Document Rpo3ryR408XJ9pyoODJGoobn8

f Particle Size in Suspension Polymerization F. II. WIV-I.OM IMI W. MVTRKYKK Iti'fl / nfMirdfonVi. Murray Hill. J. f Milfrol *>C hi/i* .iihI y< oiin (rii .|l lorlu of i(ntM`|\ i tn Imkril I > > t|r<i'tirlHiti fluid |t|l( Tit .il |Mtv dvr** uvfnl .t dI rit - .tint in rhtidii^iral >1 iidif -. Mil Ii `tinlit-H uf^i hear mi I'nriu^ im|inrt.m| in im *-\- ( h.iii^* n-iti-., ''*'* ml I lt< .1(11 ..............- Iiilllirm ini' till' |rt`|i.irl I mil of |mi|i im r ^{ilirnMil- In * i\ i-'.t,d>h'dit*d on a <|> la Ii 111.111 i - !.--(-.: Pitli \ |||\ I .lit <i!|i>l jin >ii<{ lo Ik- ,i It i |li d \ l Mi* | lif -1 ,i Iii 11 / it Inr |m il \ ii <r -rjduTmd jr`|i.t fa I mil -, I Mill r i inti ji.tr .11111' t otldit ion-. (u) in^il Innh'fiil.ir "riu)|| (.r.nlc'. (/) |.i r t i.i ll\ In 111 | v/n I jar.nh1-. ami (< ) hi^li n- < cm rainiii^ <i|` -taluli/t r uni akkiM Ml) <1 v* 1111 ^[ilu rnnN uf (ivwr mean diameter-. I he-e t:i,iM,r.ili/aliniis inter Mi^iHii'inti 'l.tlnluatinn do>*n (n mimhl> 0*1^1 Mahih/cr 1 lr*` liiinTiilrdlion limit- ulim- xiii|M>iuliii|t artinn ure, of inlcri-il. Herr it hjh fmiml i|,ut llir miiil>er of |Hl \ Mil} 1 alodiol ninlreiih'n present l>eeaii,P import.ml--ih.il o. fr njiul vifijchl cnncviUratimo in \iiiiuli nftMMI.V/*, h'Vi mnh <-nl.tr Height polwncr (19.Of*); produced -l.hdi/ed (although large) -phere* ulun as u-nj| high moleenlar miulil poUnu-r {`a.OOO) wan imflVitiw < h*-c In t he m.iMinimi |H>--ihlr , i*dd <f Hell-form, -plo-mid- h a- reprodtn ihl\ nhtimied in narron -i/,* ,|isin_ Iml inti and *ith anT.i|!i` -phemid diameter* ranging fr,,,,, a MIMT1.II' (n -e\cral iiiilltiMt-iiT" ill diameter---a tlmn-an.l. fnhl x.iriatinii in dimeM-inii-. Ml V ii \\iv \| . pt .t i u-}* t - ,iM - UMU'in.' o.* l Hi** 1 ! n ui r* ii'i. .ii * v r t i [ 'i.'?ait.. i * l if11 ( ' <n f hi u In ii. * f* ' M.h i inniu iiumln r . 1 luntHiini i-, nm-t \ lu\ ) \ miijNiui., , " p r * j * t f it -Uft <i<Ii fur -U"|*i U'ltin |m{\mi ri/ tt n .n /; p i'tn lc -1/ h-t' it <t1111 .ii i \. - ip | 111 n !i -i/* , Mhii f vT* lit . .1 M 11 \ I [in t Ii li t \ 1 ift . -t\iiin, aiui -i >iin` 't\nrie iii ri\,t: u - >ggl>Murt ,ii1,.n hi i *U']n ii'i.-H j'i'i\ iii* u/.ii h>n |ni"lu>t 1 In w.iv iS.niiiniil in tin*. 'tu.]\, imit tin* iLita jmin. i * i-j* > t 11* } fii- -t u |\ w i - t i - -t j - . r 11* i fli i t' < >t `i'!iu .tt In m \ ,i ti in- til't.UJnil frivin a miMuiv nt t-oinrt- of i t lv K in v IU ti/. t, ll!* - S \n.il ili-p t- `fit'- >i Mi'|n i 'li'ii 'I tl'ili/i i' tin \ nr 11111 .fiun\I! n/* ' Tins u.t-. -ujijiln.l ii\ (in- Dnvt Cinim, ' ninti .< >nK i.iDi.l, w.ti iv.hnii.l mill pirtiiuln impl.i-i* i-m < n uu.li-r tin ir i mil intuit t. I it ion-i-ti <i iif cu r inf^ ' in i r I tT 1 11 \ I III " ll. p( -v ; * U y -pin tl< a! p.n t f 5. - I .j t> i iii. in\ lin H/i rn i- ili ti r mm. .1 Itii,il uii-sittiiaMnn, Ii\n pt , I' l mm n \ i i ip ill 11m '> r I a\ \ in\ I iIi i >!n! u *t t|.i.i .