DERIVATIVES OF AN UNSATURATED

POLYESTER- POLYETHYLENE
GLYCOL MALEATE

Thesis for the D09!” of M. 5.

MiCHIGAN STATE COLLEGE

Charles Dan Burton
1948

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DERIVATIVES OF'AH UNSATURATED POLYESTER - POLIETHYLEEE GLHCOL

EALEATE

By
Charles Dean Burton

A THESIS
EMbnlttod to tho School ot’Grudunto Studio. of Michigmn
Stat. Collogp of.Agricu1turt Ind Applied Scions.
1n ptrtinl fUIfillment of tho requirements
for the degree of

fiASTER 0F SCIEKCE

Department of Chemistry

1948

AC. STI3LL'XEL- $12.?
98 Gathor wishes to trke this appertunity to express his
sincere thanks ta Dr. Ralph L. Guile for the encouragement and

cgofiorflt§0fl received during the procosc of the iHVOGtigation

and the preparation of this thesis.

331.615

ABSTRACT OF THESIS
Polyethylene glycol neleste was prepared by heating equal

solar quantities of ethylene glycol and maleic anhydride at190"c
for 5.8 hours and then at 205°C. under a nitrogen atmosphere.
Reduced pressure distillation was used to remove impurities.
The progress of the reaction was followed by neutralization
and saponification equivalents, which were used to celculate
the percent reaction. The percent reaction after distillation
was 91.54% and the molecular weight of the polyethylene glycol
neleete was 839. The reaction rate constant at 190PC. was

.0009 neg/nin. and the reaction rate constant at 205% C. was
.0012 seq/bin. The energy of activation was 12,760. The
.structure was determined to be GODS-geg-8-0-§-§-).

The polyethylne glycol meleate was reacted with hydrOgen

bromide, hydrogen chloride and chlorine by passing these gases

through.chloroform solutions of the polyester for nine hours
at room temperatures. From halogen determinations, hydrogen

bromide and hydrogen chloride were found to add 93.5% and 95.1%
respectively to the carbon-carbon double bonds, and chlorine
added to 84% of the double bonds it no substitution took place.
.Pure bromine was added to a chloroform solution of the polyester
for one reek. lilnc substitution took place, the bromine added
‘to 24.5% at the double bonds. Liquid ammonia was added to the
'polyester and heated to 100°C in a pressure bomb. Two products,
mlesmide and the aminated polyes ter, were isolated. Hydra-

zine hydrate was refluxed with a chloroform solution of the

'polyester for four hours. The percent nitrogen.was 66% or the

 

alount which would be found from complete addition of the
hydrazine hydrate to the double bond. nitrogen tetroxide added
to polyethylene glycol neleate in e chloroform solution, and
88% of the nitrogen, thioh would be present for 1:307: addition
to the double bond was found. 'Hitroeyl chloride was reacted
with polyethylene glycol but produced only fumaric acid. -
Sulfur monochloride reacted with polyethylene rlycol naleate
in chloroform when the mixture was heated.

The unsaturation of the polyester and the derivatives
produced was determined by the use of potassium‘bromide-potass-
inn bromatc solution in the presence of mercuric sulfate.

Although this was the only unsaturstion determination that could
he used, it was of no value in the unsaturaticn.determinations

of the halogenated products and the hydrazine addition product.

A.
B.

C.

D.
E.

F.

Introduction

Bietoricel

Experimentel

1. Synthesis

le
be
Be
a.
Go
to
g-
h!
i.

3.

TABLE OF CONifliTS

Preparation of polyethylene glycol meleate

Addition
{Addition
Addition
Addition
Addition
Addition
Addition
Addition

Addition

2e Amly‘ticll

to

b.

of hydrOgen bromide to polymer
of hydrogen chloride to polymer
of bromine to polymer

of chlorine to polymer
ot'emmonie to polymer

of hydrazine hydrate to polymer
of nitrogen tetroxide to polymer
or nitroeyl chloride to polymer

of sulfurznonochloride to polymer

Element determination-

Uneeturetion determinations

(1) Pernlngenete Oxidatiom.method

(2) Hercurio ecetate method

(3) Hydrogenation method

(4) Perbenxoio acid method

(5) Bromide - branete method

3. Date Table-

Diecueeion

Conclusion

Bibliography

00

ya
(I

14
14
15
16
16
17
17
18
18
18
‘18
18
19

L'-

24

55

ISTEEGE’R'TIOI’R
though the literature contains may references for

the addition of eimple molecules to olefine. relatively

little has been pu’::liehed on the addition reactions of un-
saturated polymers exec-gt in the case or ndditione to natural
robber. In general, double bonds might be cleeeified into
taro categories. the ordinary double bonds which add £13., £2.
flax, etc. but do not add ammonia or «remain derivatives and
hose double bonds with clectrenegntive groups ottecE‘ed to
carbons of the double bond. wljoh odd £1.71, K2, etc. with
difficulty but which add amaonie more readily. The double
bonds of polytutediene and natural rather. an eXpocti‘ld, are
inactive toward the eddi'ticne of CITT‘ITAOIlifl or «gnome derive-Lives.
lloweror. the denizlle bonds of polyethylene glycol mleate ere
conjugated with carbonyl gram and mi;,ht, tiwrefore. be
active. This thesis deecri’uea tne progmmtimt of polgethylene

gylcol mlceto and an investigation of it: eddition reectimze.

