-‘ ’-re§u:4_;4lfw';m;:..,-rnad-_- .-.. '
cuc°."... .~,-\'; ..V.

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‘n'? "r
~v’ v.

.._
"tgg. 9;. l‘n- -
‘:‘:3_' .t-a. ;~

-_ ,2,

 

 

EFFECT OF STiRRING ON THE
EMULSDN POLYMEREATION OF
STYRENE WHEN CATALYZED BY
HYDROGEN PEROXIDE CATALYSTS

Thesis fer fhe Dogma of M. S;
MICHIGAN STATE COLLEGE

Vidor Lee Halfenbeck
1948

wasm

. .J

! IIB’RARY

DAIChngH St ‘1’ C"

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. . ‘11 J“

EFFECT or arms 0N THE Eh’iUlﬁION POLYMERIZATION
0F STYRENE WHEN CATALYZED BY

HYDROGEN PEROXIDE cxmmsrs

3?

VICTOR LEE HALLENBECK

A THESIS

Wyeth. School a! Graduate Studio: of Michigan
at“ College 01 Agriculture and App“ Seine.
ummwumrmomm
Managua!

hiﬂTER OF SCIENCE

Department of Chomﬂtry
I 948

.
-:‘ 4.“
.7

331.679

ACKNOWLEDGMENT

The author wishes to mu his «lap
uppucuuea for ﬂu help ad mmgcmm at
Dr. R. L. Guile during the course a! this Mutt:-
gm

TABLE OF CONTENTS

INTRODUCTKH!................................
HBSITanBAJ. ..........‘...‘........1...‘............4...
zucpsznumznrrau;
Raga. “H”..........................
W .......................”H...”
Pm. ...............................
amt-hm ..............................
JGUth: ..,.......................‘.........1....
DISCUSSION........~................n.........
CONCLUSION..................................~

BELIOGWHY I.0.0....0.0.0.0000...III-IIOOOOO-

Page

2-6

10-13
14-18
19-39
30-“

35
36-37

INTR ODUC TICN

mm: "cont you: emulsion potymerizution has been intensely
imauﬁgatod both commercially and from the theoretical viewpoint.
The“ investigation- hth M concerned with various aspects of the
Indian: tho duct: or! temperam. ﬂu dad: of concentration of
cmumamdmmmnumma.uuumd
Wﬂhmﬂaﬂumwdmpdymu. mum
MWMcsmmuﬁomwudwmormm
Wnpmmhmmdadmwmnhm
mph...

Con-“cub“ damniammoluﬂmmm:
ngumwmﬂmnmhwmwduﬁm
mwummmmuwdm-ym. Compuim
duWMWWhmmnﬂmﬂmmmkd.
mmmmmmmumm. 01mm
WMmuMdoﬁthodedn‘una-ﬂumm
”Whit-“mi. MoMWmmm
amtonmammmumm
"man-acctuuwa.

Thismhmshﬂduummswudmm
Mdgmnzoz.mnmbmuwlymﬂmdnytm
hnpaﬂcdunmulmnnym mmwmamdm.
Thu do“... deMﬂtnMInbMdtﬂIMI.

141mm
Styrene wu ﬁrst isolated by aisﬁllatioa of Gum Stern. Poly—
styrene who ﬁt“ mantlmd in 1839 was thought to be an oxidation
pMMdmhmﬂcnﬂuﬂm
hxuvammmwmeumd
«muwmmgmdmmz Styrene-lulu
bccwwunmummmwnwmnu.

hmdmuuyldemdmmdocﬂcdmmb
McwuquudeﬁMarqum-Mh

M‘ H H
CI/C’Cx‘c ”Cf-0‘ 00-6:
HC ,9”: “H6: CH2, -—-)HC~C_ ,CH
HC=C W? H “9
”damn; HC=CH1 HC=CHz

mmmommou-mmmummm-mq:
Warm
Palydeuyn-nh-bmcmmwhbumhuhn
mammal-m5 ncmmmummummx
dﬂWMcwmoMMtgmugchm
Wm? mprocua 01“.!”me “highly
quﬁrdmwmuhlﬂs. WW1:
mranMnuMmﬂmrdcdrmﬂmuwc
cuﬂycmonu.‘ mmmmmaum_mun
WJWWM(ulMWn-)mh
u alcohol. mum. carbon WM.. and bananas”
Mukmwuuubcuymmmmpamm

wﬂchcudﬂaduannhﬂyingngMnmﬂidmmmmgmmur.

