ltretion end dried in vacuo for eppromiv mtsiy 15 hours st 50°C. The yield was 9.09 g. (65.1%). ms neutral- intion equivalent for the product was determined by titration in 7 8 sbsslute sttnnol to s bronthynol blue and point. Calmlatod neutrali— ntisn equivalent: 298.h. Found matralimtion equivalent: 307.8, 3093!. 2. Di sodium Diphonxlsilonodiolnto Three methods were surveyed to find the best way to prepare (Baohsmz in s highly pure state. The first method (1h) involves the motion of diphezvlsilsmdiol with excess sodium metal in why-- drous ether. Diphenylsilnnediol (5.09 g.) as dissolved in 250 ml. of dietrvl ether tint had been dried over sodium. An excess of sodium- netsl was sdd‘od to this solution. The motion proceeded very slowly end slthough (IiaC‘hSith is insoluble in other, no solid found in the reaction vessel efter 21; hours. Partial removal of the solvent produced e very mil enomt of insoluble modastanoe which use insol- ubie in absolute ethanol. In the second memo-d (L) 3.20 g. of diphorwlsilanodiol were dis- solved in 50 ml. 01‘ purified dim (distilled over sodium). A slight excess of sodium netel was added to the diol solution and the nixture Hes reflmd for 10 Mars. A solid formd in the reaction vessel and as rammed by filtration and dried in vacuo overnight at 50°C. The yield was 19% and the mutrslintion equivalent of 238 owed with a «waisted value of 260. Presunbly the reaction mixture was not thoroughly dry and sodiun hydroxide formed. me third method, which was considered to be the best preparative procedure end was therefore used to prepare all the (liaOhSith used in this work, is s slight nodifiootion of iiydo's toohniqzxe for synthe- siting 33051313 (12,13). A 1.939 9. sample of sodium hydroxide (0.03.97 -.- : p . ~.:‘,1.;4- .‘L’A 9 mole) was pazlverised in an inert atmosphere box and dissolved in 20 ml. or methanol. “to this solution as added a stoichionetrie asount of diphem'lsilsnediol (5.375 9., 0.0.21.8 mole) and 10 nl. of isopropanol. This slurry was then heated to reflux temerature and 15 :11. of toluene were added. About 35 ml. of solvent were then slowly remved via :1 Dean~5tark trap over a period of tron two to three hours. When orys» tale started to torn, the reaction mixture was cooled to room temper- stare and allowed to stand for about eight hours for oonplete crystal- nation. The crystals were then removed by filtration, vasi'ied with 10 ml. of toluene to remove any by-prodicts, and dried for about 16 hours in vncrzo at 50° C. The yield was 0.9165 9. (113.5%). Keutrali- ation sonivalents were determined by titration in absolute ethanol to a bromthynol blue endpoint. Chlculsted neotralisntion equivalent: 260. Found neutrslimtion equivalents 259.0, 261.9. The W)151Ph: prepared by this method was found to be soluble in methanol, isopropanol, absolute etiunol and insoluble in asst 07"" organic solvents. 3. wotijxfionmrs The orgsnotin oxide and chlorides were obtained from ii and '1‘ annual: Inc. of mm, lieu Jersey. (aza.—-t.*..,,H,)23mlz and 51151161, were recrystallized from petroleum ether while $11013, ¢§nCl and (n-C.,H,)35n08n(n-C.H,)3 were used without reorystallintion. B. Preparation of Simple Stannosilonne Compounds The reaction of a sodium phenylsilanolste with n phenyltinchloride no and to prepare ¢§105n¢,, (¢3510)25fl¢z, and (d33no)151¢, for use 10 in stability and infrared stx..~.dies. ¢3SIO§3 '. ¢3SDC1 ---9 ¢351$2Tj3 fismm + ¢zsnc1, ---> ¢§iogn05id5 d mum). + ¢33n€1 --«> ¢§DC§1°5fl¢3 In It typical preparation mm 0.0017 noise or xaosid, was dissolved in warm benzene end mixed with s benzene solution containing s stoichioo metric emzznt of triphervltin chloride. A timbid mixture fanned in» mediateiy end was allowed to stand for about thirty minutes, after which it was filtered to remove the sodium chloride precipitate. The filtrate was freeze—dried to obtain the product. The flamed, was recrystallised from diethyl ether and (983:9) 131% from n-heptsne. No solvent was rmnd iron which (g3310)25n¢z could be recrystellised. C. Solvent Purification All solvents used in this study were dried overnight over Cali, end then distilled over Cali; through a 7-0 on. column packed with 5 as. glass helices. The prmified methanol, isopropanol, benzene and toluene were stored in s desicoetor when not in use. 0. Analytical Carbon and hydrogen analyses were carried ozt by hikroanalytisches