EXIS‘IUA-JULL

The first known formation of o polyester ma accredited
to Borzalitul who, on early as liA'i, stated that polyimaio
acids and polyhydrlo alcohols formed rosin: wimn heated to-
gether. In 1914, the first 0.3. patents: for polyesters were
obtalrmd by Araamz and Callahan"5 £115. in 1929. polyethylene
glycol oxalate and. 901;.Jetl‘zyluna glycol fmmmto, along with
several other polzroatero, were produced and in'-.--eszi;;ated b1:
Carotiraors and Arvin-4 Carothora atotud that; the rumor-ate
was an oil and the mloato was a solid, a fact mat did not
agree wit. the: work of Vorlfinder‘r’ who had produced the-so
pol;;-estoro by the silver salt method and reported the apposite
physical ckmmotoristica. Caroti'.ero produood the malonta by
hootflfig an 0100:. o: mlelo'anhydrido with othglono glycol
at 200°C and «fr-tamed the actor as a. powder which mlted ut
88-9300. The molecular weight ml not determined due to the
lnaolublllty of the product but it is interesting; to note that
the molecular roig'dcl of other polyoatoro were 33mm to nary
from moo-woo. These values are relatively small town com,-
pored to t.~.e molczculor mug-ms of A-polywers.

Touzuk‘l‘j caa'aarcd the gropomtimo of polyethylmm glycol
1731th and pol;.-m.h;,'lun.o Llycol I'mmmte and found that while
the osterit‘ioazion promos in both cases was insignificant below
150°C, reaction wuld be affected at t.‘Lj.fl temperature by using
ZnClz as I catalyst. At higher temperatures. this catalyst
induced cover-a). side reactims and it we noted that- we £51:er
ate actor had a. longor chain length and ma profiuwd 1n n
. batter yield tlum the mloa‘oo. The molecular 1101.34123 were den

2

terminod by neutralization sud ooponifiootion equivalents and
varied from 43u~1¢90. n a further ItCtCflGfit, Tsuxaki showed
evidence that fialcdc acid and its ester: wore transformed into
the {untrato derivative: than hosted above 236°C which'would
indicate that polyesters prapurod at temperatures stove 13000
ghould have approximamoly the sumo chain length and composition.
The conversion of mnloio acid and maloio «stars to the
rumornts derivatives has been investigated for oavoral years.
In 1925, xmerwein and Wehor7 found that the conversion could
be nooomp§1shod by such raIJGnta as fire. 320, N203, etc. which
Lhaorotically-ahoulfi he cepahlo of adding to the douLlo band
,although their mechanisn for the reaction was on activation
rather thorium actual addition and ouhacquont splitting out.
florrex6 used H61 containing Iowa deuto;1um chloride to convert
maleio acid to fumarlc acid and fauna no deuterium in the pro-
t. indicating agreement with the theory of fieorwoin and ficber.
Ramnnushio found that oxygon catalyzed tho conversion by act-
ing a: o paramagnetic material, but nitrogen acted as I dia-
nagnotio material and showod no catalysis. Sinnnuralo con-
VGrted diothyl moloato to diothyl funerate hy the use of 31
which convoraion was found to proceed with or without a solvent
and be unaffootad by oxggono He believed that tge precess 1n-
volvod hydrogen bonding with a resulting molecular deformation
and loss of bond rigidity. Fozsckill eotolgzed tne couraraion
of diothgl maleate to diotéyl {unarato vita various amino: at
25°C from which ho concluded that tho catalyais was a process
of hydrogen bondun; and coordination (boxing the effect of 1.4
addition) followed by decomyosition to the rumoruto derivative.

5

.Tho rate determining step nos postulated as tho following:

31
a k} 23 9 k1 R-i’iiu\ 1g ii 9
R-O-C-CCL-C‘-C;;&22EJ;'I{--—> psC-q-c-ora
BC: Iii-«IR
£1

The mechanism shown would indicate that the conversion prdbobly
does not go to complexion. crtalyois by the ion: of flLl, Ebr,
flaflr, E628, etc. in: belioved to to the cane tyge reaction on
nbovo with an ionic mochonlam while tho mechanism of conver-
61011 by £23 and 2303 won unhaomzolz

Conversion by boat alone «so first mentioned by Garro13
in 192? when he concerted moloio acid to fumcrio acid by heat-
115 the former bolow the eutectic point althouuh combination-
of heat and some of the reagents previously'mcntioncd have been
uaod since that the}4 Prlcol6 has indicated that the heat
conversions probably involve an atomic froo rtdical mechanism.
Since all or those 6Kfilp108 of tho mclclo-fumcric conversion
shnu’thc case of the rcuction, it should be ovioont that the
production of a puro polymalooto cater by a hoot reaction is
probably impossible.