a
a surface ragutator. a catalyst. a. chain regulator. and I bui’fet.‘ Tho
emulsifying agent can be ammonium soaps. sapcnin. organic aulfonatel
of long chain daemon. and mama.“ ,

Many worker: have investigated the questicn at whether or not
an pazymmmuo: am pm. in ﬂat W or ch. momma phuc.
Fryun; mmmmmmuhmmm
In! mummmmuumpdmamm
menu. mmmmwm’mawm
vmmdmhumm “amt-um
ans-sup}! Luthmmmmmm
McNamWhNMG-mma‘unm
{ mum-um MWmchpI-Ivduumyhm
wmwumamuaunmm

palm-"u
Directs-m Mommmmmm

pmodhmdhmcnuhwmm mammal“
mmwpmmbyu.umupunuuu." mam»
'mehtmblom‘dmhuﬂvuuummu
muthmmhMﬂKadpumuh
mum-3mm. Vmﬂﬂlapdymhhrmdhthnm
mumpmmhmmmmum:mcmncma
an. an." Mend: dumalrlhocmmdpolmmaﬂuhm
momma. mMmﬁhanMdPMOlﬁ
aIMﬂtm‘wmamutop.thachoi-twmom
vamhmbcmwmhm/Wudfhcpolymum

4
third. none of tho polymer could be detected in the nwnomer. Fibentschen
reported polymerization to ho tn the aqueous phase on observation that
tho onmlalﬂod mucus «cream in m u polymerization proceeded.”

Tho omnldon polymerizattoa a! otyrono to considered to take
placo tn throo otepo: on activation inhibition period. a steady reaction or
propagation ported and then a termination period. Tho rato a! prepogntlon
tn diluto random” concoutrotton to nearly linen with rospect to tho
concentration at tho emulsiﬁer. Tho boot commotion o! emnlolfytng
ogmto to hotwoon 0.24%.

Prtco out“! thero on two meﬁmdo of activation namely tho troo
rodtcolmdthotouic. Tholoctthotthooctivottanportodtodocrmedby
using puro otyrcno. by mludtug oxygen. and by burning tho temperatxuo
to an indication that lmpurtttoo in tho oquoouo phooo inhibit polymerisation.

Mm typoo of cotdyoto hovo hm doocrtbod for tho polymerisation
o! styrene. 5mm 0! thou oro hoot. light. mo. porozddoo. mun. tho
moto! chlortdoo (B. Sb. Sn). {Ii-3mm compomdo. hydrogen acorn“.
porborotoo and phosphotoo. Tho catalyst and to omuloton polymerisation
tounanyotthomtor solublotypoouchoohydroaoopormoorpotu-
“WWW; ﬁohttorbdugﬁomorootddyuood.

Boron doocrtboo tho no of mm; tog-to oo oo-cotolyoto
chiming polymortnotton con ho conducted ot tumor tomporohu'oo old
at and: groom mod when ”rim roducttou "octtvotoro"oloh oo
oulphurouo odd. oulphttoo. bionlphttoo and on!” om“ proud- 0!
ddohydeo out hotonoo on and. Tho commotion o! cot-1y“ ho o
dtottact oﬂoct u polymortoottaa. Tho roto of polymortuﬂoo hoo hon

reportod to ho proportional to the oquare root of tho concentration
of tho ontolyot.

Evano hoo ouriod out considoroblo work with hycirogen peroxide
and with forrono iron oo o cotalytic old. A troce of ferrous iron greatly
docrooooo tho octivotton period and increoooo the roto of prOpagotion.
Tho hydrogon poroxido and ferrous iron tum works in the following
manor:

1.- 3202 + to” -5 HO + H0‘ + rd“

2. HO + r.“ 4 HO" 0 ro+++

3. 1-10 + 01-12 ~ ﬁn -) HOCHZ . 32H"

4. KOCHz «4311+an ~gH—9 KOCH; «98- CH; 4-9}!
Stop two to ohnoot may oliminotod it tho hydrogen poroxido to in
mooo our tho (mono iron.“

Sinco tho and mothodo for dotormining molocnhr woighto
(ironing point doproooion. otc.) oro ontiroly wouoblo ohm molocniar
woighto of 10.000. moloculor ooighto 0! high polymers oro dotorminod by
mothodo involving oomotic proomo. viocooity ond tho uoo of the ultra-
earthy.”