{ in i fi u m,i! mu', tin- u.lulnttir. (. f-hutsl \ias tint . ^rv 11 -f 11 t iii. ,i' t K- \ i11< mi- 1:1 11!* - ,i\ n! ililf iii*.w. .j i<>m- I| H Till I lull |n.l\ nn t |/.it ll. ft. MIIH' it lit*! lit t h' t ffl I t MM til* { ni i't ii tie 1 tl ipltlt hi t ii* l. :ui 1'1m' i j. 11' ii ]i -i/i I- -uli It uni. !jm\m m r. .tn^ .ui .tjijm i i.il>!e iinlu. imn ' I in III* . fi.iMi'' ft ' * - n nr,^ [i-iufi- . 1 i` lit iif.nlul.lt (.I'U- : n/.ti-It `t.il-1 in in ,i jwi iui- -v - Tom i" 11lu-t r iit ti In iu it n i!l\ ui...!. i.i it h >i n.M n mj" i .iiuM " i ii a- 'li'iwn in I'i^un* 2 "1 In- | { 11 i(> I 'tap- m tin pi .l\iin i i/at inti i>t t -u-ji* i >{. } -t. I i^im J Mi i ii iiii. 11 ilh i'! mi -ui>j. . r- t in- jit -mi>;ni n< -nil Lrlni-uli . .t ii v in \ Ii * n/i in nn\ t nn iir il!ii-t r iti . i -i in in itu .t I! - itMt ti. , \ i-i i - ii- i; i . ,u u c . In- t.. i tlm n lh ki ui I ijTun -l '1 in In - f iinl nn .-f r ut n J piii i - i ii 11 ,n ii n/ .! i e m I, -ui>. .jU fit .j. n- hi i i: 11 a ,i,r.. .i; -i|i- Siimilt ,in .j-1 \. r ip).| mi n .l-i lu I*' tin it* tfpintf jn'l^nn r ii i * hri-n^)i t) i, \> i .... -- . i - . ,( f . . r !. ifri .{i- N rM r.i t< - lit It . fin t ..|n lit (-/* / . WH it-] !>! vi'.-I n! ir lu-fi 1 -i >n 1 . . 'rt tin nrt^u. il -h.m.j(| , -inipli n.iiliiii- ) piMMiiinni. hh| tin jniil ini -i.nn --.it >! -t 4i m!i/i f... n : .- -u-j- u -1.. 11 utfi. r ,i . ni.-t i -1' n\i t ,[' i iti ..t -In n% i iw utpnt 'Lin Hit! lint ill iti I'Im-4 1- l. nil'll \'inl| til. ^ 111 H ri i irm f r I 1- Ijii.i k'\I - .[ .-I,,,!t'la-Nr- . .f ul-.i.iil.- i. M ["'Kitn i .iiiin- I. ui |"/in4 .t'.i 'i.r- n^ii-Mit tin : t n^, i i,f j 11\ \\i ik i ' ''i i '' ' i -, t- ut ii..f ' 11^ | r ,! r.. - -i i - u't h ,i p I 11111 fli - -1111- in:, ft |... I \ in* r > "In n * \ i 'H"i' t tin- .li-i up- . -: -> - . i !in I In tin I.I. ii -I Ik' I - : . ii' 111.. ' i h l- * O. . i. >t "Ul ' I- I - t. 11 v i ip 'I * - I !''* ` Uli . 1.1., p 11 t t r. - - 111. k i ! i * *'* !i<" * III It< '(a 4 I^'.p'f Ii < t w . * [ k Ml ihi!' -11 . ( i i\ k i \\ if ll til' < Ilf I * |'f ' \ ' ].|\ 11,< r 'l lie in i 1 .. 1 tin . , , : 'I, .ii.ni iii'! 11.................n.p .i Ml 1 IpiH J n-pp -* M - t lie . - U a 1> iw i*,\ l-i . i it \ 'In n i - k'i> r r -i-r i in t.. j: - a f i-m , * I *- .In- t.. ^ i-ii !`ii' t.' ` - -1 * w r i i:. v i k' i > .' - r . I., v t >4 w , r . i i ^ i;r * ' * ' 'f r..ii^K * "iii ...i i11 i ^I " k'kVl- ll* - I In I I**' r p>n * f, - . ft. I- M " Hi 1 -! I", -u-t- I - . . - il i i, .* m i'. . r' ! ,4 :l . .r i, Xt> X \ I G OG O o O ^ ' I l'*B ^ (J k-' o i ,ii IMI li! -t Ip , *! ' P 1 i' . . pii , i- tin -t, t p p< rt ' a 'In upjt r in i it i It* i ui \ , . i'! - u 111 t ' it in;.. t p"K tin r Pn \ n'U- itH.4 -iip'.ii- ' i >\i .>|i4 rn.l tliii -u-jwf- pt I \ n. riz itlf M l- Mn n |\ H . }' ! \'m i w.it i"u .in i r i .j n a' in tin- n -p , f it ii -li i r p!v I r- >in t \ pi< i! ina;- i, - u! i ;i "|....... "i 1 `-r- ' i '..