THE COPOLYMERIZATEON OF STYRENE
AND [TACORIC WDRIDE

The“: for Hm Degree 0‘ M. 5.
MICHIGAN STATE UNWERSITY

Donald Arne Kangas
1958

 

. fiflESl:

 

LIBRARY

Michigan State
University

m oc-Pch-mzmimfi or mum
my moclam amazing

Wm» Emma

Eabmttad tn the 81222601 6! Gamma swam of Iéflcmgan
Statva Humanity of Agflcultum and Applied Scimwo
in partial mum at £319 rmirwmta fer

' tiaa doma cf

“$13732" (.1? 331.“? 27’.
item'tmmt a: Chmfistz‘y

3:2?“
‘4'?“

r» r

. f\
“‘13

L

La VA

"5‘ «ax

AC: -1K-K3a3g ,.Â¥.:ai '

The author wishes to «threat! his
appreciation to 32:. my: smile far an
interest, menses-amt and guidance in
misting this project.

fie 19 also inflated to The new
(themes). COW tar manna than, any
from regala: autism, to maple“ portion
of this project and to iii-r. Killian Pavalich
of the Po 1pm:- Research Laboratory for his
invaluable assistance.

Ilfliflllfllliinfl

a"; auras: “rainy: a? SITJE
az... max :51: mama

:mld am Mags:

mural ta the Selmel at 6mm“ 3mm of Eliefr'xigm
3M“ Univmity cf Agicaltm an: Applied.- shims
in finial fulfillmt a: we requirwmzta for
the firearm af

2mm: ( F 3?: 1353?;
imrtamt at Ghexelatry

Year 1955

ammod :

 

Styrene: mi Hamel: new? So am eapalyem-iead 1:: Emma and
in teetmlvix‘amnn 001m“ with bmaayl males at bin-awiaabamou
max-1.10 catalyst.

Tee mm at capalyeermum a: 1:3. m1. ram a: ”mu am:
items-11a meg-and. m detammad 1n. the fan: mam, based an
awkward mama cmmtmtima and the sweat a: when: to me.

The rate! were few to be that emai- with We ta new m'weer
ccmeatmum. The apparent first awe: mta mutant“ was calculate.
for ma grams. 1

The cmltmn at the capclreers were also dammed, by the
eats a: aislupzmnnaa at mama", by 33.li amlysio a! the
capalyew, and by titration «1,: the aopclym by both patmtlceetdc and
man {mm mm.

a umber avenge mlmln: weight a: 23,!16: m fauna by the anions
W mam far a copolner mm in lam-am column. binge
average W Mafia. were ahmnad by the light Scattering metf'axi,
far a W: W in benzene “lame the weight average mlacalar
Wight no 155+,LCO. and far we capclmera pmpareé la tetrahyémmnn
the weight "my wheeler 1&1;th was 50-,LC-C.

1v

mm C? “$3333

Page

Eminence
I. W Cid EBOPCOQQCOcoccoacoauoaaoataoaooaaooooaacan...

II. muaaoaaoooaaoauoaooaoeaaaaaoaaaoooaaaaoqaooaaoaooa

I. mutual“ DWtk-n of Mam, Stym and
1mm Wimaooooaaoaoaaoaacaoauaoacaaaouaaaoaoaaao

A. Wt“)?! 05' IWMQ mm, W!
m on ”mt-Intimate..-cacaoaoaoaooaooaoaooaa
1. Rwanda 809M139 MWaaoaaoaaaaooaaoaaa

20 Catalyzed bmfimtifinaooaaaooaoaoaoaaoaam

.3. 31M$ bWt-iGnaooaooooooaaoooaaa00at.

B. 329?.th at laconic Anhyfiride, 2mm:-
m an the Atld WHO-float.oaooacaooaaoaoaoooa
1. Back titration Of 8:13:38. Mouton-coon...
20 Direct titration Of Mid MMaacooooo
’- Titration Of Wthyi «tar............

Co Dmm Gt Emmia‘aoaoaooaoaaaaoaaacno»...
1. Hercurlc MGM” Waaaaona'amOIoaooo.
2. BW‘ Wfiflfloaaoooaocaaaoaaa0.00...

D. Image of stream am Inmate Anhydrlcio

1n Waaooaoaocaoaaooaooaaaaaaoaauaacaaacoa

II. (1090th at Styrene and laconic AMI-lea, fate

or auction Swain-soc":aoaacoaaoaooaooococooaaaaooooao
la PMMaoaaoat-aaoaaaoaaaooccoaoooaa"-00.00...

3. WWtiflnl and Rmuuuaoaooaumcouau

0. Order a: Reaction with Respect to MW and
Itaaonic Anhylriée Cancentmuam..uu.uu.n..

Do Overall late Cr: 3L3E3$§$Plfifitimoooaaoaoooaaaoaaa

~11 UNITS“

“at! gamma:

U

5:52;:

TAM CF CGST'E‘T‘S .. Ccntimed

Page
III. Andy-1n of swam-Income We. Commas:-
Cmitmaoaooaovoaoooaaaaooooaaaooaocaaooacocooaoaao 55
A. Elmtal W1. 0: ccpomocoooooooooooaoo I“:

B. Potmtbeatrio and High Frequmcy fixation. at
Styrene-Imus: Animirma Copalyml...........

10 5331‘!” mewaoaooaanacaaoooaooaaooao

2. 1h]: cater flmmootoooooacoooaoooaua

IV. Eclacuhr weight of CWItaemde mum-1d.
Copolyem

0......0.00.00....60....OOQOIIOOOOOO0.00000...

A . Hulmlar weight at a emu-Imam“ mwndo
" by In Cmtio Fm “Wooomoooao

1. Th. C-lzmagoaoooacacia-aoaaaaaoaucta

2. Emmooocaooooaaooooao-oaaocoaaooooo

3o )ieummt. 0: (£th PWoaooaoooo

8. blank: weight at Styma-Itacanic Writ}.
CW" by ‘ Light Scattering: Hflimaoaooocoo
1. Light scattering pEeraooooooooaouo
2. Procedure [01' timing Wt‘ooooaoo
3. Outline of calculation: of molecular
vaigl‘za from light. Owner-1n; ream-t
flantlouaoooaaoatooaooococoaoaoooace-coo.

h. E‘aclecnlar Weight WtW-aoaaacoaoa
I. MIMI for Mtitative Betmaimfim of the f-‘kwnaaeati. .
II. cmmuaa a: Styx-ma and Iueanla We,

3‘“ Smdifloouaoooaoooovmlaoaaaaoooaoaaaaaoaoaaoooaaaou

55
S?
57

57

63
66
69
7o

75
73
77

73
8?

91

93

m. W1m of says-madam marched. comma"... 1.0:;

H. Molecular Edam or Emma-vitamin may

Copol‘yumaoaoouoooaoooooooaaoaaaooooooactoo-000...”... 1C6

mmrmaacoaoooooaoooaaovooaoaoaoaacacao...aoaoaoaoaaaaaaoca 11C

umumm CITED................................................ 13.2

v1

m enema-r s
137% i. Zia-'0 {a}. 3.1.};

I. mess; m: we” a:

The study of styrene am}. masonic mtnmm capokmerlzatian has
hm I. confining project in an. labs-zeta}? (1,2). ~ rue: immi-
mfim have aim the napalm» ta "be at“ an alternathag mam-m: unit.
structure mam- ta that few vim stem-ale mvénda «polymer
(3.5.5). The was a: this we. was an «latex-cans: the mtm of the
mommmaymmmatmrm
Wmmumuummimummmeama
Wm 13% In addition, mummg of mlecala: weight of
m capalymm were we to éeaemine the influence of the aalvmt and
catalyst a: the reaction.

II. £16133

LWW ‘
Mimcmmmommmmw)m1mum

(mu. macaw. 99$ W). Ana-thrm

WmmmmmumH;

203W
MWWHIWMWWWW,W
mun-auctpolsmnumdmmwthumctamipi-
Uhmthuflfimatum.
3.3a“
www.mmmmmm.
8...!ch

quW(7)mmbymmaum
mum-mam; hemmgc6546° .

fizz-mm").
hMudfld(8)hymumdthmm

(mmtqunlntmtml).mdwx-aflmm1t1mtortm

ham. mmmmmmwonmpommwc;

6.m

mwmmwwmflmmm
urban“. mmmuwmmmwummrmt
utmmtmmmtmxmummwtfimm
mums».
fluenm

m,USPm.

35.1”” ”mu.

‘ .Ea‘ iAé- Luii

I. mama-m mmmmma w :tmm, 3mm
mmocmcnmm

hmmammmmm,mm«nmmmum

mammummmmmmmm,
mmmmmmummmuwmmm
«mWMmMaummmm. mm

meMWthWMm—
mum. mix-lam «mum (9-1.3). «martin Wan-Mon
m), mumwdmmgmw (15). mammal-cu
wW7).muauuthm(m).-nammumm
mum-21). mmummwmmmmum
mmummtwmmmmmm

«mum-mm»)...

LWufle-m
traummamxbugmmmmmma
mwmammummmmmuum
m.
n-cn-czw . (masochng. when“

MI
ziflflmfia 9 01130063

unstimulmmtmmmmu. mo
mammumdummumumm

“mm mutation ‘8. camartm'i to mac cmorit'ia by asking
”dim chloride bafcra £1th of tha 1.1me acetic mm.
r-iet‘hml in W to be the beat. :01va for the routine: and was
W far the» ammucaa. In the can of 1mm flb‘Wfifififl
wummmmmummmmwnmm
mama-am (22), main: 11'. neormsal-v to flat mm tho mum
wry]. titer of 1% acid berm pmaafiing with tho We
mama motion.
Egrmm‘gi 1n “carat-313‘ mfigfizm (amtximtely 0 .3 an.) W19
mfismlvadtaléml. ctbmzm, 5%.de
«mum in! 30 m1. of mammal. Tim tcid m thm am
with mm mm int-3W0 to t mamas: mt! paint.
After 3; pm a: W manta kw! ham added the alumni
m moved to “and for cam-Emit hear) 75 ml. of.“ “mm
mam chin-11¢}. Caution were am and tho 1min umm: with
mm mm Ewe-madam solution to A phmmmmm and point.
m percent of atomic new and firmerma vars calculated :5
follow:
&. 87 direct umuan of the mid.

Percent man-mic acid I

Pmm 1mm ant-minded ' * ““393“ r an 11.2

maymmmammum mmmflm mercuric:
manta mum.

 

{)5

§ 1
Famed; income m?g*flrifi9 u ”1‘ ”353

 

 

teams: I

mam AIS'YRI'B THIT'H‘ATICH BI
$391.3 RIC AGF'EIVEE 2‘37." KID

 

   

9323313: Jimmie An? 3mm

 

ample fifi‘ati’m e a. ‘ ‘ 125. c?
vtzaatumtion Acid Mien
Mun-r- ““ _::~ A‘ A“ :: r.~--tw_-+-‘:._ VA“ ~*‘ “fir‘w M M ‘4‘ ’4‘“:
1. than“ new 92.1.3 97.56
2. laconic W, We 3. 2?.53 109.1
3. 1mm Md” ml: 2 20.3? 101.3
WWA; ‘b M :W‘:“‘ “W'WZ. ‘1‘: “‘“‘::"t:‘*“::. f“ ‘t“““w“ 1# “1‘“

 

ZcCibWbmt-im. _
mo mum at angle-m 12213.9.th m be «mad by
muma(u),pmvmmgngmmlmthodbywhmhmmw
«mmaWofwmpmfilmbodmd.
ma mummmewwmmmm
“WCWWG.15@.)W¢£1WW,
mammaafimémwmmmwmwmm.
crater. WWtermtmwfimoonx.
mmumtmwwmwmmmazu.
mama-9mm. mmmmrwm
Eflodwfiwmmommmmmm-
mnmumm “thummmmw. sum Imam“!

was: an in WW. 3339 pamt of .1me We mm"!
mm u ram.

Pam-mt income
Inhy‘irwo

 

33m: Cm W: by this pmcacMra gave a. min: for
sum mmmu o: 66.5%.