Stoodingor hoo pootulotod on oquotion (or obtaining moiocolor
voighto by viocooity:

M. W. o N‘p/KC
whoro N” to tho opooiﬂo vtooooity which to doﬂnod no tho incroooo in
viocooity producod in o oolvoat by dioooiving o unit amount o! o oubotoneo
in o unit wimo oi tho oolvont, K to o conotont. C to tho conooutrotioo of

polymor (in tho oolvont. Howovor. ot hoot. tho Standingor viocooity mothod

6
givoo only roiotivo moloooior ooighto. Prooﬁng points. oomotio proo-
ouroo. ood cud-group mothodo hood to minor which on tormod mambo!
ovorogo molecular ooighto.

Ofton tho voiuoo ohtoinod with tho ultrooontrifuo vary greatly
from thou obtoinod by viocooity. Tho oitrocoutrifogo givoo moro «qu
nohoohltodotormiutioohotdootooniiobﬂityoltho oquipmoutior
viocooity dotormiutiono. tho viscosity mothod to tho moot fraud”
and.“ Boonbo momma-«my motoculorooiahtolotypicoi
“rootimtodpoiymorwouidnothovory ooriouolyioormuioootho
poiymor ooro oxtoooivoiy hrouohod. No roiiohio cmlooim shoot
moiocuiu ooight diotrihotioo con ho drawn from moioculor woight dot-
alono without fractionation at tho poiymor oomph.“

Experimental:

Reagents:
The reagent: need were no follows:

We“

Duponol 6

Hydrogen Peroxide
Ethanol

Aluminum Chloride
Mercuric Acetate
Sodium Chloride
Methyl Alcohol
Carbon 'l'etrochloride

The styrene was obtained from the Dow Chemical Company.
distilled under new (15mm) and onlyﬁiotportionhoving minder: o!
refraction at 1.5450 one need for the polymnieotiono. It on stored in
the refrigerator {or no longer then u week holoro noo.

DisponolG. ooulionetedderivotivoolloorylolcohol (DupuCoJ
oooeoodiolﬁ oothoomdotﬂor. docoprovioeouporinuotohovoohoon
itto meiotoioo otohlo Wuhan monomer onlooter. oodpdymer
end voter et thio concocted“.

The hydrogen porouido (More): 30%) on nod to very-lea colleen-
mm .003 W ” o7, We

Thooﬁmluodioeeogulotiooolthopolymorooocmiol
95% undo.

Wellies-idooootochnicel m “mercuric oeokto.
mum chloride. methanol. and corhon mama. were 3...... c. p.

undo.

$.11, water used was specially puriﬁed bang distilled (mm a
K}.- {110‘ solution in an glut aquipm directly we tho reaction tuck.

Equipment:

All experimental polymerizations were carried out in a four
neck. one nu:- ﬂask equipped with 24/40 ground ghee Jam. The nae):
was equipped with a thermometer. a vacuum sampler. and a mercury
sealed etluer propelled by a variable speed motor. A 200 cc ethn-
meyee waa attached to the vacuum sampler and when the vacuum seal
applied a eample was collected in the ﬂask.

The nitrogen was paseed through a train which contained two
500 cc boﬁlea of alkaline pyrogallol to absorb any traces of men and
was introduced into the ayatem above the eolutlon.

The {leak waa lmmeeeed la a constant temperature vale: bath
adjusted to a temperature of 40°C and ﬁnally to 60°C.

A Beckmann pH meter was used throughout each polymetiaatlon
to follow the pH value of the emanation.

‘A cmon—Feneke—Oetwald Viacoalty pipette on need to determine

the speciﬁed vlacoalty need in calculating the average molecular eelzhta.