-t -i - :a n 'J* -1'- ,f - t r , rv* ,1 ipi* * i . 1 ^ i'1 1 1[-P"'T I ^ nd L-l-'-r1-. .! : "I pf\wr -.1 ,1'fln-i \ ".i lit in.1 M I li.ik'r.llli n( ^ t .i 11 - f I Ii-jMT-M`11 il> '*li'|Mi|'Hi|i Pnl\|io ri/.il**i|i nt l*lniMal 1*4 n/r!M' (Ift) } >4 1 V III. I|/ l f 1 (l U in n tin 4 ` i r.111 1111 at ir* t i >11 -1* l> :* `i t * -It IJaf* >1 at I hr Hilt i i i. . , Hi tin- ujUt "U- )'l.a-4` ' >, (I. in J*P Mill! l'l> i In ,, l \ noa My 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 1109 garni nut* rial- \ partial li^t of tin* organic dt^H rsvnt + that wwv ii,stigatt'd i- .i- tollow - Methv l CvlhlhiS*' Pnlvvmv l lncth\l elhri l*nlvv\u\ I dcohnl l*ul\ cth\ Irnc g]vi nl r*4\ met h ii r\ h* :n't*l t' irlw>-*\ met In I i IIul..-t Stanh * iclatm A pole and ilril- \n* tinSi'ilnim alginate Fiffiirt 2. Kulf of l*oli iiKTisal inn of i>i'in * IIm-usrnc Mivlurr ** lVleruiiiied h> l*irlicle ( huuge \ti inilttrlian |wnMl f 1 liir iiKl'Calni l. * horiuinot jHirtmit if iftrtirli it* n-it* rum h nativity (rate and modth* r ui < !iiul-i"!i -i'( ms u the -o M' I ,..i -ta!iili?i*r w absent in n-mn |ml\nn n/ilion- XI Factor* that do, fumiMt, wit hi* mr tin* rate i it poU mi ri/ item i.if the divinyIU`iu.ciw* mwtmv ah* gum m Figuiv- I ;itm! [They iiTV aclf-^xphuutory lb*t irdution dm* to nl nt<>spb* n< ii\ygkMk vjirira according tn tin* degree nt agitation i- exhibited h\ ti- correlation with pnrtude -a/c m Figure A The dcri-itu - weft ill termined by flotation The kindnf rvactor t-lmun in Figure h waMt-ed throughout It I ..jmpnHCtl :* -phene.d flu-k I it t* >i with a rmiilfin/, i-ritfwi <! rentnfugnl impeller, ami n thn nmnu tcr ftr tn* i-urwg tin -u-- jen-ion temperature Hint w - turm-hed In * w an r hath With reactors of 2 lit*, r- or more *,j oat\ *ml r nten d 'limits if we* necessary to re-orl tn a centmug'll mi|*llei >imr tin moim* iM**r (dehsitx 0 1/2) had a fendcmu to * oik i 1 in flu mrfex '( hm .!* -ign of reactor wu- *t rtamU nut -uu* d for optimum elh* i n> \ . 1 ' i m forming di-jHT-ion-, hut it pio\. d * unwin* m ami *ntin !\ rierplafe for the purf**-*- of * i ilu mug :> ) itur t ff, chmin -- m -lahilizcr*. The ratio of water tn niomnm r w.t- in *int.*m'i 1 at ippniunatch' 12 to 1 by volume Although no iter nHiu of w.iici t<. nnomer favor men-a-rd \ n*l<of *h-i n w -phcrmd-. n w i- jn,-. hie to work with e^ual .nnomit'. nf i i- h without * m ounfenng | r\ii`H>t'T clustering in the prndm t I loth inorganic and organic i ta-*s ^ u| -.U'-|nn'Uvii ^t .vhiU/cj--. wrn L<tturK`<l. The nmrganic malcrjaU h i~ imj tn- ilciuiit phosphate were hwh iatcd uith npupii' |M>l\mcr pm>l- i:> Ti, |>artly due t< urfuc rnughm 'I lav win- inn~idtpd 'nicsirablc contnnunat* * that win- (lilluult r * rviumr iin) did >t permit tlic rnngi- nf .i\ctagi- parte It '-i/* - pn-HiM, with m T 1H1 K I l iiMI'lltnnN .----- 'i.lifin, >! |.K,i ISrln'ly, ui 1 i. !i 'iii- 1< ir\a<* -i.h + t* !