3. Diract bmmtim.
sun 0. thin? mum fer mummy. (£127thth of Wade
Winn, which has been mad :0:- atyxma (1.0), 1! the €5.th
mum by a solution a: Emma in wean acid.
m 9:111:25!

I. in mantel:- wig?w& “992$me 0.1; 33.) «mph of
immmmm mmmwm
directly tin-um with mm in acetic acid lolntion.
“than mags color at mm mm indicates the: and,
paint. The pamaxt of Masonic “mam m WW
u tongue:
rm 1mm urban? -9233 .

 

human-Motmmmgmtmwdadwm
accurately weighed «may 0.2; 9:.) m1. a!
1mm Wirifia, fiaich Ind hem dissolved in human
WWmWWWMamlmmme
and film potassim We salvation m aided. "ma
inmate?! iodina was titrated with steward Mirna

(:0

tidomlmta, um; aw taxation at; m Mater.
mmmwiummmmmmmn
fellows:

Percent Maintain
Writ?»

 

w: The direct “tut-inn, madam (0.), we a V8139 for
pm 1W mhyvnda a: 5.82:, while thin hack titration: a!
~m 11mins, mom 0:), we talus tar pair. 1W
amafiride cf 5 .355.

B. Winn. of thumb: mwmida, fietlmdn M m Acid mm

my other motive calm in itacmfic mugs m which quanti-
tative Man- m M based is the warms am. In «mum to
tha m). m for GM WWW, by dim titration with
Mam}: turgid—mo: mm, 115 “Nahum“ the
mm of 1mm mamas with 03W hum Siam). and Ham
(22) Mn W that t2» mmaeter is {amend instantaneously tad
muhuvm a room mm mm & pram-m? was: and a cyclic
anhydrido.

2.. Rack tin-tim- of new base.
mm An ins-MW wished (mm: 0.2 can.) swim
at 1W We in diswlmd in «atone. To thin minim
meaddédxoo a}... of (3.12338 2! mm mm. and the nautical
In mud on u? m bath: to boil eff tin mm. 71:90:1an
mu then cooled and tho mesa new hydroxide m imam with

fim'KEufl :m-‘iwimmc mic: aeration, to a phanclptifimlein ma:
paint . ma {mo-mt of: itaccznio mas-ids m “mam as
mum:

Pmmt imam

C“! 331 5 6
made

 

 

m' 1511' main!“ we a value £51- pnro laconic aim-arms
¢£ 939-3630,.

2. Emmet titration of mid Martian.
Pres-ammo in manta]: mm 035910 at 1% W34:
(@9th 0.2 p.) m aimzm in bum. 25 mi. of amm-
odntam-a ~wm,anaummplomhatwmumum,'
term mm. Thadihuinimcm Wanna:
mutt-2.113%, to s WMhfimlain and point: with stamina! coding:
W. maporcenterimemic mmmmwu
£9110!!!

 

Mimi? II

means immm D’EWSW‘EEQTICEE? F3351 113m T'I'fim’i‘fllfi
. CF 373 ACID Fu'EISTICZJ ‘

 

 

 

 

 

 

small Pemmt mm mum-
W ”‘3 W villi—Tm"? _ ‘ ““‘m: “T'V; '3“ ‘11....
1mm acid _ 99.70
mm We, m1: 1 93.1;0
lacunae “midis, W 2 93.11:

 

WW

3. fitmtinn of mmwthyl 33:341'.
1; I In» hm: mmfim, mun: admiridaa an be de‘fimfl by

£2.th tbs 80mm eater e: the gimme acid with base.
W: in meat-ate]: mmw mans a: itawxie Wigwam,
(ammzimtal‘y 0.1; $90) , this asserted in (830331333 methane]. an?
121m mmlizad nth swarm almholic Wanna Mamida
sciatica to n Mimi-33min mi point. mm mm M lbw-unis
m‘im In than mum: as follows:

 

11.2

.. .3112 III

mama.“ gammy“. rm "W; g «.3 a: W 34.3 Ezra;

 

_.V . h.— .....I_..- .-_.; - , - L ‘_,__ _ ‘L. m 4 _._...
v—y— v —rr w w— A ,‘r v .- W
A - ‘ M A -_. T... M .1 ‘4'

W “w -

 

 

We . Pea-amt Itaconia AWQ
m V “‘ L‘L—H‘““ A“ W “A“ ‘ “SHAW iv 3: 32-3; w. A _; g 7 “h“ v“
1% field 9&,95
laconic made, m1: 1 99.5%}
1W «mm, mm: 2 £43.63

www.ms 1a,;

.-

 

$733323! CF 1:25.333 £31212?“ K”! mama? MM .-' FITS}?
BI VAELLUB brings C? $3.41; @3311}!

  

~-'-----o-.--~ m- --“mwuvmrmmm¢1w-h~~m\swu-n...-~~.....~..u_«v‘ . ' V "

 

Percent Imam
Animh'kh

M ‘ ALA ._;_._ LA‘ .A. 44._ .AA. _._.L A . M
VT fl. w—r— 7....

LUnumtionthion
1.mrumiawetata.ou.soo..... 27.7
h.mh1nwbmmtim “urn-1.... 66.3-
c.mmtmmumum...;.u. 0.8
«bwktumticncf «mean hmnino . . . >. 5.3

Zofithdmwmmn

W

‘0 hack titration 0: 332333 M39 0 I o I a 93.30
mafia-ecttitmtim Qinogocntco 93.55
e. W $1.th caf the whammy!» cater 1(6- .31

C. Datamtica at Emma

Quantitative methods fer 1:119 fiatmfim or am m but
m m tho w'wlmic mtnmticm. 1% rib-3:30:13 far 613th ethylmic
“mum In!" m mim b2," Stena (9), and mini-.5316 @313de for
W by Lace (23). A dimet bmmimtim mum has m new by .
' Mg and Levin (10), while mum and Hams. (33) have dammed .
«Wad mum of a new ems/ml applicatim. The mercuric
teats“ motion (19.21) has me ham via-3913 used fer analysis at

W¢

1. fimnfie Acetate flatbed.

mm mm“ used was 063th tin m an already has been
dam-11w: in Scenes: 1, bl, except that it w mum to
Malta tho mid before waving cut the umm.

2mm: An .0th weighed “ml: of W, (approximtfly

0.3 W m waived in L5 a1. banana, 25 :31. of m cm

chinrwacndxs ml. awhfiaml. Weddinghmetmric

mummmmmmmumtcrwmvs
i1. 01' hMted audit»! chlariéa caution m added and the
ample united with mam sodium We 39111th to :

Wm at! point. fins paremt styren- m mm as

 

 

my rat aux-min mutate Wad tar tho domticn or
W m. a “in. or 95£2§.

his-WWW.
mmmmtmuwmmmwmmtmm
Mfummcfmmmanmm.
W WWWmmcuyuhwobm
Whammyhl, tortmmmaomlyfll-
Bet-h mflmmuad (a) M timticnto the micro:
WWW mmumtm cf mam bromine, indoo-
anr. The W flmm mlcuhtad as £611.01!!!

(a) Direct titration!

ml LBJ? H at Br 5.2

Parcmt. sigma d as.

(1:) Back titanium of access tam-mm

P, 't _ gblet};a§ 0 m1! um) (3. a! lie. at; _)

maxim. w w(flw “WW fiat.
5.2

@143! mm on par: damn: nuns mean” (t), pave

ulna. e! 98 .133, mm: pm (b), m «has at 99.5%.

141%?

mm: c3 vmms ems": 2m 5W
BI vmmm *Wt-airs c2? rzkmm

   

 

83ml. Pmmt Styrene
“m”; :..w.w __.__
1. hum-13 manta . 95-6
2. Dim bum umum 98.1
3. Buck “mm of m brawn. 99.5

 

 

 

 

D. Wtimdstmomdlmc mmmmuwu
rwmotmmxmmemmmmuu
-Wmtmronmscmmmmaobmgmu

only“! of nah commit an applicable:
1. 59001110 ‘2th of We amp and teal amt.

of ammo mutation.

2 o Detazfifiantion 0f Inimirida grouy Ind Iolcotiv. actuation

detemucm tor W19.

3. 8m. maturation mmm for no}; W,

‘ tumult: was and thyme.-

h. Salsa-tin mama-sum dotammmmen for W or imam;-

memo, and tom W o: «m mmtm.

thn of method. and far the mutual" damn» a:
tweak: was nod mm, in the mainline Section, Wt. 1.23%
W: Ia: total maturation were W10 for tumm was.
We, than no no method mm. for menu minim-tum
mum a: 1mm: W9. The” Wanna: ammo
W1.3mdh. Earner, .Ipociflemmd tordetomining
We LI mm. by dire“ “tram with bromine, and income
We can In ashram-d “the“ Worm by titration of tha
and function. Thou Mind. taro tried in the following Wt.
I» We. in both humans and tatmlvdmhm solution»

It!” rm tint moorings cobra: umbmmm mt
mummmum, bmnact¢ynnucomvh1¢h
mwmmmumbmmmum. Fox-thaws»
«mm o: m m nude in tutuizwdrom‘n, but the man-
‘tnuonc: mm. mmtmmriwoutin tatnhydmmmno
W by durum. m um um polymr mm.

 

 

LBW 001nm

5W LIBS? W21.
1mm m‘mirido mazes Md.

2. tetrthyémm me! mane caution
Menu mum-1a. 5mm Wm.

 

C 06383 W310
mam own.

“1‘: _‘—‘ - :w‘flm

1-15

II. WEMZATICN C]? 51123“! if. JAE-ID moo-2m AHHIISREZE,

RATE CF Emcnm grams
wmmammmiwmmonmcntu
mm in n 101 ml. nth, rm carried on in hm ”hm. banana
www.mmmumu,mnpmmmomuum

WWW. Than“ or each wanna-1WD:
WMMMmuWkun-W.tor
tuba-mate! pow {mad and, trim” pom)... formal-mate:
mummmumtm. awmumrm WW‘MDM
mWWuanmWMtyormu. Mon
WWMttbomthMMMw
www.mdmmmdoofthopmmtmfian
Wimmmarpomromummmmw-
.umdetmmmmwnmu. 2210de
otmowmmmdnommmoftmw.
udwnmtmm Suction Human. cementumm
uwnummwmwoortmmm.

A. Procedun

The wpolymrtutionl wort carried out in 0.1.1 clan Wt,
' under a nth-om atmosphere, an Huh t new lmpling device, u tech-
nimo mm: W in thin labor-115917 for mung puma“:
mum and «caribou by that“, 0111. g; g. (1,3...2h). In thin
prawn: uu tho polymerisation. um «nixed out in l 1,63) m]...

17

that-necked mmd-bottomd nu}: with W [has Joint. fitted with

m. conduit with «lam chlorido tub.“ tho top. 12.1.th
inlet. filmmaker, and um unplug device. Tho Mk nu hated
Wuonhthonmnoomnhotphu. fluwmtmm
mmatmmmm,eo°ctormmm63°ctor
Wm.
mmwwmtdiuMeWmdtMmmwmt
aulmvmmmwm,mmmmmwarthowmo
um,mmmm,mmtmwomm1m
whntmmmlvmtordlu. summmwuwnmo:
mmmmmwmmmmmm. umuwmm
mumwatrmmmmmmmdotmmm
“mamas“,mmtommmmtmuammm
“mmgtnmum. Anwlommmimodutolyuingtho
mung device md than at appropriate Morals. W motion
magma-mum. Inthomowhmmmm
tho what and budge-WWW tha «my» fish. cumin m
WdtmtlymodfitmuduMmhth.