laboratoriim in mmPlsnck—lnstitut f’ir Kohlenforschung, Eilheinmmr), Germny; by Spang Hicroanalytical Laboratory, Ann Arbor, Michigan; and by Geller Leboretories, Bardenis, Blew York. The latter also analyzed seversl semles for silicon and tin. 11 The author also analyzed for cilicon and tin following e :mthod reported by 01mm and coworkers (9). A sample was treated with com centmted sulfuric acid in e platinum crucible, follow“ by careful heating to dryness. After the addition of several drops of concentrated mos, the residue was heated to e red heat for 15 minute: end weighed es SnOz end 5102. Concentrated HF and e few drape of H1504. were then added, heated to dryness and finelly at s red heat for fifteen minutes. m. residue weighed was $1102. The loss in weight corresponds to the weight of $102. 8.. Polyur Preparation Several polymers were prepared by the reaction of (liaChSifi, with 323nm, (R - nCJi, or it). In e typical preparetion, (woo-.010 micr- of (Re0)zSi¢1 were dissolved in 35 ml. of e nettunobisopropmob toluene solution and simultaneously wired into e 100 :1. road bottom flush with 35 ml. of toluene containing e stoichioaetric emotmt of (n-qui.)zSnCll. After onebour, the mixture wes filtered into e tered filter flask and the clear filtrate temporarily set aside. After drying the reactor and filter at 110°C. the former was ex- tracted with 25 ml. of distilled water end the extraction trensferred to the filter and drawn into I: 125 :11. filter flask. A second 25 ll. extraction was nede before the reactor end filter were dried sgein et 110%. um which I am extrection was moo m m. combined eat- trections quantitatively trmsferred to e 250 ml. volumetric flesh. ' Portions of this solution were analyzed for chloride by titration with standard silver nitrete using dichlorofluorescein as indicator. The 12 clear filtrate iron the reaction mixture was evaporated to dryness in m... end the yield of bulk product determined. when glam, was used in place of (n-CgH,)1SnC13 e slight nodi~ ficetion to the procedure outlined above was ads. After standing overnight, e mu mint. of crystels formed in the run-nu of the reaction mixture. lhese crystels were isolated before the filtrete was evaporated to dryness. hole 1 lists the reaction conditions end mteriel balance for the verious polymer prepsretions. Table 1. Reaction conditions end materiel belence for the verious polymer preparations Sample (E Holes - 1 Cl 1 Product :0) 331m 1 Temp. Recovered Recovery 91-34 I 0.00623 room 93.9 92.5 ¢~Bu 11 0.005350 «11.00 97.7 9b.? do: 111 0.009% 65°C 97.5 V _....- d4 1 0.01018 room 93.3 89.5 £14 11 ' 0.00759 roou 93.2 33.0 F. Molemzlar Height Determinations Cryoscopic molecular weight masurements of the bulk phenyl poly- ners were ads in benzene solutions with en apparatus described by Henpton (15). Freezing points were alternately determined on known standards end zanlmosm unples. 13 Gr. Infrared Spectra 'ihe infrared Spectre of the preparations in this study were ob- tained with a Perkin~31ner Model 21 recording spectrophotometer. For «mounds soluble in cerbon dieuli‘ide, the epectte were recorded et concentrations of 2% (by weight.) using Cmnecticut Instnment ileCl avity cells. For insoluble We, e spectral sesame-nu: was taken on compressed disks in which the materiel was suspended in potassium bromide. The ooncontretion by weight of these disks as close to H. RESULTS AND 1111’ 3633310113 A. Simple Stsnnosi laxane Formation and Infrared Spectre 'ihble 11 lists the stemosilomne compounds prepared in this study with their analytical data. The reported melting points are uncorrected and determined by the capillery tube method. Infrared spectre for these combo-mos ere shown in Appendix A. Table II. swuwsiloxene compounds proper-ed in this study Forums Melting C 1 i H X Si 1 Sn 1 Point(°C) Found Pound Found Found (Celo.) ' (Celc.) (Golan) (Celc.) 9.5mm. 11.0-1 69.21} n.96‘ 1.51” 29.01.” (69.1).) (Mb) (mm) (18.98) (¢3510).Sr¢. 135~6 459.92‘3 1.37).” 6.72" unto" (69.99) (M9) (6.82) (11.4.1) (¢.Sn0)251¢z 11.3-50 452.87“ we" 2.98“ 36.25)" (63.05) (1.4.1) (3.07) (25.96) .4 ._._3_ .Anelyses performed by Spsng Hicroenelyticsl laboratory, Ann Arbor, Hichigen. ‘ bAnelyses performed by' Geller laboratories, Bordonie, New York. chmlyses performed by euthor. “table 111 gives e list of the infrared absorption peeks of the coupon-ids rented to this study using carbon disulfide as solvent. Since carbon disulfide has I strong ebsorption et h.5~.8u. end 6.25- 7.251: end seeks eny ebsorptions of the cmwnds in these regions , in addition to the peaks listed there is en absorption of mdius in: tensity et 6.8» end one of strong intensity at 7.09.. These ebsorptions ere essigned to the C~C‘ ring stretching vibretione (16). ll. study. 