>(.'>,. M (he 17 II M>. " . O >1 \ H11 t<n K l V l l1 a \\ riii'i' I 0mi i meih\i`r\ lir irid iim - .y JWt111 \ \ m>t iti MI an* l \ jneal hytirophilie |nh tuet - T hev wen* U -ted ipi tli- t (fneK it -cwral enneent r it i* |>ata nil -^onu* >f tlie 1111*0' * if* * 11 \ e. pn-^'llti l 111 Faille I. weiv obtained timg 100-iut ali'|ii"t- nl Ir^.h\ vu lght of -t ihdi/i 1 suliniun with 2A0 nd nt the dn 111 \ Un n/i ne imvtvm- \ n-ld- deiui d tmn run-, e trh differ ing mif\ ty the Htabih/er, wen* weigiied and "lewd Averagi **ph*`n ilitmet* rM n-pn-^-nt givin mc\c traction- The l.eiimi, tintum, ho example, n*pn*'**nt'i that puitnm nf the pnniu* f * auglo mi a *fandard 12-nu-h -<*nw, the 0.3-mm fractnm h tint pnttiori (>a--mga -taudird tO-me-h M^'n hut V.night on the M) 1 l igun T 1 t/ount- nt -]>h ne.d parlicj * m ea* h ie\e fra< - lion wmc nude will, an optical mn tmtieter ami m < a-toh i!!v * leak'd With i -phencili gr id* r The*^' cuutlt' Wen* C NpJ>*"A d tn \* r * * nt *t the total numU r oi p irtu le- in r:|i Ii -i/e r mg* 'I In- i lu-tt n d mat* rial ,n * ntu etitrat**d in the larger -17\- r ing**-. a*iountmg for the tower -phetv (uuut4 m thw rvgmn Marked \ iriatinti- m particle -1/1 di-ttihutmn art* appm-nt Apple j*'< tin .bowed a particularly hr**ad rangi* of parti* I** -i/* ' JN*I\\in\l al*olnl (mtilmili ^llutlna Vi.-cn-llx, *olilpk`tel\ sajmmtiedl Hot onl\ g t\e the narn>wi*>t -1/$ ili-t iff nit 1**11 hut al-o !**! tn a producr with a greater degti-e *f *pheri*,it> It -Iiuiild l*e empha-t/***l tli it. with the exception nf alcohol, mdy hnut`d tc'-t- h iv mad** <m the-** uulerid-, ami alllioUgh the re-alt- wep* mil rmr t* thn-e *ht:uned witH |hi1\mh>I :i! nlml. ntle r jstniple-* might pm\r mnv effertite parti* alaflt when the\ an* u-**l with luonuinci- otlw r than the dtwn\ |1 n-n/ene tmxtun*. I nder flu- * in uni-tain,y - [Milwmxl ahh**l tp|and !* m* rit futfh r *\- iiuunUiH) or POl-TV***,LALCCOt a h<.'0 poout* Figure `h Vliniuti*' l(c|re-*-t 11 a t iim of *A|.ige*t in ^leiirn-ion |NI\nieri/atinu *f l etlmujl I )n i 11 v I Ih*ii /('Il<* M ii* {1 inf*u tu it 1*ui 1- u ail 1 hi* inflii lift r it un* on the -(ru* f u ; f /< and projK-rtl**- l i, i * I *>l poI\X|h\l Iiholiul Mule' 1* n-i**n iu i-uremetit- *>n d- -*l\;ti*vi - a- will a- tlm-*. of pulv- * tin lene gl>* *l -uggi'-t 1 that Mude- nlf - <*/ waJ* r--oJuMi* ;* *J\ in* ! - m --ifut ion t*\f nl nt i* hint** or i* rl item at -urt** < - or mn r- in*- The twdetne -upmtft*- flu e-- nmption fhvt vl-orU { llioleeilli - at th*. Water lid* rf t irrangvd leir/ont illy ratte r thm m de- Jierpeielw uf il l \-hion exemprifuii In- - latr \ 1* id- "Hieiin ui'! hm-ltergi-r . / h 'H* . 