Tho thionl at Ityrm and tumult: Wanda momma”
mmummmmSwmlfionumucthbmmm
~tiara“inauguratingttxopolsmwmu«mulling». $110001»th
M0 in Whom tolvant could not be mulyud for start-mo u
mtwmsthI—Dnmflmommmmmmuwm
ohm by «12m... 51m. tho polymer precipitates from hm,

it In. counted by marina on a Gown unmitigmhed, dried, and
trauma. 8mm”, the polymer had to be precipitated rm W
mun Donation by n manhunt. Xylem ml round to be a fitment:
precipitant and m and for thin We. A man taco of unto:-
m a» mum to mum“ m- precipitation. mm- mm; a
’W mi. of magma mum centrifugedmd trusted in.
“In W a: dmdbad above for win obtained tron aopomm~
sum in human Iolvmt.

mainlcopomermlutm mammmuhydmmnu
bytmmdimnofmlvdmulctharto mommmm. This an
1 Inch {mar Mitt“, but mum thin as. a: «on We. of mm
in tho groom. Capolymr amia- me mad; Wad with
macaw-t utmtcrto Whamouotmmbefom
We

3. Cmenndfiqu
mmadmtmhuadinmrmwpomumm
maumumwm.muammwmaumm
metmmmumxmxnmmxmgnn.
mmmwuebmnmnutmmmlau for
tho unc- m outlined below um um m1. «muons.
mranwugqubollmouod mama this nation:
n,‘ uwcmmmnotmntwum, t.
K. ammmutmemmmwuuwtm. t.
3,“:- mmummmmmn o: m.

M: I mew. scour wwmtmticn oi imagine admiride.
1% In mole {Rattan er ltwwflic anzzgnama in tha- mpolm-ar .
I. A . a itacmnd amiwirida

T31? u mm’EfimMI-m

33:}. :- 13312034. paltxdda

biwao, 1- hwmmtymnitrila

1. Parent polymiation Irma the weight of W tamed Iron
bmam Duration:

Pmt polynemnion o

. of
0‘; 13.2

Vt.
33mg, Whmlntigng
' a q - 9’ P. 3" Big-pm a -
Farcem po.amar£..,gati..n a $4 (9%) 13.2 . 6mg
2. Pusan 90th m the weight of empower tanned from
Wm mutton:
Par-cast pom-flatten I W 13.3.
ml. mum
I‘mmt WM :- {0&8- Du'z '- 15.03
Lmhrmmtntmna! W, H; tortSnl. Align inhuman
mum:

R; n We!

80ml- calculation!

R‘.W .Com

 

 

1;. am maximum or 1mm anim’n‘ide, :3” for a 5 :21. name:
in Mme mlutim:

. ELM—5'3 g hafJfl-“fi

Small. calculations
’5' . W I 0.30),;

5. molar mutation of 1mm anhydrida, H3, in W
continua

 

A want-.1211. alumni. ma Was: 93 the claw layu- u'tar . W

was or xylem m added to precipitnta mo W.
s' . 13:1. 1mg) (m a: para)
'1‘ m , _._..

 

Sm]; calculation:
“n'W W .m;

6. Huh:- mmfiw or W, K1, in WNW aviation,
tron durum. at polymer 1'0th and W. or 1W6
azfzyfirldu '

 

31mph mum:

at; «- wt (9.2;) ~ 112(0 .275)
V I1

”1 . 0.270

 

1. PM polynedntmn, from the rats of fimppmmnca or mmmma

21

Percent polymrmuon :- [103‘ (3.510 4,11) . 112 GE: 413)] 1.24m

Staph calculation:

Parent. Weston :- [103 (0.332 . 0.231) d- m m
(0.313 It 0.185)] 1.13342

Parent polymrinunn - 36.555

8. Role fraction of laconic mmfirxde 1n the capolymer, Ha:

I . Mon-H
' 31- . g1,»

 

MR VII
SIE~€RRI CF comnzmzamm

 

1; Initial

 

" ‘ ' ‘ ‘ . . amt: a! e
* ' ‘ Kind 9. Reaction

was 26.10 7.56 bum 700.0 nae. 0.232 0.915
17.30 13.60 7.55 bases. sum yaw-0.11.3 0.916
2mm 26.10 was 2:2? 700.0 Bi}. 0.232 c.925
21:30 26.10 7&3 23W 702 bio-cm 0.159 0.925
mun-um
maximums-momma thin actions

14.. I 1mm m‘vfixidc

my I Wham

BIO. (I M We

bin-«o '- human-While

23

um: VIII

mm or 5mm: er mums um ccsmsxmn or mum
(In 1:1 SW! imam ankmirhfia copolynnriutica
in human- aolvant by busy). pamxido catalyst.)

.. .,.... -......q...-—*.r.—. funn- —v--' aura-m“. a—MAv-a—uwm- -. w» ......~, »- - -~..Ur‘ CID-M.“ v---'\ ‘Wn—lfA-IuJ’u-o- .

     

 

 

 

 

Tim mui‘ccnc . {denim . 142113”
mam 3‘ sum 14. M A - W11...
a. o 0.332 0.313 *-
60 0.231 0485 0.5m:
m 0.130 0.0537 0.523
1313 mm (fist-$3 6.5314
2m 0.532 0.029 0.510
350 0.610 0.015 0.511
soc . 0.008 .
730 . 0.506 «-
h. «plum WM
0 0.330 6.310 -
15 0.318 (3.301;
30 0.285 0.23:. 0.576
60 0.221 0.176 0.550
150 0.065 0.060 0.521
2m 0.055 0.029 0.510
162 «- 0.016 .

 

2’4

Tam II.

RATE OF PCLE‘EER NMTICE
(In 131 “Wilma: Admit-ids Bonanza-nation in 8mm
Solvent by W1 Pamxido um)

 

 

 

0 0.2 .-
60 36.5 36.8
120 68 .2 66.9
150 77 .8 76.9
210 86.3 83 .5
360 90.5 96.5
600 92 .3 '-
730 93 .7 a
5. Wu poly-urination
O 0 .1 o
15 S .2 2 .6
30 15.6 15.8
60 ' 33 .2 33 .0
150 75.3 30 .5
21.0 86.2 .-
362 «s

 

100.2

 

25

QNV

.6-

\ mmxutié wSK

3m; Qam. Qm\ mad

(3
-1 ‘0
“'3

Q0

 

59m /

 

q .. i N

O . mtmk$xw
.s. x a .s H. >\ a
QQxSQw wqmmth S Xm®hxhu NQ mmw
tsfi hmtmkxxflg K8 TN. .. mtmkxsxm \..\

wkmSoS§\ aRV mutbkmeQOQQ as meQ

 

 

 

L6

5. N.Q

. 3

$6

a 0/; Oxfl/awo Q JD/OW

26

\mmfibSSN MER

 

     

figure 2

 

QQQ 930 a». 9&4 com mom, 9% Qm< 9.3 Ow Q
:QN
. %
mkmSQtQS 9 av d
d o a 0
qubkthKhmoc 39$“ 5/
a w
-I . \cmSKQqN km5®mq RACK anW
1.x a 3.3%“ . 4. m
16% 0
U
+ o q \
56(ha mammtbfl S s a
a . . . . n
Xm®bth WNm‘ Y\ . mtmkmxm \.\
tQfimewEmwoofiw g8 m\ SQ

 

 

 

27

figU/‘E’ 3

Q3»

\mofsgfit mEAN

QQm. 09m. QVN Qm\ QN\ QQ

 

 

di-

p p b
- u a %

 

,w ;

QQQQQM, mtmwfimw S \w\\b\bm NQNQ
tofbkikmkxanoxsb Y.\ n QOxmxm \..\
\wSmVoQob g8 QEEBRSOU

A
f

Se,
Q

i
V / UO/ZIJIOZ/ a/OM/

6&6

és

 

 

“Sm

 

28

m 1
RATE or nmrrmmca or mmz-zsm, camsrncn or
m commm A... mm :9 m. «w? ’TIOH
(101. Styx-unesluoonin Amwxwa Cope-lamenuum
1:: Banana Solvent with momma-isobutyronitrile Canaan.)

Ww*w—n . -“'WWWF‘ -«--~ 1”,»... ‘w<--‘-g—l‘4n‘-‘-ll"M-.' . . n “w. n

 

 

. . u.- . - yea”- ..--u¢.-r.--w-c-'n

 

 

 

Percent E.
n, H. mam-mum Hole Fraction
Tim mm Cm. Bolu- Cum. from Ht. at Ll. in the
mantel at Styx-m or 24 . “POW 0090mm-
0 _ 0.321 00309 1.5 ‘
7 ’ 00233 5.7 .
15 0.291 0.259 11.0 0.57
30 0.231 0.203 2907 0053
16 0.175 0.160 15.2 0.50
60 0.1% 0.121.. 56.0 0.51
100

0.103 0.069 n.& 0.53

 

29

figU/E’ 4

.

«WU\5Q\S\ WSR .

QN\ . . om

 

 

- p
a q a

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db

0 O

’5

0

c .w‘ \
.O mtmxfixw

'l

b0\*3\0% m§thmQ E \m%\b\~ob Oanm<fl
toxxbwimkx®onxom .VQ .. mkmxkxm, \..\
mkmSEBE 93 mythkbmowbeQ QB 98%

 

r
\.
Q

5x1
‘3
(10/71 (MW/3300‘) 10/0”

m
0‘

‘é

 

30

59m 5

 

ah;

\mmXbSKC mxtk

D P I p
d q d 4

QOQQQOW
43$}wa 36-3% a .Y.\
to\be\\m$%\oQo.v

. 9%“. 9% 8m 8m 3m. 9% aw ow

WQW NQAUQ bi

.. mmxmkxwxw \..\
x0 ”\LGQ

   

53 Q a

é
00/7sz/Jawfl/od %

4QQ\

 

 

31

figure 6

«mmx3SE\ mxtum
om

nib-Q
‘3

 

 

m 4

 

+.//'
O .
.

QSVQQQW QONQmQ S \waxbu oNcéQw.
tofiONImE®oQou .VNNmkamxm \..\
km§®oo€b x0 QSXQOQEQU

3: 4?
6 Q‘
'V 7 u0/_/ 904i a/OW

53.
Q

3
C3

 

 

32

1313 II

mm or crxmp¢mt'r2 c? zxwv‘m, cums ITICE 01" nm
comma, 1:53 mm C? Hmrmzzumn
(1:1 Styrmsltaoonic Numb-169 Cupolymriution 1n

 

fatnbydmmrm Solvent with Bmcyl PM“ analyst. )

 

Pea-cant N.
we. mz’m Kohl: m.’§1£m”§}°“ ”$1.: .Tm‘fi“
i1: £52251": 3:12.23“ka 9%
u o 0.321 0.321 0.1 «-
21.0 0.259 0.235 13.6 mm
360 0.258 0.255 18.6 0.1m
SAD 0.231 0.2% 25.6 0.155
720 0.211 0.226 30.9 0.1"”
b. mum mm
o 0.321 0.316 (:5 «-
60 0.306 0.311 3.9 0.300
2:» 0.27:: 0.275 15.0 OJJS
has 0.236 0.21:; 23.8 0.506
726 0.228 0.228 29.1 0.500
950 0.210 0.2% 32.1: 0.166
1285 0.192 0.215 35 .9 0 Ash?
1500 0.198 0.198 33.2 .500
17150 - Gm 140.1; -
mm - 0.133 um «-

 

33

figure 7

.V\

1(3on MER

 

4b
4

 

 

4 . .w .\

G. o @5393,
thQow Ikxxk S xw$§3u NQNQ
toicNkaxNERQu .V\ .. mtmk%xh \..\
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Q‘

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figure <9

ON

 

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§ 8

.

\WQNXbu NW N%

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Ox m. m %

 

thQOW [KERN S
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35

figure 9

wk

\WK§QV\ WSR

 

 

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9 m.w.w

o\\\.\éd
o

O
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QQ\XBN\\m&\mVQQ\ou .b V \ o. mtm\\xw \..\
ngkwsifiv N5 tofiaoofxob

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.36

 

 

mi

'V '/ HOG/Dbi/ a/OW

RELBZII

Rim 0? DISAPPEARAHCE OF WKCIERS, cozmma 0F TIE
canm, LR!) RATE CF Kanmmfl
(.111 swszum Wide Comlymmuon in
WWW Solvent with WWWymmm-uo Cum.)