10

3W5" gram! of styrene were added to 600 grams of a 1%
eolutloa 0f Duponol 6. Thin gave a one to eight ratio between monomer
and water. The above mixture of styrene and dispersing solution was
add“ to the Mall flask which had been previously immersed in the
Maui mum. vat" bath at 40°C or 60°C. The pH value was
Mitten. Hydrogeaporoaldewaa thmbem .003
melee up in .7! male: concentration.

Sample ﬂuke were prepared by acme; Ipptodmately 2! to of
ethylaleoheluiateaceotMCl,tehelveeelgM (lo 1/100 decrees)

«Wile-ta.

denmphMmthmwwmh
was)» “we. At each mung {he pH value um ennui-doe eae
“armada-due“ ‘
Theeoempolymeeeaaeepmtedbymdaeutﬂhge.
mwmeumedoﬂndaueeaempledlhempu-
Weumubmeﬁemmmbyﬁemm
acetatemethea. Thiemeﬁedeoeeletadotadﬂagezramadmm
uMetGalSeeuuxple.aﬂoehcbmdfoeouenﬂnnteeudm
eddlagZOeedmethml. Mempuloddmmgkppm-
lmetdySmlMu)2°eedaWeoluﬂoadeodlmnehlorldeeaa

11
added m 157 :9 cc a! taboo Morale. The liberated end:
an as M «mm with as mm: m... mm»: mam.
Emmmwodum mmeeeedemmdedm
W. The amount amended momma: wee calculated a tonne:

WC. 0! W in ample '- (we. of ethanol + Wt. 03! eample)(N.V.me¢l.l
l

N II normality d N108 and

V 1: volume oi Nam! need

meg. a Week.“ a! etyreee (Joe)

ﬁ-Wew'hdm . 1&de
Vital-ample Wham

The consumed polymu vee veehedleomtbe catatonia”
with 99% «mwmhmﬂmm Thepotyrneevee
mes weehed several times with alcohol. Medan“: beamed
we!“

mmdpdymumﬁncmnwau

%PolymeeeW__t_._§zg_lLr}ep_. utdm‘wo
Wt. umpe 'Wudetyeene

The ever-3e molecule: veiw wee determined» Mere
viecoeuymehod. Oneteumotegnmdthe ponymee Oomph... pteoed
unooccvommmmmmsoudm-mmm We

hMeeephedheMrmMehdy—Mhoupeﬂodbeem
compldeeehﬂoedthepolymu. newton-hie neekweethnﬂuedee

muewmwudwmmmmmunm

 

Wm enter 1.. 20¢ (.10) c. The link us allowed to «in. to
Womeeendthenmleduptowe mark.

l2
Vino-wee mew Inﬂuenced macaw». at e
Canoe-Imam.“ moan-a pipette. The ﬂeeces” date W
ere-need um More equeﬂoetecekﬂetem Wannabee!"

W’em
M.W. ONQ/KC
Winn: MJH. nevus emoleulu weight
XI: 1.8: 10
c nmcmmdwumm

n.1,.rmuoumaaapmuzo0c, 1
Wmdzoﬁ

Amme.mexﬂueninnoltheldﬂumm
WMWCmm.wﬂheleul/3hchhhdevu
“Menteaeeeﬂheemlldoeeym Suntuceﬁmou'emel
Mum: cmmmmmamm.
mmmammcm. cmmmeum
out!“ Vmeﬁe Stine: wee mwmm Inter-
mittent stirring on the: condition when the m wee Muddy
mmmMsmmputumMammmeu-wu
Nwmmthncmdiﬂmehnemeﬁrrueeemmu
mmmmmwmmwmmmnuumm
htheemcmuﬂngretedeﬂnbgdhem‘vumbym
«.mwmmnupmn. Themmobaoleingetncedeuthe
hem;eﬂimbythewumnhmmmdeweehkuoethem

Since even ought traces d oxygen Mubeeodtecomed by
previous wherein inhibit the tendon. «nude: end «mum

13
enter to he need in the experiment wee carried out in en etmoephere of
nitrogen {reed 01 oxygen by penises through elkenne pyreaenol.

Heinz the ebove procedure meny polymerization there cerﬂed
out end the reﬁne Wed.