1 .a ,1 h i\e n [101 f* d tlitf the prv^ m e *por- \\n\l d. ohnl nit\ p-ilma* tit* mterfa* ml t* ihiiii of Nujol in :iiU**ou~ -u-jn'Imi'in u "*'* < *.i, 1 71 _* H| ", Ht 4^ J *4 a- mu< h i- ,`gt'T ir tiinii- lu addition. th*v Iwiiti*! * e.ui-id*'fahl- variation 11 -urtam aetivitx l*ei w* *ri diff**r'tit gr id* * lu g* ne r d 1 hi p irt 1 dU K% dr*>l\ /*-*! grad-'t low*u the mnilamd t-n-mn iuo-t Othei- h m* foumt etratie re- Kay 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY nn TtBtX II. -tftbillMtOnula - 77-0 100-0 03 y*-0.08 1,10-1. 13 :-o 7* *9-0 93 ^>-0 33 V-0 34 Relative Stabilizing Phopektiea nr Vaiuoia (Ihaoea or I'oi.ymni Alcohol No. Sphem, <7 of Total F*iuilt in tarh Sim Hans ------ Kv. Sph-r Ditn , Mm Im Ov*r t Kc 1 7 1 3 00 03 02 W#tcht. ' f nf *ch Hiae Haiic* (Raimi on Total Sample Wrighti ----- 4v, Sjihrr* t>im . Mm 03 0 10 OS 13 40 30 \*0 '*' b 40 7"> 'ib OS to JO 40 90 0 0 0 10 <Ti 0 0 S 'At tj - 0 :>o 90 0 0 n b <* 30 40 no 90 93 21 - * -- ,v h 3rt o J '* ' Horv o' the mtnn*ic \i*nMt\ of 0 S2 i orn'-jHir d* to a nvimU r- ixerap- moleeulaf weight of -lpproxim.-it*dy ."VJ.OlXl S-pantnn "f thi-- gride into fraction* hv *ulul-ditv ditTrn-nti-il* xxould pn *umahlv -how the t>]ucal broad dis tribution of molicular weigfds High visco*ity and partialis h>drx>l\7x-d grille;* of |>nl\\iiix! ilcoho! wi-n* a.-v*o4*iatd with product.* of fewer aggn-gate* and ^mailer axe nip* parficli diainet* r* I*wer \ u Id* of *oherotd* wen* provided by the Imv ' _ grade** Howi-xer, the latti-r wx*n- effn - live at lower coma-ntration* than wen- ^D-i had to l*.` filten-d out of solution* of the high* r si*eoMt\ ;irmii*Mi)te with otfu-r grade* ('onetuifnftori* of a* low i* ruie*, Thm insoluble material whm actually invlevant *inee iK vinx 1 alcohol concentration anil m-comIv tneiiNurcment* OOCW^ (l>a*'d on weight of monomer) of low mol.-iular weight *tabili/er wi n- n- iclied In fun* iggregatnui tn prod w, n* mtulc on the final dilution after filtration uct* itecame appn-< table higun If *ho* t.1)*1 i fT i t on M/e dis Hun* wn* made m o-hter enpacits reactor'' of the txpe ihomi tribution w In n i oniTiit ial mu* of thn-e dtfTen-nt *fabih/i r gnnli * ii! Figure ti The rear for wa* ch irp*d with an aliquot ;>ortion of wen- \ aried Wit li a i om-ent rat mu of 2f `c of `*0 0 s2 *t d uli/i r, ,, iluhwr Holution arid sufficient dt-tdled wafer to provide a vnf- f*a?N-d on the dis ms IN-n/ ne niixtun*, a xicld of the dr- k4riit` of 3200 ml Tin* w.is *tirnal at 'JoO i pm a* 230 ml of *inal 0 3-mm *pfn mid* w i* nbtamid An might 1- *u*j"fid In h\ myllu luetie mixture containing Irc by wvight of U-n/osl higlier comentr.ition* of -tafuli/er lid to Mualli r ,n> Mp .nxide wen- added 'I he n a< turn wa* carried out at S0C (' fiarticle diamrfi r* vr 3 hour-1 Stirring wa* then ih-M-ontinucd. the product -epa- To axoid jMis-ible in:n i ur ten * due to gradual d* t noiation in *,nd. wa.'lied -*`Vcml time-witli methanol, and dried, High i flu leiu-v of tin *t ilnli/i-r, tn*h solution* Wert- u^ d with i fi ,in` charp*, accumulated by the drv -phencal produ<'t, nece*M- pn pa ration Tfie Mi*phMon pH at tlie end of txjncal }hiI\- ,tt4-d u*r of either high Imimditie*, ndioai 11\** *tatic-eh[unulur.a* iiu rization* with dixiii\ 11 en/em- mixture \arn <J !