   

Percent. H

 

, I
n» 5013516“. nong'm. ”kW? fifm?
AW# “3% A 39:9;A WWW”? g.“ “WW M
0 0.321 0.321 a» a.

35 0.319 0.318 0 .6 0.566
6n 0.310 0.312 3.0 0.1460-
350 0.279 0.281; 12.2 0.1958
22‘: 0.266 (3.262 17.7 (3.51?
has 0.231 0.230 28.1. 0.562
600 0.135 0.211 35.1 0.1489
em 0.187 0.159 in...) 0.1M
1320. 0.151 0.166 19.8 0.13235
1680 0.11:0 0.151; 55.0 0.1;30

 

3?

figure /0

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q

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38

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b D [P b P P b P b b r p
4

 

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arm/czuaw

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39

figure /2

i

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N\ S m w .v N

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L b n h [F
q 1 q 4 q

b
4 d

43%

’V / UO/7zDDJj 8/0”

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tc\\bN\ngb\\Q0\Qb .VxV “MQMKEXWFV

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8V

C. om: of mm with Respect to Styrene ma Imam: mmndn
swam-um-

m at. mien for eopclyneriation or chm ad 1%
amends has hem pmpoaaa to be (1):
1m. a k' [23’3‘
mmn’unmpmosmsmmmmmmwma. Irma
”ammwmmonuammmwumwww
utmmummmumwwxww
mutation. The tint om:- nu Won m Wanted 1::

Log [5*] u logy-41:]. £3 i

Wortbohgetuyrmmmum, auwugatum
max-1:10 ammum, fig, no chm in Figs“. 13-»20 for mh mm:
m ““13". W.

rene C once/7 fro/x00

My Stu

1
53
(>9

E

:K
N

L
5g

figure L3

 

 

5/2375 Ora/er p/of for
5719/6/72 (aflccn/ruflun

)
/./ 5/:y/‘Enei /.A. C0P0@.m€f’zaflonz
BZOZ cara/ysf M 56/726/76 50/0/90”

  

i

L i 1

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141

 

Q

2¢0

60 /20 /80

77me {mun/7‘65)

figure /4

11,2

 

5/1575 Ora/er p/O/ for

5 fyre/ée Concenz‘raz‘lon ,

L 6/5-020 cu/O/ys/ //7 benzene
50/4/7900

1

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1

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l

s/ope ="/ /2< /0 #520.”

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// Sfyrene .' / A. Capo/ymer/zail/on,

 

 

0 30 60
”me (m/nufes)

90

1:3

u:

«33ng wSR

N\ Q\ Q Q V N

 

59 We /5

 

« u q q q q q d u q u q q

 

76mm, 9. Q\ RNVM wQ0\w

QQ\\3\QWU\\\IN tx XW®CX§M NQNQ
. QQ\\QN\km&\%\OQ\OU _\ \ \. mtmxhxn \..\

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au 94%}5‘ 5

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figure /6

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Tuww 93$“? 0&me

QSXQQW KER S \thuSu QNCJQQ
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figure /7

 

Cancenfru 790(7

I
1\
Q

U

A93 M.

 

.'\
A

BANZ- Ora/er p/o7l for
/ r4 Concenfraf/Ofl,

// Sfyrene: [/1 C0p0(umer/zahon,
32 02 cal/'a/‘us 7‘ m benzene so/u/mn

   

s/Ope = 18.5 2r /0-55ec. ‘/

 

Q

60 /20 180 240
”me /mmufes)

 

figure /8

 

5/1571- Ora’en p/Of for
[/1 Concenrru/mn ,
/.'/ 57‘yrene: [A capogmer/zafir'on,
[9/54 020 60 7’06“ 7‘ /n benzene so/uf/on

g
‘3‘

I

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Q‘
'

5/0,0e =‘/ 2x /0 «45662 ./

 

Cancer/790 f/on
Q
on

9 M.

(a
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0 20 40 60 80
7/3778 {M/nufeS)

116

h?

w \

NWK3QV\ WER

N\ Ox mV Q V N O

 

59m /9

 

  

 

 

73m, m-Q\xmzmanwo\o\w

QQ\\3\QW .U\\r\K S xm\\b\6u NQ wa
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uo/7wu7zuayu09 '[7/7 60/

11,8

figure 20

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N\ 0\ m 0 .V N

 

 

d
u

d d u 4 3 u q 1

7me 0.. Q\ x %\nnmo~o\m

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QT

.awq-

 

 

uO/gnjfuaauog 'V 7 60/

flthfiaaf “£2.29:

WWmfiadmemmw, 11‘th
W Win!) 1: mm rm 23v: mm a! Lfiitdafiicn, a” u
Mummmmmmmdmw
Mg m tho M ate ”it“! (25.25“

:3. £33] ¢ {343]}
at
i
inf-”2111' + mamas} + ra[315]a](%)
[rl'f'f’ifl 4» 2 (Eryn 3.4—) m1] {3L3} 4-1:, h) ' {£13}?

 

1 51
a :3?“ a 1+
1.3 n
In,” ’3 " 3M1: '3 " kin/kn
f .. 1‘”; It"; in: km in and kn " mm
at. mm

mm ,1 uMummmmmbm-ou
unmammsmwmm.mm
ammummmmmmmm‘.
noun-(mummwmm. mmm H n
lam-p. 1......deth W, momenta

. W m
n. .44!“ng 13*: ,v «grant _'_
mama) ~ wag)-
3215—}t o tn ((1: In I- Y}. (13,35).)”
“1‘: (M) (mtxgo); ‘. (3,051.33,

 

1'?

{a

‘31
t

vim b, '- r331
b3 . 93";
*3 " ’18:.

‘g. :58.

$311.- 18 a 11m: tarmticn of firm nth respect to the meter bivalv-
tng bath m mcmtmtm, 91,. am Ea, and Q19 mom: réactiviw
mu“, 1*; and x". The alopa cf tE-aia 1mg: 1:: a. inaction of the rate) of:
initiation and tbs arose tantamtim emstant 9". Shme the mmtivity
mu“ m Mom for that malamfiaaticm c! styrene and itaccnic
WWO (2,28), from warts: pmimly £20113 in £11.13 hbcmtory, in but}:
ham and Warfare“: savanna, the rats of palmsmucn am
he minted (m the Mammd aquaticm ma values for batman
Iolvmt 3:! them in Tale XIII and Figure 21. “We valuaa for ten-aa-
max-cm Iolvmt. we aim in ”Kala XIV and Figure: 22.

TAM XIII

CWM RATE CF (Iii-{LIE ’"fiIEEflGE
(Fm BeBet‘hfl Integrntad mum at 1:1 . 3
1W mmirme in Emma 301mm.
r; c 0.615 3 r. I 9.80

 

 

 

 

 

 

 

 

 

TM ##1##— ‘m 3-4: :::L AL 7%; 44:: - ‘ ' luv—TA 1*:
. [mm Ti 4» (ME-film
Tim aw ~:~ - _:; _
1mm I (151$:sz fl" u [b.f 2515
1. Wfl W0 “ta-13W (ml-1mm)
0 2.6a: 2.5?
15 a -
13 4-— 2.38
. 60 2.1a 2.39
120 2.29 at
1.33 . 2.16
130 1.93 «-
240 2.65 2.03
350 1.83 -
2. Rim-immune am
0 2.60
7 Cr
15 2.52
30 2.53;
3:5 2.51
60 2.32
m: 2.16

 

 

52

«wmxBSKQ mSR
own QQm, QVN 03 Q N\ DQ

 

figure 2/

 

1 W q d

 

m.

. O .xwkifibu QNGHQQ
o kw®6xbw NQ Mm

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”750/

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gflzl’qu} ‘QU’NJ

42W]

{3

ME II?

0mm RATE”: OF MPCLISETEMEATICfi _
(Fm mam Integrated mm, 01’ 131 SW:
laconic Azmardrida in Tshwmimmran Solmt.)
r; I- c .1 r. I- 0.3

 

 

 

 

 

 

 

2. Em'vuobu‘bmitflh catalyst

15.3
15.5
16.3
1? .2
15.0
15.6
1'! .7
15.1;

§§§§§3§30

5h

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.3 N\ S Q .v. N 0
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< o xw \b.x\0u NQNm
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m. ”WIS CF mnrfi*ubu{m A453 :2 'A'
0131.!”4 86:4 33211319
Sample: of tha Mwitacmc mmmhfids cspc‘lgm prapamé in
MM“ mam XI-awmtmlnadto determine their
mum. m 00901me were flat purified by Win We»

.umwithbmmmgmm meternndmdriede-mm

mammnemmmmumnmmm. mm
mummwumndmuchumplum acumen: titrated
90th (1,29) and also with u h1g1 I‘m-m timber
(2914,2934).

A. 3.1mm Win at Ccpclymm

1343 mines. of summit Gas-mm in the) comma anal“ tram
carried out kw Mom-Tech Walton-an, 31:02:19, mum. m Tabla IV.
3. PMW and m mey wwm a! Emma-Imam

W“ W

mwmmmmmwumtmwmawm
{motion 0! Que “mania WM unit. The £1th m followed
NW (1.29). and mm a}: high tramway tux-1mm.
Wm ion ammunition m7 M an a. 3m pa mater, ‘equippad
*flthflAuMa-mcmdnmwmdm. Waugh
Mmy reading! m m m ; titrimtw which has ham
W by Dr. 12mm: (294). Both mamas were taken aimltanmualy
mthobmmdtmuflwMudWhyW.mtiond
both method! In and.

55

313.31?

mm or mmmmmmc gamma W5
$22924 42.4w 44mm

 

 

m 330. yes 93.7 69.141 0.5714
Bun-a 3.0, no 93.? 67.624 0.619
M BIO. ya 100.2 69:“; 0.584
hm am. no 100.2 68.91 0.538
m bin-«o ya 11.0 69.52 0.570
hum law you 71.24 69.69 0.531
mm M up 11.14 67.92: 0.6%
m nu. ya 13.6 68.10 0.608
I! no. at 3140 71.19 0.536
B! m. 1. 142.8 72.00 0.505
m m m 12.2 70.01 0.55?
a! m in 514.0 70.16 0.946
m am no 514.0 63.30 0.6014
mm run-W
ws’wm
Manna-WW0

Id.uiwm
magnuunmuiwwumm

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57

mmmmumummm.

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umwmmumu(wwymm).mm

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59

III ‘13" TVS? SEPC‘LE :33 W

 

 

 

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I Icon-II In» ”'17::

 

   

 

solvent mm W animation Pfigfia Ifiefl
3mm» BIO. m 93 .1 0.576 0.575 '
Imam mo. yen m .2 0.561 0.555
W W was 11.6 0.572 a»
Imam hm m 71.2. c. 32 0.555
1'23? 3!}. ya: 1.3.6 0,555 I.
my mo. yea 31.0 c... .525
m nae. m 1.2.23 0.568 .505
215‘ w r» 12.2 .561 ..
m W~ In! 534.9 5&6 .3535
m M: “D ‘93 .7 0.5732 4»
Mm 310. no 156.2 0- .516 ..
Bum W no 71.1; .538 ..
m MM» m 93.0 0.232 -
SW1»
229‘ I Wm
M. a bunny]. Ma

 

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pofen f/Omefr/c ”fr/1790;? ,

5 fyrene: /fl Colon/ymer I

92 % paymer/zec/ / 8202 emf
m benzefle 50/41 f/on .

A 76180615 Iowan/are

0.204850% 50/77/9/6
25.00 ml 0. 9966//V AM/I

 

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2468/0/2/4/6/8202224-

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61

figure 24

 

 

86
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Sfyrene .' / I4 €0,00/f/mer,
92 %/Do{7mer/zeo’, 8202 caf '
_ m benzene so/uf/on. '
A gaeous procedure
850L
0.20489/77. 5007/3/69.
25.00 ”7/, 0. 0966/A/. A/aO//
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figure 2 5

62

 

   
 

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// _ sfyrene .' /. A capo/ymer,

92 70 po/ymer/zeo/
52 Q ca/a/ysz‘

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m/ HC/ O/ZQB/V.