105:4... Wu“ (Md $5M (9.810) .54. mammal. 9m (1.5m 1,520, {35:01 mm 111. lnfrered Ibserptionbusde in (:5, at enamels related to this ._.L._ -—~ A‘_ L Si-Cii stretch 2.75 (H) dam e. .gpaglflib F enragessesllg ’ 223;: _ , . ( ebsegs “55% 33 333%:: . - 1 and ‘i es ugh B iiiség 3 ’31 begun. gli12§§§§::§§ n ~-a aaafla"f v "or 333§33%?213§§23§i” $3333 3 V sflg 31:33:; gigggsg rifiigéggfiiglifig 918.; i; 335.? WWW! gggggfig Zaifigaaa?§§§$§3 A . £2 {figfiifizfi‘ awnmamafigshéaiéégg 323$ eeeeeeeeee MMMMMMMMMMM W. M ——P—— wow-en: .-.;ai;.‘.....q.u.;g br-beeedw s-euek_._ shfimmflr g. __ . “a w— ._ ‘ s-auu F 16 1h. tuft-red metr- 91. the wound- ¢351050¢u (flaSnOhSMu Ind ($13510) zsag, were studied to determine the absorption bands cut-eater. istio of the Si-O~Sn linings end also to find bends cherecteristie for phenyl on silicon end phenyl on tin. Cowounds conteining the 8i~O-Sn linings are characterized by e strong ebsorption in the 10.2-40.7» region. Chem end Sugite reported tri-sthyl siloovtriellvltin coupovnds es having e strong 51-05:: stretch absorption near 10.2» (23). aim and (to-workers reported two oomon strong bonds cherecteristio to ell tetrahql-l,3~bis-(trimthylsilw)«ism-omens neer 11.00 end 10.20». 'lhese bands were not observed with either dielivltin aids or beate- utnyidisiionn- (9). strainer: end Schmidt reported to. Si~0—5n stretch bond et 10.20» for the coopomd (m3)§i€5n(m3)5 (10). ‘lhies found the Si—o-Sn peek et 10.3-10.1.» in dfiimads, et ebout 10.73. in (Gammon... Manama)” (magnesia). and at to.» in 0 (n 041.) zSn(C51d3)s (6). rat- the mo nds prep-red in this study, the Si~0~Sn peak as toms et 10.3».hp in dasioswa, et 10.3» rei- (pm) .5191, and et 10610.7» for ¢§n(0‘31¢5).. 1'22. velues for. the Si~0~Sn peeks found for 95mm, end dzsnosms), egree well with the velues ebove reported by ‘ihies {or the some cospomds. Young end coworkers reported bonds at 6.28, 6.7, 6.98, 8.1:, 5.9, 9.7 and 10.07“ es being cherectoristic for phonyl on silicon (2h). However, e camison of the spectra of (135101 and ¢3.SnCl shows tnet the bonds et 6.23, 6.7, 6.93, 8.)), 9.7 end 10.0w ere comon to both common The strong ebeorption peak present et 9.054 in the spectrum 01' ¢§iCl is shifted to 9.1.0.» in the sputum of ¢33nCL Griffths and Dervish have assigned these peaks to the Si Ph and Sn~Ph stretch vibra- tions, respectively (19). The absorption patterns for ¢3SiCl and l7 ¢JSnCl differ in the 13.04.11.514. region also, peeks being found near 13.6, 11..1 end 11.4... in the spectrum at $3101 and neer. 13.8 end 11..» in the spectrum of 03511131. 'Dte peaks in this region beve been usigned to the phenyl C-H out-of—plene defomtion nodes (19,22). It should be noted that there ere three peaks in this region for e phenyl silicon compound end only two for e phenyl tin compound. Whereas the Si-Ph peek et 9.0» eppeers to ren‘in at equal intensity in ”10 COWWW Q'JSiOSnfis, (dsSIOhSnfis, ($13Sn0)g51¢3, W intensity of the Sim-P11 peek at 9.3511. increases with increesing number of Sn-Ph linkages, being out for (113510) zSnob mom for 05510510, end equal in intensity to the Si-Ph peek for (¢33r10)15i¢.. A siniler reletion- ship can be seen for the C-H out-of~plm deformetion vibrstions in the 13.0-11.5“ region, the reletive intensities of the peeks at 13.53» (Si), 13.311. (Sn) end 111.1511. (51) corresponding to the number of Si phenyls end Sn pawn in the conpmnd. ms phero'l 51 0—}! mm et 111.111» end the phenyl tin C-H band et lb.5 appear es s single strong peek st 111.11». By observing the relative intensities of the ebsorption peeks et 9.0“ end 9.359., end in the 13.5 111.54: region, en estinte an be ads of the relative ‘enount of Si end Sn present in en unknown phenyl- stannosiloxem Wmd. 13. Stability Studies Stennoailoxene polymers having 11 regwlar eltermting («Si 0-Sn-v0) structure vi ll not fore if the following rearrangement proceeds under mild immature conditions I I I I .........