Vincentlfi found that the gelation of moleato polyesters
took place tnrou¢h the double bond and was catalyzed by heat,
light and oxywun. All of the double bonds wcro not required
for gelation since he found that a 10:1 mixture of cucolncto
and anlooto oatsra convortod on fully to tho malaata Gator
above. Bradley, firepo, cod Johnston17 found that the obsonco
of oxygen allowed the condensation to proceed further reforc
solution ooourod. but found some evidence of a small amount
of conversion when too acid value: of too mulooto polyester
approached a limiting value while the viscosity oontimuod to

4

increase. Catalytic convorsion of polyethylene glycol mkluete
can be effected by hoaning in an air ctaosphoro at 1 0°C in the
presence of a boneoyl peroxide catalyst, the product buing an
insoluble infucible solid. Krope end Bradleylfi golled poly-
ethylene glycol muleote by heating it with l/S its weight of
v'nyl acetate. the solution being accelerated by n mercury
. arc and proceeding vita Or without a bonxoyl poroxide catalyot.
The process was believed to be similar to rubber vulconizatiou.

unleio acid and moleio cuhydrido have been used in many
copolymoro with such monomers to styrene. butedieno. OtGolo
Their extonoivo use in condensation reactions is due moiuly‘
to the convcrtihility of the resin: which they form.20 The
anhydrido is more freq ontly used than the acid due to its
lunar cost. but both the acid and onhydrido are prcduced by
vapor phase oxidation: of benzene. the onhydrido being form- ‘
06 first from which the acid is made by hydrolyeio.21 The
onhydrido is more efficient at too start of the condensation
reaction although the two rote. ore the some otter tn. forma-
tion of the half esierozo

The addition reactions shown by the moloio acid double
bond era quite different then most carbon-carbon double bonds.
In 1530, Bausonzz reacted Bra with moleic acid and fumnrio
acid, .d found that the oddition to fumerio acid out releLivoly
normal while the Era did not react with mleio acid. in the dark
at lboc and econ in the presence of li;ht dad at slightly higher
tomporaturoo, the reaction was quite slow. In the presence of
hflr, the reaction was rusteré In 193;, Lucas and Pressman23

auggoated tho use of mercuric sulfate catalyst with a potassium

5

bromide-potential brmata solution (as a source oz‘ Ermimfior a
quantitativv deterrination of the douhla hands in waluic acid

and 5131816 Eflhydriafio I‘inrtlett and lifiluki‘r’A modified {fie pro-
cedure 6nd appllod it to capolymera 6f unleic anhydrido and
maleio acid with apparent success. In both of the last two pro-
cedures. the tlmn required for reaction with maleic acid and
mfiluio nhydrido nus more than faur time: thst nece gar: fer otner‘
unsaturntoa. Enkvistzs reacted a metxanolio solution of asmnnia
uflth maleic acid in a sealed tu‘e at 1000C and found a small amount
'of'aapartio aéid. Tha reactian proceedad much faster in the pra-
Icnce of certain metal salts.

The addition of simple moleuclos to othur olefin: prficeeds

without too'much difficulty. Uhlrig and Lovinzo found that
cyclohexano‘ isdbutylene. diiaebutyleno and various fat: and

011. wuuld add bromine quantitatively from a glacial acetic

acid aclution. Chlorfine has been added to acrylenitrile by
.assing the gas through a chloroform solution or the nitrilo at
10-6000.27 Bowaver, the addition of ohlorinc to totraohloroethy-
_lano reqaired tn excess of chlorine at high pressures. Jen:29
added cyanogen to 1.3 butadiena while the 1.6. Eurbon £0.30 add-v
ed cyanogen chlorides to olmfinfl by tha use of heat and yressxro.
Mayo and Katzsl-added gel to isohutylene afid rayo ané 3avoy33
added 5 St to propylene. The but h round that the addition of
hydroan Militia: or hydrogen clfinic‘m to in clut‘in ms fir‘mmgzd

.

by wave lengtha of light of less than 3&0u-33 g dragen cyanide
36

3
. ‘ A -
has hoan added to aorylonztrile.é‘ vinyl waters,35 atuylane,

butadiano.57 etc. the last two additions balms catalyzed by LuZCIZ.
Organic paracida add onygca to the double bonds of simple olefiu

6

to farm epoxldea.3a whlla hydrogen peroxide Earn: the 313031 with
the double: bcnd at room. tGI‘pr‘rls.‘JL‘l‘880‘"‘g Fort!“ ’ yrn; rare} 63.31
dlwethyl Lutyrata by adding CO to projylano. Schulzél adfied
mercaptafia and h3drogen sulfiflc ic dangc Lands using the latter
procedure as a method 01 nre :arat3 .’1 of Larcaytmns. Snow and
Frey42 reacted 802 with olefin: at high tampsruturea to prfiduce
high molecular uni at BuL onas. Turn:r and (:.nn:r43 added

“’31 sulft .231 chloride: to unsutura ad corpounds £11116 :‘etars m
and Detlin344 added turtiar3 halides under tze influence er
antimony or aluminum 6:110r1d03. Iodoform.45 chlnrofonn nd
ear‘oontatraohlorida4a Lava bean ado ‘ed to olefin: under t o
influanco of paroxides. Hamblut and fickler34? funnd Lizt the
addition of 1nr~elue“*“e to but3lane prodzcad 1.3 butylem

glycol. ?ho a fidltian prodrgcts of N“ 3 and F204 are tue'most
aidolv used of the nitrogen addition gunpouncn sin-e che3' are
used for unsaturatian deter iuaaions. Band43 applied the addi-
tion of N232 to styrene and found W.fl& t.a gravi.etrio de er-
Lination of styrene as the nitrosite gave res lts clone ta

160% of the theoretical. The use of H 0 in this manner was

2 3
applied to other Olfiflnfl by Santa and Bond49 with 300d auocots.
Last of the work or. tha addition of 132204: to dumle bonds has been
done by Lavy and Scalfeso who added H304 to thyleno and progy-
lane. tith at her olezlna, dinitroaarafflns, n troalcohols and
ultra alkyl nitrates ware produced in good yields. LeckLa * ‘
added HoCl to tao bonds 0! ML3le: o and pr0p3lene in tho
presence of Eifilg, FeC12, or Caz C12 at ~2230 while Colawan
and finawllflz added FC13 to l-anfiE-butcnea in the presance of

an acid sulfite to :rcdnco tn a ino chloride. The nfidltiom sf

?

ammonia to olefins has been of interat in the lnat few years.
Fora-255 added a mania to acn'lomtrile at {JG-150°C and prmfuced

alanine. Several patcmta were air-mined by J. is. Tatar-54 for
the annex-301:5 .8 01‘ alarms and} as prupg'ltmo, 'l-dodecanv. etc.
in the presence of 2:21, Go, or snail ammnta of.water¢ In each
case an excess or armada was used at te‘tpereturOI on hi}. as
800°? and pressures rungglnb tron tam-sow] or}. 11:.