63

figure 26

 

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I Haw/ff: e5 fer procedure
0.2057 9m. sump/e
25. 00 m/ 0. 0966/ AM/IOH 1'

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57/yre/7ex / A. cope/yme/j

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0. / 908 gm. sump/e
25 00/271 QOQéé/M A/IOH

 

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m/ //C/ Q/ZQcQ/V.

65

 

  
 

figure 25
_ #95 Frequency fifrO/z‘xorz,
57‘9/73/78 .‘ /. A. (0/00/7er r‘, ’
850- 92 % po/ymer/Zeafl 8202 car?
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0 2 4 6 8 /0 /2 /4- lb /8 20 22 24

m/ HC/ O/ZQB/V.

 

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CEZQRRISCE G? W CF 333.1353 GP CCPGLIEM DCEWCSITIGH

. .0. . Av “luv-“m, . - -~.h”mmW-Im‘¢~.u. -‘Iwar- .--.-w.-.-Mmmg*wvm ~QA

I 1' .13,
' ‘ ‘ 5mm;

MW Pom car-hm
301mm Cam than mum Anal.

       

 

 

Win; _- _ ;MI:::: W
Emma me. am 93.? 0.57:. 0.936 0.5420
W M. m 93 .7 _ MGM 0.9.;2 0.534;
ammo M. are; 150.2 0.55:: 0.563 0.500
Bum M. no no.2 0.533 0.515 5.500
Banana bin-“o you 11.0 0510 (2.572 8.570
W bin—cm yes 71.1; 0.531 0.582 0.506
8mm bin-no no . 71.2. G .6134 6.533 0.550
m m. m 18.6 0.503 0.605 0.1m;
m age. yes 31.0 was 0.52; can?
W In. yea 252.3 0.505 0.53:8 0.520
m bin» you 12.2 0.557 0.551 3.3
III: M m 524.0 0.536 0.536 (”ISO
w him an 53.0 6.6024 0.1m c.2430

mmmmn‘mw‘fiwfl 4;...
mm 7.“ —-——-

 

MW ._.LA LL..- mm m <
' ‘ "v wwv—v— mv—m

 

a7

mummm WEIR}!!! CF m7“ am? 23338
EMITJLI. CCFCP' Ind
mwmtdawmmbemmdbywot thy
tannin; mm. (3.39).
I.) 3mm
b) m: m dabonfimtim
a) may
«1) W16 WW-
9) mm W
2) L1?“ muttering
mm mm, csrynacopic prepaz'uu am and map datamismtmm
m We We! a: the number at particle: in Minion, hmce, a
maim- cm:- mloeuhr «at; hf. is obtained:

fin £1333 £3313 thmrbwotmlmlea
2 E1311 2: 31. Hi I m night
night. mm“ m a. polyaar wlutim, on the ether hand, is
dapmam upon than an or one}: particle in Iolutian, hence, u might
nugget” m1” , Night 18 01W ‘ ‘ ‘t
, a
a
93'“ ., :31 a

Z F1133}.

The may (21' a. pclymr minim is a. m 0013;111th madam
or use, sham amt mm a. muwm' partials: in mum, “W3 In
Why flange mlww weight 13 cbtainai- ,

W
W

Z H1331. a I c con-m

Wmmcmwwm maplacmmwvaiffamt
WWW wastes, 03:31 cf the 35m mgmvfll We; dif-
twt tuna. Tao mm of 2.2m mamas mimic: night 1. an 13:61--
catwn at the W at tho ammum a: mlmhr night...

In ammlthotwmmflmcréar :4. >1“; Hg.

The mailman: weight». at than Wu or charms-1W
W&,memWM¢n-bymmmm
light muttering unmade.

A. Human.- va’dght of Shrmecltacmic mmma WW by; s
cm Fm Emmi
1. m- cm.

The W and in $12.6 ayn’aawical 093.]. block type, decrement
h: M and Find (30.32). 1m 0311 «mists of m skinless steal
bloom, not: or which his mm moaned Bantam widget with
avaumamlmmgmmmamaapmmmmm.
The madam In W 13qu the tam blocks. Tho mater ridge at
”h block m mam Mam? um: km supporting ridge: no that the
Wmchmdugbthmaunwmt. Pimmz-cpmvmw
to 1mm propa- WC 0: the My. & Janka m widad tar
mammal-mg: mamuminm thalamumcta
W Wm. WM, mm m mm to be Mutants

I}?

imam. m1. Therein”, the mm.“ were man in In .1:
mashed constant flatware mm mm ma emanate: insulated by
Wit mummmxuithchemcloth.

1%.: upper parts lend to was «2.9111317 tubing, 1mm: we con-
wtadvzithgmmdghu Joints. Thalwalofligddnammin
the «5:111:17 tubing by m of a mam-mm. amour: pm
mm: me man by we mm 91th .-' (.33), 1.0., the
mlm‘umtowmmmgnmmmmutmmm
mammtandjuatmadwacmtuprmm. Mashhad
a: Want m and. in NW to tho Gym: mthod (31.31.).

mmm,ofmhm,mwmmadtpltmm
WMMom. Mmmmtanmd tmmmmm
in; the can chums-I !m the bottom. 30th wheat and solution can:
we” rinsed men}. that to am aermct maximum and W0
a: :1: mm. ,

 

2. F ‘ '.

The 0313ch and m‘mmticn 01‘ ski-2.6 eternal-mama man-am to be _
and far 032mm pressure mamasmm is mot isms-taut, an mocm
121 3)?er a truly iampanmala mzmmm damn” that mam of
WW. Wmtarifla Mabmnwd (Kolmwhinhm
* Mun. wimp”. gelatin, mm:- (neat, mm yam, metallic
{an and poms m. calm“ mz-bm mm by dmuuting
mmdimmumd for the” W3. Germain» mam too
had in mm sanitation am aid not term A tight ass)... Thu pmodnra
(35) w to paw w nahmnaa fellow.

71';

H. 8. P. Canadian m usad for casting tha films. Fifty ml. of
00W mu poured. into i brads flag, 1:5 can. in War, which was
flatwamacmmcoozmmv. AMOJM'mpluedmr
thorium dam; Comm bubble 1'6mequ W'
or that Iolvmt. After drying, the common mm m “Rad my
Immonngmduullodutar, fiatflmlbiu dwmmm
mm rough «1m out or: tin film.

an damning mm a: W a follows:

we all. mutated m (35 3.)

an W .- “mm with lawman mind. by bubbling the
”mammmm. EMMmrm,mud1-o
tum water, aux: planed in the ammmg mm for hm hours, use.
th taming and stirring. LM m mm mm {imitating
mm mm film m mum-d mm). um. 11: M11106 131m: tom
by ”mud.“ Ming; in 50-50 mmml, ethanol, 50-50 am}..-
«mm {Wigwam ma WWWWm-mm and
may 03.1mm! to dry at.

3. mm of auntie prams.

C) swam-1mg NW. Vucpolam W in humans
What with bin-.031 gamma-ta mm .

1:» mac gm of mama: minusc- of tha mum of
WW@ tmmflfla cabana": fret: polymerization in bansma

71

muamMWthtMmm
m. mmuummumnmmm
mmmmamwmmmtwm,h.u
mwmamgmzmm. WWW
w

1! Chad
dun,
gummmcwmdummwd
m,
“mm n 5% mien.)
mmmummummmm
mtwmmma
‘6'.- E. 0 30
3In

cummtiannfflmpolymrumfim
nnwmshnt
Tommmm
Bulimia-m
mam-mmumsammumcuvbwc
mun;.mmumo£mpe3,wmnmutm
Am, (1.... infinite mutton):

is]. - g;-

mmummcummmm.wmm
unummmnmxm.

72

figure 29

«wKEQV\ wafik

m.» S. aw Q S. m\ 3 .3 8 9 m. m a m. o

 

 

- q 1
1 u 4 q q u - J q q - K.Q

%

 

 

 

U/
3 a
no
0/
IT
. m/
mQQQ\\Em OQQQQ uh << Q ! 44 d o UJJ
I I o .44 ...m,\ mo
I Q kw H
J
r9
(0/

3
.§ m/
w
0.35%..“ 3&6 n u /\

Q < <0
q q q a q 4 a
O .o o o O JMN
u .1 . , x .
oQQNQNV S axotfi \meQQQxQM V\ ..m§mk%\h «Wkkhwwkq SXQSWQ

 

 

mm

73

59W. 30

 

 

 

 

 

 

 

p/m‘ of WC agar/05% C J

nyrene: / A Capo/7076f

prepared m fienzene Jo/w‘m/z
20-
/5»

O O O #-
/0~ 7T
(‘5); ”0
5 r
0 l 1 1
0 0.05 0J0 0/5 0.20

Concenfraf/On, C, (gm/mace.)

7h

TABLE XVII

maul-Ion a? in ma cmmm or ssrmn-za-mcuuc mum-ants
911mm: ma mama ammr um;
amazon. mum; mmmw

 

 

 

0.0989 1&8 1.16 11.? '
0.0597 0.83 (2.65 10.9
Wtion o: in: ‘

[glo 011.0 0%

3 '- 3.1.79 3 10‘ m..m./°K/mlo
r - 293°x

fin- 23.0w

 

 

75

b) Strum-imam) larval-id. “polymer propuod in W.»
rum Iolmt with bamoyl peroxide oat-.11».

the osmotic pro-our. or on motonc Iolntion of the oopolymr or
Mankiuoonio world. pm in tatnbydromm solution with
b.3011 peroxide ably-at m W. 1310 malts of three moore-
m m shown in Figure 31 when the W height “time, h,
in plottod awn-t tin. or mine in tho amour. Bo «Isolation
o! noloouhr might in and. boom» the height difference never
ruched . constant union: but increased for n time And then duct-mud.
B. nolooulnr b’oight or Btyrmo-Itwonio Amuydricio Copolynoru by 1.

Light 3oattorin¢ Hathod

Tho no of light mttoring from dilnto solution. or polymer. bu
ban adapt-d to m dmmmtwn of their mm weight (36.31.38).
The average molecular weight obtoinad in a flight “one. 3nd will
ordinlrily have u cum-m ulna thou tho number average room by
osmotic pm mm for untmtiomtod Implu. The light

culturing oi' main-laconic mhydrido oopohmm m matured in
“W.

l. The Light Scattering Photomotar.

A Whom: 113m. muttering photometer (39) m and to
m the aunt of light mttarod by untono oolntion of thus
I «qr-m and 1mm anhydrido oopolymn. m. comm components
or the photometer an

a) mercury are lump

76

figure3/

mnkb QV\ WSR

 

 

  

 

mNsNaNNNQNmQS i FQQa Q
. . 1 1 1 q 4 q q q q q Q\
_ 4 o .W/
.uumm\\&\m. aQ\\.Q U o 3 rm
. 7
33 xr
m/
e f
a.
J
m
13m. 3
a
W/
./
3
w
AWN (
QQ\.\3\QW Kink t\
\omxhbfikavx Km$®0©®u “\\ nmaxwkkkw
Mkbwwwkq u\\QR\m.Q 19m.

 

 

77

b) tilt-n, to Adjust intensity and to provide muocm'omtio
light either 1.3583, blna, or 51.6QX, mm.
o) n light tight dork box containing 1) mlo cell, 2) photometer,
nomtod on o alibntod tam-table.
d) wording 91mm”.
nu ample ooll m amt-01ml” in flaps, to allow light to
you out At w anal. without rotnotion. Tho tum-tabla mounting of
tho photouotor panama the sum: or mattered light at 0°. 25°.
90°, and 135° tron the inoidmt light beta or at my denim angle.

2. Procedure (or asking W“.

Th. mt or non, mttorod n angloo of 0°. 15°. 9o° and 135°
from the incident boon I” named for six commutation: or each
”polymer hoopla in untonc wlutim in the following We.