> I e ~Si—O~-Si- O ~Sn-~0~Sn- I 2 ~Si 0311-- I I I I I I ' 18 , The reaction of hexaphcnyldisi loxanefl) and bis(tri-n-butyltin) oxide (11) was therefore studied to determine if there is any rearrangement of Si-O«Si Ind SMO-Sn to Si~0~Sm Four «thonssndths mole of (I) and (II) were mixed in 110 cc toluene at 75—30%. for four hours. A white solid thought to be (I) crystsl- lino from solution lifter cooling. The solid was separated by Intro- tion‘ and the filtrate was concentrated to about 10 cc. Infrared spectra were obtained {or ths solid and concentrated ti ltrate snd com-- pared with the spectra of (I) and (II). Five-tho:.z.sandths sole of (1) nod. (II) were then reacted {or nine hours at reflux temperature (110%.) in 75 cc. toluene. This was re- peatsd in the presence of I won}! organic acid, a strong organic ocid, and an organic hue ss catalysts, their concentrations being 22 by weight for benzoic and trichloroacetic acids and 331 for pyridine. In :11 ossos, s white solid crystallized after cooling. Infrared spectra . were obtsincd for the solid snd concentrated filtrate. Stannosilozmnc compounds are readily identified by I. broad and intense nbsorption peak in the 10.210331. region (6,10,23).. I! (I) end (11) had rearranged, e new peak in this region would indicste the ‘ formation of the Si«O—Sn linkage. The spectrum of the crystallised solid was i‘mnd to be identical to that of compound (I). The only absorption found in the spectrum of the concentrated filtrate was at 10.163:- ond was slso present in the spectrum of compmnd (II). The absence of my new absorption peaks indicates that, under the reaction conditions copioycd, there was no rearrangemnt of 51-061 and Sn~O~Sn to 5143611. 19 Stability studies were also aside on ¢§i-O~Sn¢3 and (52(35n0) 231552. Toluene solutions of each Wand containing approximately 0.02 g. per cc. were prepared and reilmd at 110°C. At various time inter- vals one :11. aliquots. were removed from the solutions, the solvent removed by evaporation in vacuo, and infrared spectra taken on the residue. A decrease in intensity of the Si~0-~Sn absorption peak would have indicated the cleavage of the 'sr-oon linkage. Also, the appear- arms of a broad and intense absorption peak in the 9-10v- region onId indicate the formation of the Si OSi linkage. No change was noted even after heating 152 hours indicating that, under the conditions enployed, the SL—O‘Sn linkage is stable in Whenylstannosilmmne and bis‘triphenylstennmq-dipherwlsilane. Similar studies were initiated on his-triphenylsiloxy--—diphenyl stamens [615310) 251155;]. Humor, it was previously reported “in this study that no solvent could be found for the recrystallization of this compound. Further investigations revealed that hosting this coward with toluene or benzene TBSthEd in the appearance of too new peaks in the infrared spectmm and a decrease in intensity of the 51-0-sz absorptim. One of the new absorptions appeared at 2.75»i I! I sharp peak of Minn intensity and can be assigned to the free SiGi stretch vibration (17). The other absorption appeared as a broad and intense peak at 12.145», which has been speculatively assigned to a deformation vibration of the Sim group by Richards and Thorpson (17). These two new absorption peaks are also very prominent in the absorp- tion spectrum of tripheznrlsilanol and would imiioote that flaw is one of the decomsition products, which would be upset“ if moisture were present in the mixture. (Manure and coworkers (9) found that 20 moisture promoted the decooposition of bis-(triuthylsilooqy)~diellvltin compounds to mummldisi insane and tetrullgyl~l,3~bis(trimethylsil- any) «distannoxane. Triathylsilanol probably formed initislly and «(sickly condensed to torn hexanetlvldisiloxane, since (CHQfiiOH is very mstable mad condenses so rapidly that it csnlbe isolated only by opeoial techniqes (25). Deconposition of (11,510) 251151, was also oboorved after standing in benzene for two weeks. However, unlike HessiOSnEtzOSi‘ih; (9), a bottled maple or ($19310) z5nd, am not de- cowoae after standing for several months. Apparently ecu-pounds of the my. ngsmsmtgosmg have a greater mm: stability when a! - phenyl than when R' - methyl. ibis is in agreement with Roenig and Hutchinson who found that stanmsilonne polymers containing phenyl- siiioon mities were sore stable than their netmrlsilioon counter- parts (34)- Clesvnge of the Si~0-Sn linkage us also observed with crude nomads)” prepared by the cmdensation of damn, with naosMJ.