Kory little has been done on tiie add “aim of s all molecules
to polymers. licrmawr. t was mund L-mt r:.4b'-.)er would roact with
molecules containing the - C O C . C a O linkageafif’ the re-
oction taking; place at 13°C in the 32.16an of 013,505. It is
also well known that natural rumor will add 12, El, 8, and 82
(.712 to form rubber halides. ruézbar hydrohnlideo and Valentina
rubber reamctlvelyo Miwhoidt and M1955 subjected u batedfiezm
polymer to mild oxidation and treated tue solution with 302.

Tn. viscosity increased but no indication has 31 um 01' the tygo
of reaction taking place. Several types of inorganic acids and

nihzflridas ”wired we same effect.

LEE" . 1.711". 1453 21.7; 5L

. 31'
Proaratlon of Pol ro'tiu'lene filzgcol male-sate.“

Four nolol of moloio onhydrido and four molol of ethylene
glycol wore minad in a liter throouoecksd flush equipped with a
motor stirrer. thermometer, gas inlet tuho and a condenser set
for downward distillation.

Tho mloio ardlydrido W's! purified by Roman distillation.

a fraction distilling at £300 under 15 mm. pressure was collect-
ed and used while the ethylene glycol used had a rotructivo index
of 1.450d at 21.006. The system was kopt under nitrohon to pro-
vost decomposition and convorsion by the oxygnn of the oirc

The nitrogen was pooaéd throngh o 10% solution of alkaline
pyrogallol ond a tube of conoontratod sulfuric acid to remove
oxygen.ond water. The roaotlon temperature was maintained

at 130°C for 5.8 hours at the end of which period, Lno torpora-
turo was raised to ZoLOC for 3.5 hours.

The prohrooo or the repetion was followed by neutralization
and ooponiflcation equivalents. Tho saponlfloatlon equivulonto
wore determined by booting the polymer with an excess of aqueous
potoaoium hydroxide followed by book titration: with standard
hydrochloric acid while the neutralization equivalents were
determined by direct titration: with mothsnolio potassium hydro-
xide. In both cases a phonolphihalein indication was used.

The difference between one neutralization oq 1valonto and one
ooponiflootion equivalents was equal to the num or of reacted
carbonyl grouyl. wuioh when divided by the ooponlfioaiion equivo-

lont gave the yeroort motion.

The following results were obtained:

T1 3 (linutoa)

 

fojporaturo (fiogroes C.)

 

LLRooctlgE

0 60° 49
35 1900 64.8
90 lflOO 75.4

165 150° 73.7
240 1900 82.1
515 190* 8301
zoo - 1900 63.4
430 205° 85.9
435 205° 88.6
5¢5 2b5° 88.8

Tho graph of 130 vs. percent reaction is shown in figure £1.

The poroort reaction at zero tiso (43$) no: not dotorwinod,
during the reaction. but it was assumed that the half ostor no:
formed immediately when the moloio oohydrldo melted and o
homogonooul solution was formed.55 To prove this. .49? moles

of othyleno glycol wars added to .437tmoloo of moloio onhydrido
in .49? moles of acetone at 2U°C and then titrated with aqueous
potassium hydroxide and with a solution of potassium-hydroxide in
looprOphl olcohol I: soon as possible. The following results

mars obt‘a fined:

 

 

minutes After fiizing_ Aflrfioootlan
3 49.15
15 43.65

The reaction product “on purified by distilling off all volatile
matter at 130°C under ZQ-SO mm. pressure and when cooled, it was
an oatroaoly viscous rosin with a slight straw color. After
purification, the carboxyl groups were found to ho 91.34; re-
acted indicating an overu3o polynur longto of approximately 12
units and o molvcular woight of 339.59 The composition of tho
polyethylono glycol meloato was found to to carbon - €0.6dfi,

and hydro;en - 4.25%. The tgoorotiool percentages for the ester

10

Pox-cont reaction

8

q
9

 

FIGURE #1
GRAPH 0F PERCENT REACTION
VS. TIER A? DIE'FLREE
TIEPERATURES
——-— Tunpornturoa 60-190 C
Temperature 190 C

' ~Tmpernturo 205 C

 

 

J l 1

 

300 400 500 600

Time in minutes
11

. . .. 0 H H 0 231 Ii;
‘dtu a stroctuul unit oi n a ‘ .I . ‘ are cur-
- C a C- . C o l a O u C, a- c a 0-—

bon - $0.?Ofi- no hyérohon §.203.