'in mm nook Iolntion oi’ known oommtntion (approximtoly 1:21 )
ottbooopolymruoplotobomwod,nopropuod. ivoigbod
quantity of purified and filtered «atom to. placed in the oomph call
am tho Outta-d light as mounted at the several angles motioned.
Incl-unto of flock collation var. oddod, with vigom stirring, by a
spam. stirrer, weighing boron ma sitar such at of 113m. scatter-
ing Wt! to mount for vaporization low or occtono. With nob
‘ odditioml inommt or stool: uoluticm the mttorod light m measured
at tho moral Anglo. motioned obovo. The dock solution addition:

mondobylvpodoroio gringo, equippedvitbn filter, tvoloyoroot
"diary extra-«fine filter popor m and u filming medium.

78

3- (mum of calculstion of molecular weight from light «scattering
Mus

a) The limiting equation.
The limiting mtion relating tho turbidity, ”I", of a polymer
in solution on: tbs weight orange mlamflar weight, K, is:

[13%.] 0" 7%.. (53))

o a concentration or polymer (gnJmlc)

when!

3%.) a correction factor from the diaomotry
P 6
W3, [%]o s

a , amacm/w
3 7‘ Ko
:10 I refrootivo index of the aolvent u the an lmgth
used for tho mmmt.
(cc/dc) . immontof change of refractive index tor change
of polymer concentration.
A . wave length at light (and
B. a ivopdro's motor
T, - T . T.
T «- turbidity at 90° or the pom solution
To 0 turbidity at 90° of aootono oolvont
Fro: the uniting equation it can be sum tint a. plot of Ho/Ta .
values for no): concentration of polymer against concentration of the

polynsr m ho mum to are mmtrotion to and [no/7.1, .
i’ns ulna or tbs flight mango molecular weight, 3', on than bo
maul-tad. m- mpn- urge/70mm; c m- uch c: tho thus
oopolyunusnrodmohominflmfiundmtodinhhlu
xxx, xx, um xxx.

5) Rotrutivo indoor or wotons, 11..

m mm c: mm c: um um um. 1058.35 A? in
W ot 25° was round from o plot or rofmtiu index ot tour ms
Maths (MAJ), at 1.9.1;0 c. From tho nus sou-cs A nuns aim or,
53 1: m‘“/domo c. '

3 19.130 _
1&3ng . 1s357 2;

It 25060 a no I 1.35523
113581

c) Lotemimtion of (Sn/do.

Tits inormtol clung. of moths influx of tho oopolymr solu»
tion for inoromtol ohongo in oopolmor oonoontntion no mound
on the torn “stout stock ”Minions. A Edam-Pm diffcrmtitl
rsfnotomtor (he) as used, fin readings vsrs mused for web
Mornintion. m. calculation of own/do from tho coon-rod findings we
' sham below
so . 2.4.9.
no Ao
An 1- mmtntim of polymer in solution gnJ .

130

k - 9.53m x lo” (a aomtamt)
Ad - (drdi) - (co-m,
o, and a, - reading: at 0° and 18o° for the polymer solution
c,“ and c,“ . macicga at (P and 130° to: the solvent
solution
Acetone solvont pm- a rains for (elf-cf) c: 1.30, om: was mad
for s11 thm staples. The! ralnoa of (Sn/do obtained are tatmlated in
mm m.
6) Calculation of the value of tho constant 5.
Thu nlns of tho mutant 3 can be oalmlntod tor wotono solu-
tions of strum-1W0 anhyfirio‘a W using tho nation:
1-! . 3%. I grin/dc).
3 7\ go
when no It 1.36523
cn/cc a 0.1903: mm.
A. 14353.35 1 10.. on.
no . 6.023 x lo" one”

I
then a :- 1.0275 x 1c?“Ii £394) E13
m' on}

0) Calculation of, "I", the turbidity values.
The turbiditlas, T , at each concoutmtion of the copolynor in
‘ wanton. “lotion were calculated with this emanation:

1m" " .
. ,
T F;- x ifh a: t
o
i” an intensity of 913° tattered light

mg XVIII

Ema-”“7103 CF Woe VALUE or mommccgm
W ocngm

 

 

SW31. 1.
Cnmlmor Prmmtim
Von ' “W 11,4, 0 oc/do
ammo one. 2128.5 1.0372 x 10" 0.19033
no mo, 2014.5 1.01m. x 10‘" 0.19090
no bio-um 236.o 1.1792 x 10" 0.18963

Amen ulna or tin/do 1- 0.19032 nlJm.

 

i°° - irttonsity of: C° light, no ooluta
10° . intomity c: incicm light initially, no cell
Ia ." intmsity of mcmm light for each reading, no coll
t . Sign] Lucas 3: 10"”
0.0
T. . T . T.
T. - tummy c: the saints at 90°
1; :- Minty c: ccctccc oolrmt at 9o“
Manolo: T.mtaholatod form orthothroacopolamm
mummxn,n,amm.

2) notomimtion of tho oorrootion motor, (We), from dimmotry
WC, [2]“.

m intonoity or light scottoroo at angles of 16° and 135° tron a
paw-outimmnlotodtotm stupoondmootthopolymor-olo-
ml“ in solution. The ulna for own}? zmo was calculated from

this nation:
2“ . horiiooh
no _ no 0
where
1., . intensity of mttorod light at 35° Ior tho polycar-
solution
(1‘90 " intmaity C“! WtWPM light at 145° for the acetone
solvmt
1m . intensity of scattcmc 113m at 135° for on polymer
solution
“m’o I intannity of mattorod ligfit at 135° for tho acetone
aolmt.

1121:; III
MEET”! A31?) "1‘33? Sinus.

 

(3 WIMmic 3331331123166 u Gugwlym PM in Bmume 5101th
with Rmzmrl Penman 03W)

 

 

0 68.1100 :31. T. lie/T. 2“
0.0253153 24.01.33 :3: 10“ 0.6708 x m" 1.1:;
0.0343711 1.0573 x 10" (2.7672 x 15"” 1.1::
0.0631355 . 9.1.591 3: 1:“ (2.7397 x 19"” 1.13
6.632665 12.£2§5 3 16" (2.7539 x 10'“ 1.15
6.15935 1.3.5657 :10 10" 0.7513 x 113'” 1.19

.5

6.134355) 1.835%.» S a: 3.0"".I 0.7367 3: 10 1.17

‘4 1— ...4 1...... ._ ._ A- ._ H A A. _.._ “1—; - ._.

‘v-v- w v- , y‘— . —.,— _ r W V M

5‘

warm H.11- mam-z 3-.- Emma
(Emma—Immuic Anya-1:333 {Myanmar Prwad in 19mm
561m with Emmy). Par-m: 1&0 Catalan)

 

 

 

 

O W :11. T. WT. 1”
mousse c. 39 x 10" 2.6986 x 10“ 2.1.0
0.6:.7273 2.532s a 1:." 1.8813 x 10" 2.51
0.: 2362.53 3.5953 x 10" 1.5.171. x 10" 2.76
0.056%0 mass 3 m“ 1.6531 x 10"” 2.30
9.107551 5.9702 x 10" 1.8551 x 10"“ 2.7a
0.12:2.27 6.8232 x 10“ 1.9639 x 10" 2.52

 

 

“IVS-’32.. “m $.17.) LIE” w. ””5! mama

(:5 WQ-Itaconic Aniryfirizi a chlatm 3' ml in TetraMmfux-un

.A.--__ .A.._ ...__

A

Solvent with Bimw-isobutyrcmw Catalyst )

M

 

 

 

a .../m m. T. 30/7. 2..
0.035975 Jam x 16“ 3.6933 x 10"” Ml.
0.063361 3.3.123 z 12-“ 24:56:. 15" 2.3.3:.
mam? M719 1: 10“ 2.1873 x 10" 2.39
0.128033 6.0706 :- 2.3“ 2.1679 x mo" 2.52
c. ”5331 7.2770 x 19" 2.1911 x 10"” 2.53..
0.1761293 9.61.61 3 10" 2.9968 x 10"” 2.59

 

 

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50/ X 54/9/1

£7

A plot at 2“ mm... min“ cancmtmtion, c, of the polymer
32mm 32:53th u. “night 1% match can be mctmyolated to new
concmmum t0 gm [2)... the intrinsic magnum-y. The plots at
Mumcmrthotm-Npowm.mmmflgam 33.
Assuming that than polymer molecule. .3. pelyuiaperse com a value or
mm m be tom: me published mks a: (22]....5 1W we) (37.3.3).

is. 3101304313: weight mucus.
I.) Emma-itaeenic an‘miérieu «gamer «maple med 1:: lemme
wlvmt with My). pemadfie new mimic- ueight mm.

[359...] I- 0.62.0" x 11.32:"5
T: o

naming migrate-«yew ecu:
[21‘s . 1.113

PAW) an LC?

1: . 3,, 1
[fi] 0 7‘! (33(6))

Fag II 1.57 .134:ng , correctmi for fiiflfi‘flMW

b) Stmueuitacenie 3.12m 3.21.33 00130157111331“ Wm in tat-.mhydroc
Min solvcmt with bmzayl pemvide ca PM , molecular weight

calculaticn.

a— . , - '3';
[Ta 0 2.00216 E

K. ~som

‘3)“ . 207°
(“(9’). 3.“

[3:] .- 3. (M

F. ~na,om.nmmm.

”WWWWMhW
mmmuuunn-Wummw
m

[3.] o I» 2.09me a;

T-

I. ~ 50.000
(1)“ . I."
(“(00) c 2 .29

M We»)

3. amm,mtwm

89

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QOQQQW QONth a .28 46.6wa
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is... GET AVERRGE rmma It. .flfiS CF 8Y1?“ ~..'..s "’E-ITACCHIC mm REE
GCPOLTESIE FRCH LIGEH SCRI‘I'ZRIIIO *mTLX‘;

 

 

 

W W __ TL :Eifwm
Styme I. 1. _ a.
W %£m Corrected for

E Iv-unt. 906 Turbidity mm

W m I: w I ..._. “

32mm aw. 155,060 167 pm

CBC?" . 3..“ '3 1'13!

     

I c Qflh’rme 13...; -~-°E33.LRTIGE OF meet-11:0 AXE-if“.

A1121 sm.m I-KARZEEES

14am for thc dmmticn or masonic We manner mule
be based on motions of either the .ctlvlenic mantion or the acid
Wide mums. Beth reaction: were mud maximum
mwmdmxmmmwmmm
mumnuhtioucmhmgbothcttmw.»thssiho
nuutmmmmmmhewmnmmu:
Wealth: mm; W.

The numeric ”out. reaction is a rapid prccmc tar we do.
Wmacmmmmmw. nmbcenccmly
Wierutyrmcmlymmummrmwm(n)tom
wwgmmmmummdiummuaimcum. It
utmmcmmmmmmtommtoxnswm
Romania vacated“ the extent. «£923.

mu Ha nut-mun mu notified at mm “fiduciary (or
mmumuamemmmmmo:
mWwiionuiflzthoiW Wchmx-uim,
vhichmlcumfiitlmfcrthoupecific mmamw

far the mum 0! to“). mi of mutation.
' resumed thmmdtor museum-manna
mflwtwfimtfiwmfcrimmummomm
c: was. brown. mum. name.- the direct 1.1th at the

mmumnmtmubmmmmcmum fiVQW
alight medium a: bum 11c imamc We.

The testbed for deiermmen cf Hermie aniwfirflc, with Ulrich
W we not interfere, in the £3.th cf the said We
mm. “the cream: tunable were three: a) «mm titration with
here, i») back £1th at a misled. «we: or beau, or c) titration of
mummy-mammal. rmmcumcmcxmumm
uwmfimmchcncnummtew tepid. WW1:-
and to am it-ucenie Wade «mutation independent c: the
mamm. “Intercom-mum“
mmmwmmmmmnmmwmmwum
can he and on ; «polymmuca mom.