H

 

 

Dncuuuonnumnu

Gena-1:
Amount 0‘ 9079.0 1532::
amal‘ﬁmpoodGWOe 600m
Nitrogen Amoepheee
Teble 1
Seraph ' Time pH “7.13% M.W. ﬁve.)
1 1590 mine 0.05 9.10% 132.000
1 1625 ‘ 0.15 10.90 251.300
3 1150 6.09 - 153.350
‘0 I”, 7.10 an- “4.500
S 1040 1.10 10.90 “8.500
0 2035 0.0! 83.80 931.600
1 2145 0.0! 36.14 031.400
0 2805 0.80 30.05 439.009
wan Beth Temperature 40°C: W sum
Cehlyet Conﬂuence .10 order Hydrogen Perodde
Table 2
Seraph um. pH ’27.de“ MM. ten.)
1 150 1:11” 0.60 0.95 % ~-
3 1.0 ‘0” 0.3! 9‘
3 2!! 0.5! 0.“ -
4 265 6.55 1.9. ~-
9 120 0.1! 1.40 110.000
6 358 0.65 1 1 .00 399.000
1 500 1.20 41.19 319.000
0 “0 1.30 62.31 351.100
9 1295 1.20 “.96 300.500
10 1350 1.10 11.31 309.300
Weter Beth Temperetere 00°C: mm Stirring
Cetelyet Concentrettoe .33 melee Hydra- Peroxide

Table 3
Semple Time 91% 7919017111" M.W.(m.)
1 140 mm 6.05 4.31% be»
3 235 6.60 16.56 131.100
6 295 6.13 39.96 241.100
6 333 6.15 - 242.800
6 395 6.10 50.81 256.900
1 520 6.10 69.56 212.100
6 615 6.60 16.81 115.500
9 600 6.60 00.00 260.000
10 1320 6.00 09.01 830.000
Weter am Temperature 60°C: W m
Cecelyu ceeeeeereuee .19 meiee W Penance
Tehle e
$139M 7:
by Polymer
Seraph '1‘1me 1:3 mm Veluee manure.)
1 110 min 6.70 0.557. 1.66% --
3 110 6.90 6.59 - ~-
6 105 - 6.80 1 1.61 36.100
5 265 6.30 20.01 11.30 35.500
6 293 6.30 14.61 19.63 11.800
1 31! 6.60 16.69 31.61 19.800
0 386 6.80 63.96 69.12 95.000
9 “5 6e” ‘0.“ 53.93 ..
10 683 6.66 04.11 11.66 06.100
Weeee Beth TM 6006: Gee-bet sum-g
Cetelyet Commence .1! we: Hydrogen Peroxide

mum.

 

15

16

Table 5
Sumpu Time pH 09¢” M.W.¢eve.)
1 66 min. 6.60 6.30% a.
2 80 6.50 6.60 e-
3 95 6.10 9.60 62.800
6 1 10 6.66 15.86 121. 300
5 160 6.80 36.63 162.000
6 1 70 - 62.26 175. 800
1 20! 6.80 82.91 173.000
6 260 6.60 69.10 166.900
9 330 6.50 90.82 160.500
10 385 6.30 87.23 130.600
Weter Beth Temperehre 60°C: Nee-uterus
can": cmenueuoe .16 under Hydrog— Paulie
Teble 6
Semp1e Time 911 $0301” M.W.(ere.)
6 ‘0 1111.. 6.79 3.60 % '1’"
I ,3 7.10 2e“ ..
I 70 7.00 3.10 -
6 100 7.00 6.60 67.200
6 160 6.60 36.90 132.600
6 220 1.00 66.10 166.700
7 215 6.10 66.20 136.200
we“! Beth Tempereture 60°C: W 511mg
Get-1n! emanation .15 under Hyde-cg. PM
'reble 1
Seraph Tune p11 1'» Polymer M.W. Cove.)
1 300 6.6 2.07% m»
2 360 6.2 2.16 33.600
3 620 6.6 2.19 38.600
6 680 6.1 6.36 . 66.000
Weter Beth remade" 60' C: m at Bantu 600 rem/min
Cetelyel Commence .1! melee 111mm Peewde

MMCW

 