Using the n utralization equivalonfit on the concentration
of acid, the reaction rate conatants (1) for the osterificntion
reaction at IQOOC. and 265°C. worn deter inod. The reciprocals
of tho noutrolization equivalents were plotted anoinet tug tiga
of roaction in minutes and value 0: k was found from too slope
of the ;raph. A3 I chock on tho araphiool method, tho values
of k were calculated from the equation _l_.: kt & C where a is

.~3
the initial mount of acid, 1 is the acid reacting in time t and
c is a constant dotorwinod oy setting 3 and t equal to zero.
The values of k for tko two temperrturoa were than Food in the

eqution log; 1:; . F (T2 - F1) (
k1 2.505 n 12 T1 ;

notion rate oonatantu. T1 and 22 are the absolute temperatures.

N115". kl and k2 are 13510 n"

and R is the gas oonotant (1.9;?) to detarfiine the oner¢y of
activation, E. The out: used and the results of these do-

torminntions are as follows:

 

 

 

Time Concentratioa Reciprocal Calculated Value of k
Swag.) '2£.Aoid neg. g. Cogoontrution Falue of k from firoph
0 ‘049 .223
60 3.81 .277 .00090 .0009
135 2.82 .331 .00097.
210 2045 .4D8 obGOkB
2H5 2.31 .433 000074
330 2023 .0439 0000b5

Reaction rate constants at 205°C.

..50 ” 1097 .508 .0012 00012
135 1.62 .617 .0013
225 1-65 0506 .0007

The value of the energy of activation was found to be 12,7LO

ooh/ mole.

12

C ‘

_§ddltlon of dydrOgon hromido Lo P-lgefiaylone filycol Enloaia

Gaseous hydrogen bromide. which had boon purified by
passage through coppor turrings :nd dried throth a calcium chlor-
ide tower, was pssaod thraugh a solution of twenty-one grams of
the polyester in 130 cc of chloroforu for nine hours. Eho excess
gas was obsorbod in s woter trog. Lur,ng the roaotion. the
temperature rose to 54°C and than returnod to 20°C aftor four
hours. The product. after the solvent was removed under a
xacuum of 30 mm. at 14000 {or three hours. was s viscous resin
which was slightly darker than the polyester. Dno hwndrod and
fortg—oight noq. of tho polyosoor gained 136 moq. of a Sr
which is $3.36; of the theoretical amount for a polymer wfith the

1 . . .
.«r‘i‘i? £191
structural unit of 0 - L - g - 9 - L - O - - L Holo§en deter-
fi Br

ainations shouod 33.42%.Lronino in tho polymer which was about
F .ofi 10 -ho o i v no - 5.: L ‘o oo "mar 0 he
93 i of t} t or t cal a1 (3 7,) 1 r a ‘ l, f t
structure shown.

~.ddi‘ci o ' drOLon (hlorido to ‘001 Ralsoto.

 

Gaseous hydrogen chloride was purified through capper
turnlugs and ooncentrctod sulfuric acid and then passed through
I solution ( of 23.333) of tho oolymor in 150 cc of chloroforn
for n no hours ot 2490. Purina the raaotion,-thoro goo no chsnse
in temocraturo.. Distillation for three hours under 40 mm. pros-
suro at 124°C loft s liLht yellor viscous residue u.ich showed
signs of crystalinit; on long standing. Tuonty-eight and fifty-
five hundredtns g of the polyester inor.ssod 5.87 g in “night
which was QSOlfi of tho tnooretiual aaount for complete add;tion.
to tne douhlo bond of tno polyester. Halogen deter inationo
Chnwod toe polymer to contain 13.573 chlorine whioh was about

13

I

94.6E of tus theoroticol valvzo klfi. ?,) for s polguor with
I Q 2'! fl 0 ii; 13';
thsstnioturalunit-O-C~(:~§Inii - 0-C-L-
:5. L1

figdition of Qronino to Polyoinvl one_§lyool Valerie

Forty-four sand six tenths g of the polyestor were dissolvod
in 2L0 cc of onloroform,snd 17.9 00 of pure bromine. and excoss
of tho amount necessary for addition, was added, after u ich the
flask won ILOfLOd and allowed to stand for one week with occasion-
al snaking. ?hs chloroforn solvent and unrosctsd bromine were
removed at QLOC and 40 mm. prosauro. The product was slithly
darkor and less viscous txsn t s poljos oer o:zd on Ion; standiné
hogan to show signs of orystolimity by forming a red-brown
,posty material. The product contained 13.02” brodins which was

only 22.59, 01 tuo theoretical value for s pol:*m«:r wi v.1 a structural

‘9 4 '. 9‘ I? #1
uni of - 0 - é - g - o - L - 0 - i - 9 -
hr Lr h E

Addition of {hlorino to Polyethylene

 

Chlorine éas which was dried through sulfuric acid, was
passed thr ouch a solution of 40 grams of tlo polyaster in 20C 00
of chloroform, the excess boing removed by a water trap. The
temperature was 21°C, but roso to sooc soon sftor the rosction
started and remained there during the rust of the reaction poriod
of nine hours. Distillation of the solveLt and gases present
was effected in vacuum at luOOC for 1} hours after which time,
the product began to turn dork. Cu sounding, & vory viSocus,
clo;dy rosin :ormed. The porcenn chlorine mas found no to