Wmmmdmmbchudmiu
Widowmuon. mmw-mmtormmm
anon. catalysed uranium and mercuric “mu mum can not
ammfcrmwa imcwwrmammmm
m now than. The direct mum meme (lid give auntie»
hunmdwmmmmwmmtutm
mm of m. mmtmtica withcee interference from 1mm
ammo. Mommy. immune in an emu-notary oclvmt

tor the anemia-tide, because 8 yellow color, termed on first caution
of Wm, med m an: point. Wang and Levin (1c) have mortar
that m calm were militiamen for the nether tame the we
point been» Wefmite.

93

:1. mm: «1124111121 or 2*:2 :1: ram mascara Arm,

Emir Warns were new ta 3* t? .e «Wmmetion oi‘ a 3.31 mole
ntiootcmmi ifiomficafivfime. Mmcafimumetm
acumen and We autumn.

The We mm differed in tint the «spawn! momma in
m,mmmmmmmmmmm.

W M «W used were beeccyl peroxide.“ him-1mm
entum... emyipmm in «Myme initiator
ad it in known to new am Wed ewmm (Ms-116). mercies-c,
its} «companion in no“ rim].- i'im crdermtienhinybo
«Mac. by orange or «Mme. The dammit-ion a: him-1Com
awommmwimowm tantrums (highbw)
in! it! decemaitice in Mme of mlvmt change. The oopslymriu
mummmmmummfi We. Tommio
mammmmammmmmMmm
Winn: 00.1va the «grammar were use me with
Wimmmtrne u «We.

mm «mm of the «polymer fume-.1 from a W of We
. mm has been mural: steamed and a «power emaiuon
mm m hem rem-name (531,512):

err . (
"EEH', 55“.]

i

 

Wic-

were {all we [‘3] m the mmantmtices of mm [14;] w: [32.]
in the meme: name and .21. [:1 ,1: and era-13} are the cemmtmtium of
the masters in an Laramie cf «pawn. 1:11.. «name! :3 and r.
em the many:- reactie ty rat-ice and repreamt the rec-tie of reactivity
cf 0. free mafia}. fumed {me (me mumm- with the cezreepczaling manner,
We to the made}; of ”the tree 1mm]. with the ether W.
tall (31) he: «gamed for an 113ml. «polymerisation teat the
reactivity of the campers 13 indwaami c: the mum of the free
radical.» In this ideal. me the mace medium! ratio: would be
the mipmcul. at one weather and the value of their penance, r115,
mm be equal. to cm. Hourmr, the usual. value {we fer rzr. in luau
than one. 111 crimes «are, in mean am an new, the ulna
u! r333 .Wm mere. Tim the critical product qr. my be team
as. a macro cf the «Many to:- the manner: to alienate apex: entering
the wpoiymfl.
The nmiivity miles at star-me, I!” am theme We, 33.,
have been determined , from eupolyaarleatiunc previously curried cut in
this 18120th (1,233). me Vance mm for «mum: in

amaze culvert m

r; a 0.91
r, «I 6.36

mu values fence for polgmazizatienc in teem-Mfume «Irene

were:

r; I- 0.10
r, . 0.3c
211'. I- 04:33

The: mluu m? thu pmreuct , 91:93, in bath cams Lw‘licatua a strong:
animal 6! the: mac-steers he alternates in the} ccgalgtmar. Pae‘atmrm re},
that aka-mum; tauiazqr is atmngm' in bamma than in tutmfmmmm.

Thu auburn cf the ulthmtfing underway in ccpclymr tomtian has
baa: sum-21a. Lads, $512.30 and. MM (532) magma: scam dipole mer-
notion m- omma: tenant-1a: bump" th- mnam. Cum (13 £655,520
have them that the tazzany W33 titanium 1:! p018: in origin.
Thu We. mum: (Sfifié) has been derived on the M: «21'
mm elm-3a! arising I‘m the polarization ct radicals and ammo
WI and assuming that the cfmgu in the was for both the manual
ms! the mm.

In the with man of murmur ane— «late We that m
mum II to mm or net the WW1“ fight proceed 32.5
a mania: or the two mm, whiz}: mum be this ranting spud”,
team-.33 tn the W3 chin (SQ). Wt Ind 0.1110 (24,57) lawn damn.
that this 1: possible in tho mu of flame and mm animal
Which am am. (1) has fame Wane that W and
“manic surgeries my cmhmdau in t 31313;: mm. W an
m that the raw 01’ 120903323: fumm that tho mm in. that
W fith mapuct to m assume mama e: a 1:1 mafia: of straw
anti itaumic mama.

For the four wipomamuam «38* as: studied first era}:- aways-o
me was fame with Inspect to oath-aw atyrmu or 1mm caveman
camautmtion, :9 03mm in Hm 13.26. Reaction rate constants
were calculated {mm the alias-s of than linen and they are name in
Table XXIII.

Thu rat. must-anti var. wily eqml, whether basal or; the dia-
appuunnuu or W or 1mm ammirieu manner, in each c: mu four
War. Tho umcmtmticn c: a 1:3. mitt: of styrene And ituccnia
m‘wfir‘afiu amid be Waited by firm ecmaztmticn c1“ 3 that monomer,
and maternal: tho c105»: uppz-saimm of first. urcier dupeaclmcu with
tweet to either mmnur would ixu‘ficats that the ccpoWrisation a!
styram and lacuna mmiridu might. procuue gig the 1:]. amines: of the
mm.

The «1:13! of the rate cmntmtu, Tabla XXIII, and relative rates
at copulymur fomtian, Rama 3:; , a; 811m: tint the copolynum'imtion
a! W 1nd impede grammes was faster in barman, from which it.
an precipitated, thus in tetm‘évlmmmn, in which it rammed in
”nation. The rat. constant, with claim:- bamcyl panama cr bit-aza-
mummim as catalyst, was many was greater for Ware
than for immemfumn solmt .

Thu largo dfifuramu 1:1 tutu of 1:0th in am tum 3033th
ml womanly the result. at a large diffuz‘meu in the mean rate
mutant, kt’ m the we ashram-.8. Ccnsicihrim; the case at In): one
W, x, the tutu u! puLmarlmtm, %, is fiutunrfinud {ma th-u
renewing rate mania (215') a —

TMZILE XXIII

FIRST Chi-"13:21 R?ACTICR F3373 CCRSTAMS
(1:1 Styrenmneconie wartime Cowman!)

«’“‘.- -w‘----—W~~Ww"«mw wa'u-oWOWOMMAWm.wn—fimmwammwd*0..-l‘r~-. ‘

   

 

 

 

T33? bio-nae 13.0 3 JD

98

«wmthkQ MKQN

9% gm» . 9N» gem 3m. new mmx m3

 

figure 34

d‘

 

tQthw wQMNQmQ «Fob NQNQ

 

 

wto\\bN\\o§\%\00\ou V \ ..m%m\%xw \.\ kg
wabm\ *0 towC‘GQQQQV

3+ «‘3,
[10/7/DZ/J3Wfl0fl 05

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K9

0Q

09

 

 

P? a (“49* [31)
kt.

emmmanmmqummdmmuawm
mm,unwwuuamormnuorpom¢nm9n
max-Lounumu. amu'nummumm
the ate at mention, at. or the «to constant at my“, RP,
minerals}. ammuummmmumnu
m:ummxvmmm Wmfiuotpolyw
“IMMOMWIOIWWGMIMWIW
Int-(smuaomtmmmpmmmummm
mmumwmmmmm. Inbothmum
mmtmnummdmmmmmmw
uuowocxpmtmmbyomormmumm
flames-mm.

munn»mum-twuummwmmw
mu WWW m with mm W «m n
mmmwmmmm. mama-mum.
mammaummwmmwm-mmdmm
otthobwfiwmddoam.

Witwatdmpmeatmamwmwpumm
«mat-mm nu www.317mbymufl'l), tor the tour
mmmtmmmmw,mamzz. whammutnn
mmmmmmtmrwmmnmmmmvm.
mmmmemmwmorrlmrumrmmnum

III!

or W and swam. in this comm. m, the point:
.10 “mm tor mung-mam in mm me. was

m previously determined mm at r; we r... {or @90th or
am: and mm [amends in tmmmmran.

The mmmmmmmmpgmm rm.
unnltmoi‘nmd nrorpclmx‘nauena mmamm
amawwxmcmmuoflmmmcuw
We. The mum {and by mtnpohtm of the plot. or
Wmmwm, Figumsnmé, tot-mummi
(3.60 ml. {action at 1W0 wwxma. The new napalm cowo-
siticm Minted from the values of r; and r” gravitas}: detest-Mme
tar «Wm nlvmt is 0.51; ml. {mum inmate W0.
Whom. the mm mm by «wwth to um was, new“
9mu.mommmmaamoamwmh melamine-1y
WW0: gamer. “tantrum tandem.
mohmrmum in WWW solution «it: nut predict we
Initial wpelyeor mitten fame in 1.111: study from the rate at dis-
Wo! them. Telnet! er awnm «1.me
on the Wine that an amtmpie exposition ecu-urn n 0.}; m1.
mum laconic Wimp. In this we the eopolyw manna
mm rectum to:

”102?. a 1

It as MW teamed mat the degree of :1th ms the m

u Ihmfmthepmimavelueecf rlanérglethat:

fir. ‘ 0003

1111

23238:: tram mum: were valved simltmemaly the foaming
values were rounds
I", II 0.33
r. - ¢.CB
Using then. estimated value- fer 1', and r. the rate or disappear-
can: of the women m minted true the 2:33am: integrated at.
mum. mmthmmmmMmfim
35. Timpomu immuuatnightmemmsimm
Figure 22.

1L2

mm in?

0mm RATE OF CLWLPSEIZ’ATEGH CF ’ g :1: «3.; 52m ITAGCHIC ATE} {II L- m "E
(1min: r} In 0.38 and r. I- 0.08 in Wmmnn Solvent
hath Sim-isolamymnitrm Catalan)

 

   

(b mm" * MIMI)"

 

 

 

 

Tim
mm mm - (him!)
0 16.3
3" 10.1;
113.0
150 ' 9.8
230 10.7
1520 10.2
ace 9.5

 

“:w u “A.“ _-_ “A _—_A _.A__.
r wry“ V—fi ‘7‘. V w. w “W 7‘" v—v _, ~—-—r r—V’W f

103

r A‘

figure 3 f)

«kaQV\ w SR

 

 

 

 

N 9 mV e v N Q

q q 1 q q 4 q 1 a u 4 a m.Q

I o O O IQ\

C
.NV
ix
%Q.Q “0 390% h? mwsethnnhv
SENSE“. K\\.\ S .Y\ 6:?me \..\
t9xb~§m$®oe®b mo mflbmwx \\exm§§

 

 

we] 50/
MW

 

2/,(Z‘W729/ ‘aylfl
([ZW]’9/*;I,([

{2'
/ [I

III . acre-t. 317m: or meme-mascara mwme mmmm

Tim ecmpoeition of cepclymer maples m detemlned after tint
extracting the sax-@139 ccheuetiveh with bemmo in I. W actuator.
This was done ta tree the ample: sz any residual 30mm. The emu
merit beaten the «magnesium: {mm from titration mtiwda and that
rm from clmtal emigrate me good for extracted amen. A «iii.
fame was noted, Weaver, Ween the camitian o: Wotan}
nan-91m detmined by the titratien mm and that calculated from
91.me Analysis. warmer, the cempceitiee o: the «polymer predicted
from the rate of disappear-ems at mmm m the quite wfmt m
that calmlated 2m culminate). amlyeia of the comm.

Scam of the m why this ciiffemce in cepclymer ewmeiticn
may have mourned are:

a.) not an at the eepcknm was precipitated {me the advent.

b) The mlymr pmfermtially “amine new of the ma all

it w precipitated ..

c) A fraction or the pelymr was wluble 1n bmem and was

mad 1n the Soxhlet esctmc‘bien.

:1) Trace! of was. such as W, affected the accuracy

of timtim mum.