>etwia-n 4 S ,t? d ,,r graphite ducting in order to endin' trouhle fn-e M/e analx*r** oO I*n*umallv inhibitor and jirrhap* <`atalxKt fragnunt.* plt- *p?icroid* of fulls [*!ynieri7e<i divinx IU n/ nr mixture an* i ,rd. tnfu*ible, and < a*il\ fractured Mon over, on llmg in N-n- caiwd this The de*ir:ible jdl range wa* found to l** 3 To 7 IVlow pH ** 3, c!u*t*-nng In i on es a coiiMderable probli in In- , ne either at rooni ti mjierdun- or at St)J f dot* imt exn-ed cn-a*ing tlie pH to 10 apj* an d to ha\e little t-fTi ct on the -phene- i >< ' The-*- projN-rUi * indicate the high degn-e of im linkage its , hut opaijue product* from alkaline run* Migp M< d oi<lu<l<d |,ii h constitute* tin fraim work of the molecul ir *t rln fun* of the iin[>unt * and pns.siblr *urf ici roughness iner Many m it< rial* act a* pniipitaiit* for jMilxsinsl ill oho' \ I he n l tine rlTi et i \* ni ", a* M]*jNnsi<>n *t ibili/i r*. of s arum* Mi.'l add* call In1 tolerat*-d in fair colicellt i ation* but -N.lutn-ns 1 j* 11* of j*olxxih\l aleohol 1* given in Table II and I igun- S arv unite -4 iiMtise to alh dte^ witli the ]io**iMe cxirption of an, v an- arnnp-il an on!mg to their .-ohition \ i*co*its and di niomuin lisdroxidi- I,ow n-oli a ular weight grad* * m- npor'.ij of hxdroh-t* I Mu wen- obt iim d UMtig 0 -tiluhrer to In.- sijr]iri*mgls *tn*iti\e J) to i lei 1 ro|\t* * t**o<iated with `M^doti the weight *1 di\iu\llx-n/i iie imxtun* pn ul Sieve lianl water Higher ittoliiular witgfit. pirtiadx fisdroi\/..i -r m tiom an* expo -** d i* wi ight to j* r o ut b.L*cd on tin total gradi * an- li ** ifTi ct* d -.iinple weight I In h "j the MX f* ir graph* m I igore S repn * nt* shown in Figun * S and 'h it ^ entin \\ |>o*m!.'c to u-hw o .n rap' x it M* obtain* d is i th i -ingle gra<le of *t dali/er Hr pro* -harp *i/e di*tnbution* tliroiigli a nmaiL ible ron of parta'e a-ilulit x of mdi\ idu 11 run* \ an i| a* - the main fraction Tin nuinU t* in e-ich gnpfi ivpn- i.i the j-r .n inti i* * o* t in n -j* c - up} r l ft -hand eorm r i\ . 11 <m \ -i* m-f inf runic *i/ * liv sjmpls s ar s mg the tut nn-n \ w o-it \ . < i* gne of h s drop *i*. and i oiieent r-it loh oi polx s m \ 1 t !< "hot *t il alizi r ( ot:f i ol . f a git it ion fia* a *imi I if l\ pr i .t' uiiu i f fa < f ( '< mi Mr, t r i,,/i ih oMtx of the *t duh/i r u-* d Inn ' - gullied \ fwihxmxl Ji "hoi giad.-, ' ip!< , t In omulnt PS t) >2 h \ dmlv /ed, with an ilie*i'fictor*[NTmit'tln pn-piiitioiiof-plin *i/( r o gt * is i r i mg from two mn roti* to ^ ral nullimi t i- m 1' oi . t. r u*'"g t mii'ic Xt`Co*lt\ m n pn a >11- -oiuti,! nf o ^2 \i i ording to fspe tpparatu* *houn m ! igm> i- It i- n,oo did < n!t to n d- I. I.