‘ The ends product had a nelting point of lfi~l°€. Found! 70.51% C, b.9331 H, 9.71;: Sn, 8.38% Si) Calculated: 71.30% C, b.5933 H, 11.61% Sn, 8.2m? Si. Infrared analyses showed the presence of pherorl groups, phenvl on silicon, Si-O~Sn end Sic/H bonds. all of which indicate the Wide product probably consisted of ¢3n(C6i¢3)3 with ¢35iGi as an Impurity. The elemental enslysis s .pports this since the tin content is less than the calculated value and the silicon content is greater flan the calculated values. The cleavage of Si~O~Sn occurred during *l‘his compound us not reported with the other stannosiloxanes since it wild not be isolated with sufficient purity. 21 an “tempted recrystallization of tho product from toluene. Infrared analyses showed the complete elimination of the Si--O—-Sn absorption and I greater intensity for the SiOH absorptions. C. Polymer Formation Several stannosi loxanc poiymrintiom were attempted by the com causation of #151 (ma) 2 with 014.14.) 1mm, and ozsnczp m products formed by tho fizSi (ah);- (n-C.H.),SnCiz condensation we may oolida and insoiubic at room temperature in all of the solvents imntigatod. However, they formed clear solution: in hot. n—azvl acct.“ Ind remind in solution utter cooling to room tempenturo. They also fox-nod clou- soltxions in hot carbon tetrachloridc and after dealing to room tamper» tux-c, with overnight standing, precipitated tron solution to white solids. This behavior in CCI‘ was used to fuctionnbe the butyl pro- ducts into a COM-insoluble and CCIrsolubie fraction. Fractionation data are given. in Tabla IV. Table IV. Fractionation mm for an {iguana}, (11441,) 1.21151. con- densation prod zeta. * Same cm 301M. mum {his immanaon Polymer Weight (9) Fraction (1) Fraction (2) Tampa-aura ¢~Bu1 0.123 53.8 141.2 room 1.021; 58. 5 1a.: ¢ .91.. II 0.13:; 69.L 30.6 41m. 0.120 70.8 29.2 ¢"BU In 0. 1“ 71‘08 23.2 65°C. 0.221 83.9 11.1 22 mo hulk precincts tamed by tho ¢ZSi(ma),-¢,smi, condensation voro brittle polo yollou solids ninth in barium, toluene, carbon dioulfido, carbon totrochlorido, and xylem and insolublo in n~h¢ptono and cyclohoxam. The. small crop of crystals from this roostion (about 53 of tho product) ooltod iron 218-222°c. ond mo oporingiy oolublo in hormone. Bocoroo of I lack of o suitablo solvent for oryosoopio ”noun- unto, noioculor weighto for tho )3qu products and tho phonyl oryotoio m not dotorninod. Lou “hi-II for tho viscooity dotorninotions of tho hutyl polymoro in o—wl ooototo indiutod o low unloculor might... Tho moloculor weights for tho bulk phonyl producto, oo dotorninod by cryoooopic mom“ in bonnem solution, woro 1350 and zinc. Amlytiool onto for tho hutyl ond phowl products oro givon in lhblo V. Tho calculatod voluoo for tho rogulor oltormting O-Si-O~Sn Mango do not ogroo with tho «primal vain“. Tho low carbon poroontogo, tho high hydrogon porcontogo, on! tho largo ootol carib- oomplo night rotio for tho Cry-insolublo faction show thot this froction hos o tin~oiiioon unit rotio arc-tor thou m. Sin-Univ, tho high carbon poroontogo, loot hydrogon poroontogo, ond snail notol condo-sown might ratio for tho car-soluble {notion ohov thot this fraction has o tin-oiiioon unit ratio loss thon mo. It follows thot on incrooso in tho tin nononor units, which contain butyl groupo, would inoroooo tho unit night ond hydrogon contont whilo dooroosing tho urban contont moron: on inoroooo in oiiicon nononor units, which contain phomrl growpo, would docroooo tho unit Hoight ond mongon oontont vhilo increasing tho carbon content. ‘iho high percentage of 23 tin and low porcontogos of carbon, hydrogen, and silicon in tho phony! oryotols show that thoy sro meson of o tin-silicon unit rotio greater than ono. Mk V. Anoiyticol dots for butyl and phomrl products. A. _._4__ V—V—w—v. vw Poly-or C S H 1 n9 ootol oxido/ng , i. ._ x - L 9“?" tom non. 52.12"d 6.22", Loni/11.33%, (53.71) (6.31) (sates/11.387) Butyl CClrinooluhlo 140.51“ 6.88‘ 3,135/5,537. Botyl CCl4-~solt_:blo " 59.32‘ 5.60‘ shes/mm" sag - Sig goon: 55.11”, L22”. 25.69“. 