2?.GdE which was about €4fi of too t.'zooretioo1 ((55.51,) for u

9 f}: ii .3 211 £12
polymer strdcture of - 0 - u - 9 - o a t - o - c -é -
L1 Cl

14

Auditlcn o? Inferinlfic Pfilffifhfl??3 Clgccl Pg} ate

Twanty cc of Liquified unnnnia warn added Le £4 3 of tie
polyester which had provioualy been enolad in 6n aceioneodry
ice bath. The mixture was hjntad to 1:006 in a high pressura

bomb where the hi,hest pressure attained ans 125 9.8.1. The

prassnre dropped steaflly in giant {5 vinutaa to zero ;.s.£o
oltnoufi a. small £220“ ’3 of ms man 13‘ m2 Yfliul'l tier: 15072:: tars-.8
Opened. There were awn grad;cta of tae cumonulysls, ens &
brawn res n whicn was aulublo in dilute acid but inauluhle in
alkali. and a white aplid which was soluble only in concentrated
acids. eqh prcducts ware placed in a very dilmto acid srluiion
and the whffis solid wt: filtered off. The remaining 801 tion was
wade alkaline to preciyitata the firown resin which was then
dried under vacuum. The resin cantaized 11.3?E.nitroghn as
ufuinat a theoretical value of 11.235 for a polymnr which has a

C ‘ V ‘ ‘ I
structural unit a! - 0 - é - g - g - g - 0 - 31; 31. It

£52 5

was net oxidized by gotnssium gerwaugnnate and ahwwfid 7E na-
satfiraiion when titrntnd wit} hrsfiatusbrmuida solution. Th8
white aolifi'dec0npnsnd wignout melting afl shout 2330C, ShOWfld
88} unseturazion whun zitrntnd with &ruwatedhr0mida aclut an,
and gave off awnnnia when heated wit; elkuli. The svlution
formed wheg aha whitv selid the heated with alkali WES acidified
and a white solid precip;tnied witn eoatwge. This solid Wts
filtered and “flaked with alcohol aftur wiles tna alcnhél mrs
evaperatedtto a small vclume. ?hia resulted in the precipita-

tion or a white crysta14;n solid which nultod at 150“L. 1.0.

the Melting paint of maleic uu1%. The paroant nitrogen of £30

_ 1 . . -
bright}. land was 22.86 «41:21 1mg about 2;; tints tno timer-91.2.cul

1: i: a
q
for t f‘~012’3'i¢r with I atnzctnml unit 61‘ - 0 c C - IC «(0 - U «- 0 -
1. H1. fad H

n- C - ind slightly lens tint: taut of allow-do (1-1.8. Enu‘m
(donut-‘29.)
#:3172340!) 02' Hydrpsine i'i'j'drafnjm Pfllifit?'ilfi§16 Clfl;o;:ll’fllnaiq

Twenty-flu” and three tan-tbs g~ 01th. polyester were flit-.8011“!

1n 1G0 on of“; 1:1 ratio of a chloroform-Ilcohul solvent. 32 g of
hydratino hydrate urn mined mm the mixture was reflux“! for (“our
boars. I}: ntillatinn at 80°C under £0 an. mum-n for three hunts
reunited in t transparent bronze-colortd rusin Inich was lens
vflonoua than tho polyester. Tunnty-throa and throu tenth gram:
of the polyeakor gained 5 gram. during the reaction. this value
beamg 61%.»! tho thsoroticnl amount fnr*t polymer: tn; structural
unit ofvhlch mauve-bug 7g-g.o-iz.§z.. The
percent n1trogan.uaa 10.5é3 or c4.9£ of tha thnoratical awount
(16.09;) for the ctructuro ahmm. The percent unantumtim. could

not be determined.

ga-fidgtinn of fiitrcgnpjfirmfid. POMPOL'G‘Jthjrlana {31 . ,

 

A sciatica of the 32.4 5 polyantor in 115 cc of chlorofom
ml Placed in . mmd bottnn flask filis‘h was cleared of air and
mum by passing through nitrogen. film-agar: totroxido ma passed
tingx the solution for five ham-n at union time the solution
an assumed to in saturated vita the gas. The. nitrogen tetroxide
was prodmud by drawing coxmontratad nitric amid m waist 1301131133
”omits and heating; when necasmry ta produce a Miter volum of
gas. In the early stag,” of tine reaction. acme heat ma given
eff. Thirty-two and four tent-En grams of tin! polyentsr incrmaad

.16

50.8 grams in weight which was a little higher than the theoretical
amount. Distillation.at 35°C under 50 mm. vacuum produced I yellow
whit. owl-50nd. M. higher temperatures. large volumes of 1320‘
were given oft". rm and fifty-four hundredth: percent nitrogen

no found in tho product which no slightly less than the theo-

retical (11.96%) for a polymer structure of - 0 - C - q - C - C «-
a; a; g a I; a #2. $1. 02% W1
O‘CQCQ”-O- .lc? -C.O- ac...
hozhoz

Addition of Nitrogl Chloride to Mlzethllano Glzool Holeatos'?’
Thirty cc of glacial acetic «id in 20 on of onyl nitrit-

 

Ioro oddod to o oolution or 22.6 g or the polyester in 150 on or
chlororom tollmd by Q drown. addition or 11 oo o: conoontrnted
hydrochloric gold. during tho addition of unloh tho temperaturo
In: minnow“! below 6°C. The chloroform solution ma war-ml on
the atom both for ml hours. A ‘Ihitfl precipiuto appeared
which no filtered off Ind “shod with chloroform but .I-vo no
tutu for chlorine or nitrotgon. Man heated. tho procioltoto
lublinod It 200°C. malted near 280°C, 1nd proud to be female
acid.