- 1 Pi .ill Figure 8* Itelati'e 'Mahih/mg l*n|M-rl ie-* of hthviinl tli-oliol nf \arxing 'fnlicular ^-iulit and Degree f 11\ drill > is Kimirr *1. FtTert of \ ing tux I \ltailml Staliili/rr j i'<ti4-'iitrati*ii on Sj,|H-rr >i/t* Distribution *s||||,ilirrr riiilrrnlniliiin. * , lui'nl On nrnlil ntf ntrtmi-r 1110 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol 43. No S c l n v t y **r I igurr 1. I(,lc of Pol> mrri/ation of IY limc.il Di\ ii > llien/ene \ iiritut* frm linn (rm^falnrf. ilftrrminni In futrt i lr ifrn-il v r liMiigi1 TiMt >*4 M0uS AT Figiirf 3. Kate of Polymerization of Terlinirul |)itin\|. benzene Determine*! by Purtiele l>riiUy ( lun|(r Rrtardalion fur iliffrfTQl partirlr iir i* ilijr to |irr>ritrr of iimikphfnf imyfn mi!h \\ it It ;m i| \ um 1 alcohol Miliitiimi t I.trki- uni |t|. nn m \, tfatoii vCHij; pin immi n:i aful fouinl carl-nnsl function iht s to * ihtu n hi in |ml> v lti\ 1 alcohol. TK*`\ wIa '1 th it k t l f,,r, lualmn u t- tv-lxm-iMr fur much nf tin* nl^-ru .l ,rili o!Trrvl, ih -uppoit of flit--, the fact that -l:ilIo p<<lssinsl iili.,fi(|| Milutmh' N* prvpana! hy boating for -a.`\ r t.1 houi- w/l, (UVJ \ K\ilrochloru ,H hi laght .-cat ton ng -(u,in * have -jj,^ that nu-li < ular aggn 'gafion occur* with tin- partialis hv*lrol\/. ,| fxtlssmsl alcohol* ( /) hIiuh' -aiIh! ulit !*- m api*nii- -oluti>t * <lrcna-r with an incn-a**- in tcm[>cratun\ In -pitc nf tin- n,,,. t iv it v ,, l`lor\ ali'l Lutnir (?) ihrckcl tin* correlation U`tw*-Mi intnjHU' \i-co>ity nt polvsmvl alcohol -olutmn ami nuinU-r- a\rr.oii* molecular w, ight w hilt1 examining it * im>li nil.ir -tnn tur> \ wrii * n( |M>ls\in\j alcohol- \\a- ti -N *1 tor -U'(Nm-i>ri -t.i- hili/cr filiation !htnn-tr \Hn-itirs uf their utiutou' miIuTim'- at 'Jo0 <' rangml Innu 0 33 to 1 13, nr a vim o-it s - is* rage mult * j. lar w* ighl nmp' from Ih.OOO to ha.000 {?} A -olution . f it h gi.ole s\a-* pP'paml In<i\v \ i-coMtV gra*le- g is e cl*- ir -oiu turn- \ sirs -mall ijuantity of mvilahl** mat* rial w.i*. prt m t I mttri' h, <>Mi*|M'iiMon I'ulMiiiTi/.ilion Iti .ii for \ mi! with Trclmii.il I >i% im \ ltn-n/4-m- I i^iirr 7. I 4'i liiiii a! Hit im\||h ii/i ii<- I'nltim r ^ptorr- 111 ii-t ra 11 iiil I 4-4IIIO I mi I I'* rli t hull \ l t r i b- 114-41 to '"iiIutumI I r.ii lion- >ti I .mil II I ho i' 11 |in .il II T-,iim fr^i't |uii. I'r < ii< tffi'H-i>i,l|-|ilMr** l- <t<i* til .ii i 1(111111,11 ion t>f -- t .it i<~ r It inti' l>` 1 ii t in it ( 'ii > ill 4;, ufj|iliili- iliintmit, w lii> h rnlm i> lln> 1 ln*r|,i * 1 - ii-i ,t fur all iinr iinii|t<.i % 4. * 1113 IMDUSTBlAt AlfD IXQIX*SKtX CttXMXftTXT VoL 4% I 1. hhawCI Dhtoyltnnm (4-90 Microns) Figure 19. Polymer Spheres from Technical Divinylbrnxene (Rolled Sample) definite size distributions in the extremes of the above ranges. This is especially true of the small spheroids. Judging from sty rene (10), the divinylbensne mixture should have an interfacial tension with water of approximately 35 dynes per cm. Besides considerable energy in the form of high speed stirring, visrous aqueous solutions