5.51". (59.17) (Mb) (214.36) (5.77) d Crystals 50.525" 3.60” 3h.b8° ’ 2.1.1“: 4“ v-o— ‘Anolysos pogi‘ornod by Hikroonolytischoo lobes-storm: in m- Planckolnstitut fur Konionrorsommg, vitamin (Ruhr), Got-may. bAnaiysis perfornod by Gollor Laboratorios, Bordonio, Nov York. cAnolysis performed by author. - ‘Coionotoo for o ”@2181" alternating (én(C4H,)z~&Si¢z~O~) 11mm. ‘Oolculotod for o rogailor altos-noting (-Snfiz-O-Siflrod linkogo. ‘iho intmod spoctro of tho butyl Ind phonyl products In M- in Appondix A. Only ono spoctruo for tho butyl ond phonyl products is ohm sinoo tho difforont ottomts govo prowscts with similar spoctro. Tho infrared opoctro of tho bulk 15qu poly—3r ond tho butyl CClrooié- uhlo froction oro vory sinilor, both raving proainont ohoorptiai who at 3.15, 7.0, 8.95 (wry straw), 1.3.5, lino, out! iii.» Ind o brood 2h hood strotching Iron 9.1 to 10.59.. Tho absorption at 3.15:; is tho mhon-hydrogon strotch vibrotion in tho butyl group ond tho obsorr tions ot 7.0, 8.95, 13.5, lino Ind liin oro ossociotod with tho phonyl group and phonyl on silicon vibrations. ‘l‘ho brood bond from 9.1 to 10.5» is this to Si-O ond Si-O-Si obsorptions with tho Si—O‘Sn oboorpo tion appearing oo o shoulder on this bond noor 10.14:, which is ooro pmoimt in CCl4~soliiblo fraction spoctm. Tho pottorn of tho ob- sorptions st 135, lino and 1h.” olso ditfor in tho too spoctro. 'iho spootrnn of tho butyl 0614«-insolublo {action is quit-om- t'oro‘nt from tho bro proviouoly notional, booing any of tho observ— tions ossociotod with tho butyl W 1nd grant in tho spootrun of (or-Coil.) 154161,. Also, tho brood bond so proninont in tho othor spootro tron 9.1 to 10.5» is oboont on! tho phonyl silicon obsorption st 8.95:; is poosont with lessor intonsity. ' rho inrrorod spoctro of tho bulk phonyl product ond tho phonyl crystols oro similar in tho 2-99 rogion but dittor oonsioorobly in tho 9-11.51; rogion. lho phony]. silicon-Winn nous 9.0» is such stronoor in bulk phonyl spoctruo than in tho opootrun of tho phonyl os'ystols.‘ s brood bond strotohing 2m 9.13:: 16.83;, with onsll points 0! axiom intonsity st 9.35, 9.8 ond 10.25», oxists in tho hulk phonyl spoctrun shore“ in tho sons region 0! tho spoctrun for tho phonyl cryso tsls strong obsorptions oxist st 9.65, 10.2 mi 10.8». Tho phonyltin obsorption at 9.355; in tho bulk phonyl spoctma oppoors so I shouldor on tho 9.65:4 absorption ‘in tho phonyl crystals spectrum. Tho obsorp- tions at 10.2 out! 10.8.). on possibly Si-O-Sn absorptions and tho obsorption at 9.65;; nay ho duo to Si~O~Si vibrations. Tho oboorption pottorn in tho l3.5-lh.5u rogion of tho opoctn-m of tho phonyl crystals 235 is cimctoristio of pining/1 tin hydrogen absorptions whereas tho pat» tern in the cams rogion of tho spectrma of tho bulk prod-Jot is char- octoristic of phony! tin Wagon on! phonyi silicon Ivdrogon absorp- tions. . ‘ Tho procoding ihfnrod onslysos of tho butyl sod phorvl products ogroos with the analytical dots ond confirm tho conclusion that tho 0C14~soivblo fraction is prodoninonthr silicon monomer unit, tho CCI‘w insolublo trootion ond tho phonyl exyshls oro prodoninontiy tin nono~ nor units. ‘iho isolotion of products with difl‘oront spootro indicatos that oido motion ooourrod during polyoorimtion and that o polymer with tho rogvlor oltormting stmcturo did not tors os prodiotod. Tho physical charootoristico and molooular night of tho phonyl products differ noticoably from thoso proparod by loonig ohd Hutchinson (1.), who obtoinod o hoovy syrup with o holowlar voight of 830, by tho in w condemtion o: ozsuom), with ogml, in dim. Soho spocolotion about tho structuro of tho products con ho mode. Disodiun diphotvlsilémdioloto hydrous” to torn dimlsilsmdiol ond sodium Wide. mo disodim salt could met with ootinhol in on analogoss way to form sodium wrdroxido our! the dioi, which hos o strong tendency to form $i~C~Si linking“. Haro (26) reported tho syn- thesis of o compound with tho structuro Ph m.Ph 0 Ph m Ph Homosmsxoaroswsmmw PhPhPhaPhPhPh from tho roaction of diphenyisilanodiol with m1 chloride. Tho infmod qboctrun of this commd has tho strong 9.1~9.8u absorption (Si-~06” which is olso prosont in the spectra of the bulk bvztyl and 26 bulk phonyl prod cts proparod in this study. If the disodium salt- methanol reaction occurs with the formation of tho diol, sclf~conden- ostion could occur forming Si~G~Si linkages, which could react with tho tin moor to torn o choin with o Si :Sn atom ratio grootor than ono. Howovor, onolyticol dot: rovcal tho ohsonco of chlorino in both tho phonyl Ind butyl products which eliminates the possibility of a structuro with tho organotin monomer as an ond group. Eucloor