17

Table 8
Sample Time pH %dem M.W.(ere.)
3 no 1.: 12.71 “.500
4 210 1.1 21.43 64.500
6 300 1.1 14.29 10.100
6 330 1.1 31.39 11.300
1 360 1.0 40.14 03.600
Weter Beth 7001mm. 60°C: Rete of 51mm 300 Rem/ode
Cetelyet Canteens-e116. .16 under Hydrogen Pm
Nurogenneed only» eweep ”meme-adoring eempuq.
'reble 9
Semple The 1311 51mm 61.W.(ere.)
1 08 m1ee 1.10 6.09% - 1
z 140 1.00 11.11 16.000
1 203 1.20 11.11 03.100
4 168 1.10 40.13 106.100
6 198 1.16 86.51 101.100
6 310 6.90 62.11 101.800
1 350 6.90 11.01 93.300
0 388 6.10 11.66 16.600
amnarw soccgmummuOme
Ceteiyet (:ch .16 moler Hydra. Peeoadde
rm. no V wwwwwwwwwwwwwww
Semple The pH ”Polymer 1.1.W.(eve )
1 100 1.90 16.00 406.000
4 115 1.90 43.00 416.100
5 130 1.90 65.10 431.300
6 145 0.30 04.80 431.500
1 119 0.30 96.64 "360.100
0 , 206 1.90 94.19 129.300
We“: Beth TemperMe 60°C: Non-earring
Cetelyet Ceeeeuretlee .10 under Hydrogen Peroxide

unwmcm“

13

Table 11

1 45 min: 1.1 1.63 1. 309.100
2 15 7.7 29.26 440.500
4 105 0.0 50.46 493.000
5 120 7.9 11.02 492.000
6 135 8.2 81.83 462.000
7 105 8.2 92.13 389.000
8 195 1.9 94.23 392.000

wan B4111 1W 60°C: Nan-m

CW Comm .03 m: 11W PM

Tabb 12
5432914 Time 911 %demu 101.104.“)

1 35 min- 1.0 10.11 9'. 449.000
2 40 1.1 10.01 539.900
3 03 1.3 33.13 408.400
4 70 1. “.12 731.700
5 05 1.1 03.30 792.300.
6 100 1.1 ”.11 183.100
1 113 1.6 03.13 144.600
0 143 1.4 03.66 604.100

WM Bah 7mm 60°C: Non-m

only“ Gunman .01 molar Hydrogen PM.

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Discussion:

This workwumﬂdﬁmthcmuiondmsﬂpﬂum
aﬂoat olhydroga world. as catalyst oath. polymnhsﬂald styrene.
mommuwmmuumdouummmummuxm‘
cumucmxmmwuwaumy ("autum-
{mumpmdnmgaumuytmvudmcwhwnpuuhn
dMmemvutdmumuwmht-mpmo
polymuualonwuwnxuwocm. ummmmammm
mdwmdwmmmommamdyu.
Wamucwydwmwhumbumapﬂm
W nmdﬂanMVumhhnn
mmmmmmupmedmmmmcwm
Wdhuumlmwdmm» mount-um»
«mwummmmdmm WW
amnmwummusoocamommmauu
ummwmuununmum. Quantum-ﬂuke!
WWW-d. Amamamwmmmm
ammummmumum.mmm
ammutwamlumuumdmun.m.
whommdwmugmmm

ltmobmdﬂntﬁnﬂmﬂhhuhﬂnmﬂudm
ammummouduumnumuhomxyw
MmthMWvWMIuMMMM
Wmmmmmuwmthn-ruamm

31
amao‘Mswidomdnmhnmo‘.
zmuznuawumuuw°mmupm~
m4wxzmmamuww. %
Fm‘mdyolﬂg.luum¢.n.mcﬂectdmﬂa¢cub¢
«In. mmammcubcmnbycompuﬂmmm
umplu‘mdeI-MMumplo-nauqu
«puma. mmmmmmuwpm6m
tum-Immmmnmmmn. WNW
mmmwummmmmmw
“unﬁt-Moms. wmcmmth-W
“mmmmmmummmmuw
.mmmm “mum-atrium
ruppndthormﬂnmhlupMdede
mummcdwmmm
mmmummaummdm
“Wuﬁuhmthyucmm Mmh
Mwammnmuummumntumd
cmvuhemdhmam Wand-outed. mu
mxymummMummrammu-umm
havuuhcmcmm mau:w¢mmum
Waaumumoucnduamhmm
“ﬁamuhcmcmm;
rimmundﬂptVIﬂwumeerwamm
cMWuﬂm-Wmm mm
than was. named and the worm melanin yacht: m mm