Addlt an of Sulfurmonoc‘ orido to Pol e

   

Thu. ond flu tenth. ; of mmmmochlorido were minor!
with o aolution of 5.3 5 of the polyestor in 50 no of ohlorofom
ond hon-tad on tho Itm bath. The yellow opener recipitato which
appeared you utnhod with.nloohol and dried. It won found to'bo
insolublo 1n.311 of tho solvents used 3nd no determinations could
ho new. Tim .9114 no air dried and placed in tho hot row for
several days with no dootruotim: of the elastic properties.

17

ARLYTICAL
A carbon-hydrogen determination was run on the polymer by c
mthod adopted from the macro-method oi‘ Fin}- er,“ aaonrito and
dohydrit‘o boing uaad in the absorption tubos. All of the holicio
and hologon addition compound. were analyzed in duplicate for
halogen. A weighed canola in a cellulose cup was placed in o
Bur Bomb with sodium peroxide and small amounts of potassium
nitrate and bonaoio ooid.55 The bmb woo ignited by flame and
tho content: discolvod in an acid solution after which the Voihlmd
method“ for the denomination of halogen In: applied. intro
benzene no used with the chlorides rather than filtaring off tho
silver chloride. All of tho nitrogen dotomimtiono were can-10d
out by tho mcro Kjoldohl method67 with sodium sulfate and copper
aulfoto catalysts. The dotomimtiono of the various clement-
oro mmworined in tabloo l. 2 and 8.

Seven). motimda for tho dotomimtim of maturation were
used but only the brozzido‘brmto method was of my value.
Pomnfnmto Oxidation lipthogitgr tho Botqngination ofwfihaotnraflon

Each of the product. no titrotod 'ith a actuated solution of
potassim pomngomto in acetone to dotomino the relative mount:
of maturation of the effects of oxidation. The permanent red
color of tho pomngomto solution on: and no the and point with
no outside indicator unploycd. The maults oro listed in 1:3th €43.
mercuric inept. hedged reign. mteminaggon or Unsamratzon“

Five gm: of accurately weighed urcuric metat- were added
to o solution of the ample in 25 cc of dimm. tor ton minutes,

a saturated oooimn chloride solution. moths-'1 alcohol and carbon;-

18

tetrachloride were added and the mixture ms titrated with standard
potassium hydroxide to s phoziolphthaloin and point. [laterainetiozu
were made on mlcic said. polyethylene glycol stiletto, the hydrogen
bromide sdditicn product. and s that sample. See table #5.
Eg'drotlemticn ffi'otnod for the Inter-"inflict: oi" Unsoturation

Eg'dro'gcmtim was curried out on the some products as for the
mercuric soetste method using low pressure hydrogenation in the
presence of s palladium oxide outshone”, A saturated chloroform
solution of the product to be reduced was plsoed in the hydrogenctcr
along with .8 grams of analyst. 5 cc of ethyl 31001101 and 2 soon
crystcls of terms sulrste. the pressure gauge us calibrated
with mlsic sold. the results m sham in table :38.
Pet-ban c c Acid Hothogicr the Detergiggtggfl or Uggaturctionm

The perbonsoic cold as prepared by the new of Brunch“ using;
benscyl peroxide which ind been recrysteliscd from absolute ethyl
clcohol. Brcun's method consisted of coding s cold chloroform
solution of bonsoyl peroxide to sodium mothylats followed by
scidii'icction and extraction with chloroform. An excess of sodium
nethylctc was used to counteract the effect of bcnwic acid which
seemed to be present in the peroxide. Iitmtions of the pcrbcnsoic
acid solution with standard thiomli‘utc determined the strength of
the sold to be .9554 nillicquivalsnts/ml. Trusty-five m1. of
this solution were sdded to s‘ chloroform solution of the sample
ccntcmin; about 12 nilliequivslents of unectumtion after which
the volume. tits and. up to 100 ml. Iith chloroform. After standing
for 86 hours in the cold. 10 ml. portions or the solution were
titrated with standard thiosultste solution using potassim iodide

19

and u aux-chant] point. The results are given in table 1:8.
23933333131 firggdo—Pojzffisrimwflrogmte £01:lietcflim.t1@_o£®sghzmgo§
Two methods. those of Lucas and Prosm,17 and Bartlett tnd
Ecumm var. used in those tltmtiorzs. In {219 Lucea procedure,
an. excess of $1461.03 and a mall momt of sulfuric acid were
placed in the flask followed by .2 l mercuric mlfato. the carry-la
to be titrated, (approximately 2 milllequimlents of double bond)
and 20 cc of acetic acid. After shaking the £133}: in the tbsonoo
or light for 30 minutes. I sodium chloride noluticm and potassium
iodide «era added. The solution! taro tltntcd with Itmdard
hlomlf‘ate and gave utmnely low results. The same method nu
used on two more ample: although it was modified slightly by
initially evacuating; the flask with m asplntor. An increase in
the percent maturation was shown, but the results were still too
10' to be of value. The best results wars obtained by using; the
method of Bartlett and Honk:- L motion flask with an attached
separator-y tunnel in mcmtod. und 1 solution of the mp1. aw.
minrithfico offiRsto‘ und lOooorwataro Warming 1
the flask for 10 nmutod, In mono of th- bmldo bmto-aolutlan
and 20 no of a M mercuric sulfate wolf. added. At the and of 30
minutes, the excess bromide-brunt. was titrated lodometrloally

with thiaaulfato. The results in 51m in table :38.