Emu 01mm analysis cf the (mute ample gave 3. 11133181"
faction of than“ made ten the arrtmcted samples, it was
tame tint 1W anhyfiriée swimmer was 0.690% en the ccepolyzm

WWMitat-m. WW1W Wu moot!»
modbybmoutmtm, lime “manpolyaaamedtapclw
1% We mung thin mum which was carried m for long
parted. or than .3 30° 0.

races of mm much u 1mm mm hays prudently um
ohm, in this label-gm, to meet tha mu w W 01'
the titration methods «played (28), in determining the much of
WW mm. W. 1% flu M W that. to
find differences hm tho @0th mm rm :1th method:
MWtMMIMdmemWW
Owl-o

1C6

IV. HEMP! HEIGHT GP STYR'I‘WI'EACCHIC 1mm WSW

The main» «mas Holman“ weight of polymer- hu‘ hm comm;
datamamdbymotmtiommmmu. Mashhad“:
Wfimmmm to am. the mlocuhrwim of:
Whom“ mm oopclymr which had bean prepared in human:
calm with buoyi W. «m. Tho umber W mlmm
might round It. 23.060. Emu, the min pro-lure of tho napalm
{if-W m Wuhan when: did wt «up: n comm «31mm
mm. 1210 (name 1» height. W m two liquid larch, ”guru 31,
mmummahm.mgammmgmum. mm
indicate that the mm m M. m thy: 001:0in mic.

Since the m mm I“ and tar mum“ of both come:
m1” tha 60cm» in height with time would suggest that the oepolymer
prawn-w nmmvmtmdmmlmrmm than
that mm in bum Iolmt.

Tho problem at much Mm”, which «1% W10 to polymer
mimics, phantlmuummmmmmnuormlwmma
wmdmmm mutant!” labs-attain“ mm
mm (60-62). The difficult“! as grater for WM polymer
mummmmmummmmz. 11th.
W m “mum calvatt ti of 1m molacnlar weight,
Wmafiuamompiamtmmmwmsmmmay
to W tn: m avmgo miemhr weight.

1L7

himtaatm mimingd‘polmer untimhavobm
W for tho “taming“ at m wig-ht “man W mm.
mambmmumtormmmtm.
mwumammmm.muumomma
WWW mm madam. womuoamboohmm,rm
manta-3w nan “munch... morning tho :1."
mmummunm.

mow-13m umpwmmm tron-90° mum
mummmtorum. Wom,mmmmr
fathomhpmndmbmoulmtmtutbomm
pupa-ed In Wm ooh-us. mumammutim, F.
mbowbfimt

F - am

A doom-ninth: who: Wtioumldbo mated to 1mm
the average claw of polymerization. wherefore, the act tint tn.
helm: “wt in higher far copolymro W 121 hamm- 001nm,
m which thq m precipitated, than far the 00:30th propued in
totruhydremnn mlvmt, in which they were Comb]... wmm tha
prwim evidence or a «Wine morale in the rate ct copclymri-
nmubmmmlmtduatogdmmomthonummcf
“mum in I precipiutmg mm.

mountain Wmmfimmfidfluflmmdew “polysa-
mtmuthomoorulolvm. ThocmngomWéagx-«ot
polymriutim, a, aims cm War, 1- mm .- remu- (as) a

103

a 03%
M

.1. 3;
F F,

hmcumcmmww,8umumtmw
mtim,mflummmmtm

Mammarmtmtmmtbmmfldfarwm
1n tmwmnm, MW, 11. has been reported (63) that both toluene
sudéimnhnmmmmwwmmmfwboth
umwmmwmhm men. Wax-9.3%»
Wmummmmugmmmonmwommn
WWW. “mum-Mamasumt
Wmadmmflmnmgewmght,umrmmdm
emmmvmrmmmhwm
' mmmotmmmmmntzlmrmmm
wtummmtmnmmmummmmr
mmmumwpom. mmwtzlflmmmmm
by:M4ficflmflmottM1wm1mhrwdghtumlu,arumu
mmmumwm. Lehinotnltomtmglmm
mxmommdommuummummwwm
:Wmmmmmmxymmmommnm. Poir-
memalmdhhthaihapeotthawpohmmlm
to wmmmu the man-mum actor. r"(e). Warm
mammqurodbotoroawmueomluimmbodm. Mira-n-
nor-,thowcrmmumflmmuuammuotmr
in light ”than: mm. which had often been Wt ta

1C?

We. rho pregame of dust Mich: would be impactod to afloat

the éiasymatry value of. the low-at mlamflar weight. mp3.“ mm than
the highsr mlm weigh 32:21:15.5». For these mm, the uncorrected
values or the weight average melamin- wight we midsized ta be the

mere accumta Wrath.

(K 3313333021;

CIJELUSIEfiS

1. Itascaie anhydrido mmtrstim can ha aster-finned 1n the mama
91‘ ”may by dimt utmticn with base .

2. 5%.er warmth: an be data-mm 1n the prams er lunatic
mmhido by direct 1.1th with 23m in acetic ma, whm
both mu m in hm ”hum. Tha method it mummy
to mm aim meantth in tatmhyfircfmn mum of

the We mm.

3. The at: of «:1..an a: 1:). male ratio of “mm and
1% W appmzimm first order dapmdema with respect
to the mutation of similar monomer. The: apparmb first other
mhmufammfmmmml

 

W Saw it (33:3
3mm bemoyl pat-0mm 1.8 x 10"!
3mm bm-iwbntswnitfila 2.6 x m."
1'me bmcyl ma 9 ,0 x 10"”
MW ‘himwmbutymitrno 13 .5 x 10.3

is. The Mu ”mg-a mlmular wigi'at, En, ct an untrutiomtad maple
of DMD-inmate amends ccpolmw, mm with bmoyl
W0 catalyst in bmmma aolutim, was mum. to be 23,660, by
the «mom pram mathca .

5. Tim mm “m mm weights, E" or mm mm
man a: mmmc Wcio oopclymorl, prepared an an.
:m mt”, mm mm by than light mum-1n; mauled. rm
valua- or E, m:

 

HTM‘BLTPJE CITED

LITERA'NRB am

1. a. n. W, H. a. Mo, woman at.“ mm» (1955).

I. no In M)... G. H. W“ J. W. W WAJJ.
m. (1957).

30 R. 30 ””3 II. 3. MI' mm M mm” W).
he 8. R. Whit. a. M. W 8h“ NM” (19318).
S. rommzom’ J0me“. mo'fl’ 20H: (”I-£5).

6.3. R. m. R. 3036“” Jo 39W, 40%. all...“
116 (1992).

1. L. P. “one, ”Who in (fir-ate W.‘ 3:6 mm.
D. c. new: ad 00., m. P. 289, 292.

80 a. W, J. “0 Chill. 300" m 3138 (1952).

9. x. a. 8m, “WM a! 0W W,“ wan,
(1956), PP- 15'21‘0

10. ‘0 M and I. m, M. "0 Ohm... L31. ”a. a, 90 (mm.

n. J. ncmwno 30W we”. Chm. We 36.
387mm. ' ’ '“'

u. 1.. n. J. run-m, m. m. chum, an. m, 2, no (1933).
13. r. n. nun-no» and z. m, 4'. An. can. In... Q. ms (191:6).
1h. 0. I... can: t. J. m. an. m... a, mac (19w).

:5. o. n. and. m. .3. M. m. u... n, 692 (m6).

:5. n. m. a. n. a... so... a. mm mm.

11. x. x. mm and w. A. um, J. can. 8°C., 3060 (3.925).

18. a. Ioor and I. a. 8m, M. Ma. Am, 5,. 550 (1951).

19. a. r. m and x. l. m, m1. can... g. 1.191: mm.

20. a. P. W um! 30 ll. IMO; m. Chat. my 751 (191.3).
a. a. w. m,‘m1. cm... g9, 92:. (19.9).
22. E. I. 513801 and n. I. ”can. J. Am. man. 300., Q, 1557 (192.7).

23. I. 8. Lace, ism, It. row”, Comm. and Buintivu,‘
, edited by n. 3. mm: a. 1. Bow, led (1952). pp. Jae-11.6.

21.. R. L. mu. me! 3. mm, '14me Email. for Plastics,"

25' ,o J: Flo-17, W at POW 011M} 69mm PM.
(1953). pp. m, 132 and 11.1, 199-203.

25. a. x. nun-u, am 9: mm Rmttm.‘ haw-nu, (1951.). p. 21.5
fl.x.a.m:.mmm.,mm(m). .

28. J. W, punk mum.

29. s. 3. mt“; L. mu... J. h. Chan. 30... n, 1633 (1951).

29.. v. r. 1.th m: A. Mck, mu. on... gg, 1690. (1956).

292:. 1.. 5. Jam and A. Molt. m. cm... 2;. 889. (1955).

30. A. Enlarger, Why-1m Remod- of Organic Chemistry} Vol. I,
2nd Ed... Inna-um (191.9). 99. hes-51.9.

n. n. x. m and n. a. and. J. m. Chem. a. 59 (191.3).

32. w. R. Krishna as P. s. nor-y. a. An. Chan. Soc... 15. 1775 (1953).
33. r. J. F1917, J. u. Chem. 500.. fig. 372 (191.3).

32.. a. J. rump... J. m 3a., 2. 371 (1951).

35. a. 2. mm ma L. r. 3111:, J. Phys. Chm... 52. 1371. (192.1).

36. H. M, "Chantal Architecture,” «Mod by M and mu,
moraine. (191‘s). Pp. 121-173.

”dd-“W "1.: teen 13’ f c. "udMO
PM. (1956 . ppPBO, 31 andlngB. W W.

38. I. 8. 8%“ m ’0 DO”. J. ”a Ch“: 803.. ég} 159 (19%).

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39! BO ‘0 81.10.. H. rm m R. Bpaiaer, J. Opt. 5000 £30, El.
753 (1950).

1.0. n. A. Brice and a. ram, J. em. Soc. Am. 2;, 1033 (1951).

' 1.1. firm, mommmuwmume
Comm-fl Eluviar Pm, (1950), page 356.

ha. Intmuml cum M100, V01. 7. pp. 12 und 350

143. I". {My tad a. F. Steiner, J. Chm. Phys... 21. 1211 (1950).

2.3.. £6811», ”Physic“. (it-{$1116. Chametr-y,’ mama-31111. (1955) pp. 1.12.
:32 .

as. P. 5. W1. and x. Beau. J. Am. Chem. Soc... 552. 2299 (192.7).
1.5. P. D. Barth“ find 8. Altodml, J. An. Chm. 300... Q], 312 (191.5).
£370 JG 60 W; J. Ch“. 500.. w 3707.

be. c. 00 “W, H. To C'mmw 3M 80 811113, J. Jul. Ch”.
Soc... 1;, 2661 (191.9).

1.9. r. a. mo and r. 14. Luis, J. An. ch... Soc" g. 1592. (19341.).
50. r. x. mm sad 0. wining, Chen. Rm... 3.5,. 191 (1950).
510 In To Vin, J. m. cm. 3%.. fig 2550 (19M).

52. ,0 )1. 10m, P. R. M mu. 1" mu, Jo LII. Chm. 3°C.. &
17131 (19155)-

53. x. Rea-kt, J. Polymer 5.31., L 1.55 (191.6).

53.. c. 0. Print. J. Polymer 5:11., 1, 83 (1936).

55. 1'. All": and C. C. Price, J. Polym Sci... _2_, 151 (191.7).

56. c. a. Price, J. Polymer 3a.. 2, 712 (191.8).

57. n. n. cam-cm n. 1.. man, J. Am. cm. 303., 12, 3953 (1953).

58. C. H. MOM M ‘i P. $1735.11”, Pmc. RW. 3060’ (140113011), 3223
220 (1955). "'“'"

59. R. a. w. Hex-rim and a. a. 3mm», Ram, 2.3, 335 (192.2).

1.13

{£0 P. w. Am 6114M. ‘- P1533, J. chW 861., as; 386 (1737).
61. J. In Garden and 3. 0. m3, Jo. Palmer 3010' 2-6" 255 (1937).

62. 2v. Béfcmwt, a. math and a. Heyefiwff, J. Palmer sci... 21.591
19S .

63. n. s. (3er m r. a. Eamo, Tums. Faraday 30.3., g, 328 (192.7).

 

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