32
with 3 decrease in the ennui a! egitetion. The emege molecule:
edght eureee iudieetee tint decreeeed earring tureeee the maximum
emege molecule: weight» In two respects. namely thet menu!
with percent polymerization end that concerned with molecular weight.
the etirring can be interpreted as a. definite chain terminator in ite
effect on percent polymerization and on average molecular weight. at
the polymer (armed.

The effect 0! stirring rate may be eeen in Fig. V end Fig. V1.
The induction time in almost infinite with e repid rete oi earring (500
rem/minute). A: the rate oi etirring ie decreeeed. the mum time
is reﬁned and the prepuetion rete ie increased. A comparison oi
molecular weights indicate the chain termination; power oi ﬁrm.
With an increased etirring rate the molecular weights ere decree-ed.

Perhaps the chain terminatiug eﬂ'eet a! the earring my be he
to the inert etznosphere (NZ) being mixed into the system. An inverti-
getion of Fig. vn ehowe that the effect oi stirring to not due to increeeeli
N; in the system. Experimm 9 is that oystem where nitrogen in rm
through continuously during the reaction. Experiment 8 in M "Item
where nitrogen wee only need to ﬂneh etmoepherie oxygen out a! ﬁe
eyetem endthentnrned ed. Acmeﬂmdthetwo experiments
indiedethetnitroaendoee nature e “places inhibiting enact. l!
the nitrogen were b have an inhibiting eﬂeot. it would increase the
.WMewheotheemmtbeinszintothe eyetemwee
inereeeed. We wee muumwum mappodte duct tee
observed. Time it one be concluded M the inhibiting eﬂect a! nitrogen

33
ieieeiniﬂeeet. TheatedineruuhieduetimMemprobebly
dutcuygeegettinxinﬂmﬂm

Ftpvmueeemperieoedmereerieeeetetetitretioeveleeed
meeetedmeeemereeemeredtotheveiueeiorweectedmeeomer
eeieﬂetediromthecoeguldedpolymer. Thereineeiormeeeted
monomer eeleeieted {rem the caplet“ polymer ie beeed oathe dit-
(webetemtheedghteitheeeemetedpoiymernethetheoretieei
weighteipoiymerileilthemmeeietheeempiehedpolymerhed.
Themethodeldeterminingtaeeereeetedmeriebeeedmthe
reutimbeteeeemereerieeeeteteedthemteddeubiemelthe
W. Theeiieomeeitheummerheereeetedteiormdimere
ortrimereehiehereteeieeiemoleeulereeighttebepreeipiteted
by the eleehoi need to eoegulete the polymer. the reaction between the
embiebondeﬂmereurieeeeteteeouldnottekepleee. Thirteen
meeethetitretioeveineeeinbeieeerﬁeethoeeiertheeoenieted
polymer-

Areletimoiemegemoleeelereeightetothetempamre my
be eeeein Fig. 1):. The emege moieeoler eeighte at the palm
ﬂeepndueteebteieediromreeetioeeethigmtemetueeereioea
theeﬂnueeienietedtromthepeiymerieetieepredueteobtdedet
Mertmxperetnre. Theteoemeeiethieeeee were ebteinedtrem
reeetionemettmperetureeetm°eed60°m Thehighermoieeuiee
edghteeemeiromﬁe reeetioeetio° cube lower moieeuler eeighte
cemeirerethereeetieeetoo°c. Thieieauetotheteetthetetthe
mwtmemuymemeieiueeetieetedummu

34
eenee formation oi away more ehort cheine. Thie ie in conformity oith
the romlte oi previooe inveetigetore.