coupled with appreciable surface activity of partially hydrolysed polyvinyl alcohols are required to reduce the average droplet me to the 20-micron range. In a typical reaction, a 2-liter spherical flask (Figure 0) was charged with 1200 ml. of 2% stabiliser (77-0.99) and 92 grama of divinylhenrenc mixture catalysed with 1 % benioyl peroxide. The suspen sion was stirred at 740 r.p.m. for 5 hours at 80* C. Foaming was not severe (9). Foam that did form was unstable and con trollable. Removal of the stabiliser and other impurities from the product was accomplished with repeated washinp and centrifupl separations. The dried product consisted of spheroids .111 Encountered in Jjnufinition Products ranging from 7 to 38 microns in diameter (Figure 10). Thephytecal behavior of this powder closely resembled that of a BU, These particles can be retarded as hup nncrogel mdMntft (j^ which, however, sediment from sohition quit* completely mnfe gravity. Reduction of the stirring rate to SOS r.p.m. resulted A a product varying between 14 and 03 microns average psrttafe diameter. Urn of a homogenising miser gave a particle Mae range of 3 to 8 microns with the mine suspension. Various defects commonly found in aispenaon polymerisation products are shown in Figure 11. These were the attributes 1 be minimised by this study. Scrutiny of the individual pari reveals twinned and clustered spheroids throughout. A cemoapheroida, some of which are cracked, appear aa the lighter particles, and occluded bubbles can be seen in a few othn. Most of the sample is composed of well-fanned spheres as shown in the rolled sample, Figure 12. Tear-shaped spheroids, not illus trated, are frequently found among products with an averap diameter of several millimeters. . ACKNOVLKDCMK.NT The authors wish to thank W. O. Baker for many helpful sug gestions. urauTTJii errid (1) Baker. Inn. Ena. Cwxm., 41. 511 (1940). j <2> Biehn and Emsbarger. Ibid.. 40. 1449 (1948). I (3) Bunn. /.Client. Sot, 1947,297. (4) Clarks and Blout, J. Polymer, Sri.. 1. 419 (1946). (5) Coulter. Ckem. Kay. Preyrtte. 45. 227 (1949). (6) Cooper and Bay. J. Polymer Se*.. 3. 345 (1948). (7) Floty and Leutner,/bid.. 3.880 <1948)- (8) Frytin* and Harrington, Iwo. Eko. Cwiu., 38, 114 (1944). (9) Harkins^ J- Polymer Sei,, 5,217 (1950). (10) Herkina. Brown, and Davies, J. Am. Ckem. Soc., 39,354 (1917). (11) Hohenetein and Mark. J. Polymer Sei.. 1. 127 (1946). (12) Jones, Brit. Phutico, 15,382 (1943). (13) Richardson. J. Colloid Sei.. 5,404 (1950). (14) Rushton. 'Technique of Organic Chemistry," Vol. Ill, p. 109. New York. N. Y,, Intersrieooe Publishers. Inc.. 1950. (16) Snell. Inn. Eko. Cam*.. 38, 107 (1943). (16) Taylor. Pm. Roy. Soe. (London). 1464. 501 (1994). (17) Timnahetr. Bier, and Nord, Pne. .Well. dead. -Set. V. 3.. 35.164 (1940). ) Kacsrrn Dinabr S. 1940. Fmsstod hWors ten DlrUoa el Hh rhy mer CWaliS) at tea Hath UaMlw at tte Aamcu Cnnu Soctcrr, Chinan, HL