magnotic rosonanco studios of tho bulk,phonyl products showed tho prcsonco of only phony]. hydrogons. Tho obsonco of an infrared obsorption peak noor 2.7Sp indicates tho absence of tho SiOH group. Tho procoding ovidonco indicatos tho oboenco of o suitablo ond group and.doos not favor o lingo: structuro, but seems to indicato tho prosonco of cyclic products. Cyclic stannosiloxano compounds have been reported without proof by Koonig (L), who isolated two cyclic stanhosiloxanos, one with the proposed structure 0 ‘\0 ¢ ’5; st: 9‘ \c / if from tho reaction of dibutyltinoxido with diphonylsilanediol in dioxang and tho othor with tho proposod structure 9!. Sn 27 from the reaction of diphznyltin oxide with diphcnylsilanediol in other. Diphexwloilanodiol also has a tendency to form cyclic trimora and tetra-tiers as products of Belfacondcnsation. The cyclic trim: and totramr of the diol can be differentiated by a strong band (Si~-O~Si) in the infrared apoctmn at 9.1519.ij for the tetramor and at 9.8» 9.951 for the trimr and also by 3 characteristic intensity pattern for tho peaks in the 13.5-lii.5p region (214). The intensity pattern in this “glen for the bulk butyl and phenyl products is similar to that of cyclic prod lots and could possibly indicate the random inclusion of tho ~311¢z~ unit in o ring containing soc-.51 linkages. Since it has provioa..:.si;-,' been established that the balk C314~insorib10 fraction and tho phony]. crystals contain predominantly tin units, it would follow that the bulk phonyl product would consist of predominantly silicon monomr units, which would explain the strong Si~O«Si absorption and tho cyclic structure because of tho low nolocnlar weight. Assuming that the ¢ZSi(t}iéa)z~-Gi302i reaction occurs, «513124) 3o limmges could possibly fem and combine with ~Sn¢3~ units remlting in tho formation of cyclic products containing n 5125311 atom ratio greater tinn one. An excess of onroactcd tin monomr would then bo present in tho motion mixtzro and would form by-prodccto having a high tin content, so proviozcly noted in the Cay-insoluble fraction ond tho phonyl crystals. Elimination o: the ¢231(ci~:a) z 0sz reaction would eliminate tho {oration of Si~0—Si linkages. Thorci‘oro, tho reaction of tho disodium suit with on organotin dichloride in on inert solvent should form alternating ~0~Si~0 6n" linkages, slthongh thero would still be cyclic stmctexos present in tho reaction products. 23 D. 'I'nonral Studies Differential thermal analysis curves were obtained for gigswswa, (¢3810)15r¢2, 0633110) 33155,, and tho mm phonyl product with on appar- atus described by Sistor Strooth (27). Tho curvos oro given in Appendix B. Tho uniting points from thooo curves ogroo well with tho uniting points obtoinod by tho will”? method. Tho initiol decomposition occurs m: 13060. for 513310521915, near 32:000. for (dasw) .519!” ond noor 1.30%. for ($13510),s:¢,. no mum docouposition for tho bulk M1 product than» o axiom st» 3300c. IV. SUMMARY Semi stonnooilmm commas how boon proporod Ind tho tonta- tivo usigimont of tho mjor'poohs in tho introrod spectro tron runs» for thoso comm: has: boon node. The stability or a. Si-O-Sn link- ogo in thoso commits Hos studiod by infrared mlysis. Kc roorrongo- nont of 31-0—5! bonds Ind So~0~5n bmdo to Ska-Sn bonds as found to occur in o nixturo of Mphonyldisilomne and bis(tri~n-butyitin)oxido imdor tho motion conditions oniployod. ‘iho poiyoondonsotion motion of disodiuo diphonylsilonodioloto with dibutyltin dichlorids ond diph'fiyltin dichloride has boon studiod. A polyun- contoining tho oltornsting linkago ~0~Si-O—-Sn~ linkogo did not form. A mixture of products Hos obtained which soporotod into two factions, ono of which contoins s 531351 oton ratio grostor than one ond tho othor o SniSi otou rotio loss thou on. 29 l. 2. 3. 6. 7. 8. 9. 10. 11-. 12. 13. 16. i7. 18. K. P. P. J. H. W. J. J. C. J. A. R. D. BIBLICIERAPHY F. hpport and G. J. Loigh, Devoioments in Ina:- ic Po (homing, 81min Publishfng Comany, Row York, so , p. 1110. A. Andrianov, 1‘. I. Ganino and W. stulova, Izvost. Akad. huh 585R, Otdsi. Khin. Rank 12%, 798. E. Kocnig and R. D. Groin, HADC TR 58—111, Part 11,5111! Doc - mnt No. ADZISLZS, Juno 1959. E. Koonig and J. H. Hutchinson, W.» TR 584%, Part 1, 15m Documnt No. ”151197, Hay 1958. I“. O'Brien, HALE TR 57— 502, ASTIA Docuuont No. 011.2100, ()th3: ISJTo Thios, 1m: 1 Condonsstion Roactions. I. Stamoilonno s. rum and n. o. Rocha, J. Org. Chou. .11, 1555(1952). Papotti snd H. H. Post, J. Org. Clan. 33., 526 (1957). mm Us Go Whit.’ Ko Fuji“ w H. 5‘“, Jo Mo Mo Soc. é}, 131.2 (1961). . Scimidbaur m1 H. Schmidt, J. Am. Chem. Soc. 9;, 2963 (1961). r. Roichlo, Inorg. cm. _1., 650 (1962). . F. Hydo and O. K. Johonnson, U.S. 2,163,092 ““9““ 5. 191.?)- l". I-tyds, 0. Ii. Johonnson, H. H. thudt, R. F. lining, H. B. laggsxsiagor, and ii. P. Rocho, J. An. Chou. Soc. 15, 5615 F. Gibbs, H. Tuckor, G. Shkaponko, and J. C. Park, mac TR 55 1.53, 15111 Documont lo. m13i036, September 195?. Hampton, 50m Sil ~Chrominm Chomistgz, Ph.D. Thesis, Mich- ignn Stats University, 335. 1.. Smith, Spsctrochin. Acts. _1_§, 87 (1960). E. Rich’nrds ond H. U. Moon, J. axon. Soc. 191,2, 1221. H. Hhiffon, Spectrochin. Acts. 1, 253 (1955). 30 31 V. S. Gritfths and G. A. H. Dervish, J. Roi. Spectroscopy, 2, 1116 (1960). R. 13. Cross and v. 1. 9.35.1, J. 1... am. 800. 11, 51358 (1955). R. C. Pollor, J. Inorg. Nuclear Chem. 33, 593 (1962). F. 'd. Bahnko 3nd C. waorski, Technical Document”)! Report ia'o. Emma-62421., Fobrmry 1962. R. OW ond K. Sugits, J. Am. Chem Soc. £32, 111.80 (1961). C. H. Young, P. C. Semis, C. C. Currio, Ind ii. J. Huntor, J. An. (in... Soc. 19, 3758 (19118). B. G. Rocha, An Introduction to tho Chemistg of tho Siliconos, Jam “11” '5: , Mo, CV ark, 9 , p. 9 mds Ph.D. Sister ii. C. Strouth, Thorn]. Dccommsition of Yttrium Sandi-am and Hal; Lunatic—{baloney and Carbonates. 155.15. fish, HIE-Hg... '55:; URI vorsi :1, 13362. mm: A 32 33 .onfimHSmuv connmu.cfi Hofimmu mo ssnuoomm Uopmuth .H .mmm Amconoazv cpmcofio>mz mH NH HH OH m w 9 w o Jum_q m u . q a 1 ~ . u _ voopfiSO 1mn: commom Ca 8 3 ouaqqrmsuoql ‘ 8 (quaozad) a O [s OOH. , C O “I“ “H Amcouofizv pmeoflo>m3 0a m m . N, OH ON / ‘ O m l 2 qimsuesl O m 3h (guessed) aouaq 8 O p. 35 «H OH .ogmfismfiu cognac E mfiocmmm mo 5:50QO nopmnMCH .m. .mE Amcouomzv 593283 m m w m fl . _ . o .3 @3280 amua aofimom . Oo- OH ON C M 3 8 8 (quaoaad) zoom; unsung, 2. 8a 36 .ovaHSmHn cognac a“ nacmowmma Ho ssnuooam wonwpmcH .4 .mfim Amcouufizv camcoao>m3 . - fl 2 2 . 2 2 m m w o m 4 x m .1 _ _ d 4 . _ . _ _ _ o " Voupfiso 1mm: cofimom _ - 8 1 on 1 o: .. om i -s n o» n on 1 0m aouaqqymsuaql (quaOJad) OOH I 37 ovaHSmHU conumo a“ wacmwhofimmuv Mo ssupooam UmpmuwcH .m .mmm Amaouowzv camcoflo>w3 4H ma NH a“ CH m m , m o m 4 m _ w a . 1. _ . _ 1 _ _ _ o Umppmeo 1mg: conom 1 0H 1.8. n Om ; - o: 1 om . J 8 - 2. 1 0m J om OOH aouoqqymsuoal ) uaoJad (1 38 oUCHJmHU conumo 5 ~Ewm~ Aocmné mo 8:30QO woumuHcH .0 .m: Amcouofizv camcoflfifiz - L :H ma NH 3 0H m w ., w o 4 - m .. _ . . _ . . _ _ fl . g _ o . @3380 1m1: aofimom 1 OH _ 1 ON 1 on J I. m . u 1 04m j .1. C m u 1 om» am a J D 1 8... 0 - 1 21 \J): C .1 00 1 0m _ .ooH 39 HH OH q .nmx 5. puscouq 55 T32“ ho 52.30QO woumuudH .N. .mE Amcopomzv cpmcowo>w3 . m m 5 q 1.. 1:. m. a q . _ U34 :8 amua cofimom 1 .1 OH 8 8 2 9. 8 (111139.124) zoom: moon; 0 F 00 OO~ ho .nmx cw cofiuumum oflnsflomcfi1ofloo mo Esnoooam wonmnHCH .m .mfim Amcouufizv camcofio>mz .2 2 «H S 0H m . m . o m a m m q 4 . _ . q . _ . . UoppfiEo 1m1: cofimom Oa On 2 8 91 (quaozaa) aouaqqymsunal O p... 02 111 fi .ovmmfismun.connmo a“ coupomum oflpsfiomuvfloo mo Esnuommm commuMCH .m .mmm 2 NH 2 2 m m N o . Amcouufizv camcoflo>m3 . , , L a m . q . . _ fl 1- . fl uoppfiao 1m1: commom l O m i 91 19. (quaoaad) aounqqymsuoal é l O p _ . OOH 62.3326 connmu 5 posuoum on?“ Tosca Ho 85.50on nonmnmcH .ofi .mE Amcouo :6 59.3 963 i Q 2 S 2 m . m N o m_ a m . a q q . . J n . . - _ J O D 2 - g @3380 1M1: cofimom 1 OH 1 0m 1 0m n. - 3m m. m M 1 0mm no» a J 1 8% u M.\ 1 oh 1 Co 1 0m .1 OOH .umx a“ manpmhnu demnm we Eonooomm woanMCH .HH .mHm Amconufizv cpmcmfio>m3 NH HH OH m m "‘N .3 m 113 4 . 4 19fié!:.;1. _. Uopp«Eo imua cowmmm OH ON Om 8 8 £91 (quaoaad) aoueqqymsueql O t» 0 co .ooH 1.9933111 B 01mm IIERIIAL ANALYSIS URVES 115 .~ufim~ Aocmnfiv cam nmmcmowmwfi mom wok/.50 mwmfimcm HQEQB 33:88th .NA .mE . - ,. Do onsumuoqeoe cop 08 com . co: oo... 08 - ooH . _ _ _ d. 1. . nucmemnu Q: Aocmnnv 8110111111111 “1 21512113 h6 .uuswonq fixdmca xfisn Ucm wucmonfimmav pom mo>nsu mfiqumcm Hmsumcp Hwfipamnommfio .mH .mfim 000 0o ousomaomsoh 00m 00m 8. ~ oom _ 00: _ JacmNAonmmav fixumcm xflam q fl OOH _ SQIOAIIIIN UI afiueuo -.-‘~...o--- —A~M_.na _. Illlllllfllllllllllllllllll 1293 11111111111111111111