Meet oi the poiymerieatione dieeneeed up to thie point were eer-
ried out with e eeteiyet concentration oi .75 molar. ‘iith ementretioa
of eetelyet below .7! molar. experiment! were inhibited eo notch by
earring they could not he etudied. Ae ehowo previooely eome expert.»
mente were carried out using e concentration at hydrogen peroxide et
.75 molar with metirrina. Enerimeote eere then eerried out with
mam... end with lover connotation oi eatelyet. The results an
em in Fig. x end Fig. X1 ehoe the induction time to he prectieelly
eiimineted end ehoe the moleculer weighte to inereeee with e deereeee

in catelyet concentration.

3!

Contain:

l. Surriegeeeeeeenteereeuieiedutioedmeeededeeeeeeeie
unieeeier weight. We ie eepeeieiiy tree at the lover cementum
deeteiyet.

z. M60°c.eitheiiminetioeeletirriegtheioeereeeeeedretind
enteiyetredoeeeﬁeindletienumetopreeﬂeenyemeediureeeee
the moleculer weight (800.000).

3. inertmetneeeneeeeeiureeeeiemoieeeiereeighteeod
nhereeeeieindoetioetinu.

4. Acmerieeeeimeeeurieeeetete titretieoveioeeeiththoeeeeieee
heeedumeumuedpoiymnieﬂceteetheemutdetnne
eadetiegudimereoetrimre.

5. mdutdnheﬂguiﬂﬁontheeyetemieelim

36

Bibﬂoenphrs

l.

2.

3.

4.

7.

9.

10.

ii.
12.
13.
14.

15.

16.
17.
18.
19.
20.

Meek. 11.. end Whitby. High Polymere. 1’. 2‘78. Intereeienee Pubiiehere.
New York. 1940.

Berthelot. M.. Am. .111. 181 (186?).

Ellie. The Chemietry oi Synthetic Reeine. _1_. 232. Reinhold Publiehere.
New York. 1935.

Hohenetein. W. F.. Yingieilo. F. end Merit. 1!... indie Rubber World.
112. 291 (1944).

””0. ’0. COMM”. Ge. NM“. He m mat. He. ’e Phyl. Chm”
32. 211 (1945).

. Mark. it. end Raﬁ. B... High polymeric Routine. L1. Intermime

Pubnehere. Nev York. 1941.
Cerothere. W. 11.. Chem. Rem. g. 392 (1931).

Burk. It. 22.. Thimpeoe. 11. E.. Weith. A. 1.. Willieme. Poiymerieetion.
Intereeime Pohiiehere. New York. 1931.

Fryling. C. F.. end Herringttm. K. W.. Ind. Eng. Chem. 32. 1,14 (19“).

Men-in. I. w... Solubilieeﬂon end other lecture in Detergent Action.
in Adveecee in Conoid Science. _1_. 124 (1942).

Herkine. W. D.. Paper et Meeting of A.C.8.. Chieego. 1’46.
Herkiu. w. D.. I. Am. Chem. Soc.. 23. 1428 (1941).
rm. 1». 1.. .1. Am. Chem. 8041.. g. 24.1 (1937).

1:21". C. 13.. An. N. 1. Med. 5.2.. g. 351 (1943).

Pooere. P. 0.. Synthetic Reeine end Ruhbere. 156. John Wiley end
Sane. London. 19‘“.

Willieme. c... J. Chem. 50:. 1319. 775.
Cohenend Seal. 6.. I. Am. Chem. 8011.. g. 17. (1945).
Beeon. 11. C1. 11.. Tune. reredey See" 2. 140 (1946).
pan. 6. c.. I. Am. Chem. See.. 23. 1674 (1945).

Kline. G. M.. Br. Pieeﬂce. _i__8_. 101 (1946).

37
21. Gee. 6.. Teens. reredey Soc... 22. 261 (1944).

22. 31121:. R. L. Thompeon. H. E... Width. A. E.. end Willieme. V..
Po1ymerieet10n. Reinhold Publiehere. New York. 1947.

23. Bexendele. I. 11.. Even. M. 6.. end Perk. (3. 5.. Tune. Fuedey
Soc... 35. 156 (1946).

24. Shading”. 11.. Die Hochmolekuleren Degeniechen Verbiednngen. 1“.
Julia Springer. Berlin. 1932.

‘43..) (“731 5Q1‘EY Lib I ; BY

 

 

 

 

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