1:91. TA i‘lflihfi
Tabla f1 P:rcc;ta¢es of carbon, h3§rc;cn and oxvgon in the poly-
M ' 4 i U
ethylene glycul maleeta produced.

{preartages Fognd Theore+1CFl Pwrggyta~ea

 

 

‘1'

,xSC :33 710 7H: :33: $60

$0.73; 50.55 4.12; 4.55 45.12: 615.09 50.70 4.26 135.04

Table fl” Fbrcwt halouon in tho Micaenatod Imd hydrolulogenntod

 

polyutoro
mel’rpdugg f: ihlgfien Theoretical E fialol-tgcn
H‘Br 33.433 33.55 85.87
H Cl 18.743 18.60 19.87
012 28.103 26.75 33.31
3,2 13.02 52.95

Table is Percent nitrogen found in the afidltian products.

Adaition Prodnct fl Vitrogpn Egaoretic&l_§'fiitroggn

 

:13 (solid) 22.84; 22.51 11.23
Eda (resin) 11.09; 11.54 11.23
(121192 9.99: 10.58 16.09
R204 11.15; 9.93 11.96

Table £4 Relutivo unsaturatlon expressed as 1:11 of mint; solution
per gram. .

fiditlm Product. 11:1. 01‘ K:.§304/g

 

 

Pblyethylono glycol malenté 35.8
3 Br 3.1
E CI 44.6
Bra 40.0
612 5.4

Tobi; fl 6011:.

 

 

 

 

Aédlflfflfioflfixct m. or mace/g
3:13 (solid) 19..
:33 (rosin) . 2.7
(may:
Tabla i§ Unauturatlon found by tho mercuric acetate titration
mothod.
filllloquivalanta Theoretical
fgggflg; of base Used___ glllioqgivnlonts
walolo-Loid 12.52 9.49
Polyethylene glycol aoloato .38 5.58
Polyethylene glycol maloote ' .19 ' 2.71
HB r Addition Product ’ ‘ 1.82 " 4.16
HB r'Addltlon Product ' ' 1.59 ' 4.25
Table fig Rolntlvo unsaturotion as measured by the drop in hydrogen
pressure.
Pressure Dre In
M lbglggo 1m‘fmglg 3:3
£31010 told 90 ‘ 44 min.
Polyethylene glycol maleato 50. 18.8 hrs.
Polyethylene glycol mateoto 62 16.8 hro.
ma 1' Addition Product ' o 21 hrs.

Tabla £2 Unoaturttlom measured by porbensolo acid titrationa.

 

$83210 Esq. of Acid Eggorotlcal flog.
Used
Polyethylene glycol molest. ‘1 .15 1.40
Polyethylene glycol maloato .11 1.40

22

Tabla f8 Unsaturcticn.mccsured by K3, - KBrOS titration. 1n.thc

presence of Hg 80‘.

 

 

 

flag. of Theoretical Percent
Brcmntc flag. or Unsaturaticn
gddltlpn Product Used Unsaturution
Polyethylene glycol maloatc 2.01 2.09 97.89
Polyothylcnc glycol maloatc 2.43 2.60 97.36
LBr 2.36 3.46 66.30
‘ Bra 1.40 4.22 32.97
8 Cl 1.64 4.12 39.73
Cl: _ 3.09 3.79 81.34
12213 (solid) 1.09 1.21 90.01
1121,, (send) 1.00 1.40 88.00
ma (ruin) 0.15 2.22 7.00
£33 (realm) 0.18 2.63 7.18
Hz .06 1.51 3.31
‘ 32 .06 1.26 8.10
(nu2)z .. An excess was used in all titratlcnc.

DISC-US$114.

Figure fl shows the effect of time on the consideration of
mleic enhydride and ethylene glycol. The temperature was raised
after 6.8 hours of esteriricstiozi to effect c larger molecular
weight since the reaction rate me approachizig zero. This action
resulted in In increased rate of osterificsticm es shown by the
graph which in in agreement with the foot £319.13 most of the 1.....-
distilled off during, the first. 133 - 2 hours. . It can be coco. that
as the reaction proceeds, the temperature necessary for condensation
increases which is probe'tzly due to physical rather than chemical
factors since the increasing viscosity would tend to make the
collision. of hydroxyl and carboxyl groups lees frequent.

Stirring tends to mice the mixture more homogenemu in regard to
both chemical cmpociticn and temperature 811100 in condensaticme
where no stirring; ace used the gelaticn begac earlier and. due to
localised heating-.3. the portion of the materiel 0.1: the edges of the
flask nearest the source of heat gelled much comer than the rest
of the mixture. In all of the condeneltion mm wide. e white,
solid material we found suspended in the cooled polyester. The
solid melted ct 130° C end proved to be nucleic acid, which eublimod
off dining; 1m. distillation so mu. acid (259. 290°C.)

lie signs of the suspended mclcic acid were found in the
polyester at the and or the distillation process. The presence
of excess ecid use to be expected since 3 mll amount or the
glycol distilled off with the water during the condensation
mum. The presence of free ethylene glycol would soon: 1111--
Oxplnlnlble 1n the light of the lat-mute hilt eater foncation,
but It higher temperatures. on osterii‘icstimohydrolyeis

24

equilibrium is probably set up. Since mixed esters undergo ester
interchange it is reasonable to assume that the hot polyester is
in s dynamic rather then s static states.

ince free acid sos.found in the final product. the percent
estorificetion values calculated during the reaction are probably
someshst lower than the actual percent reaction values. The
molecular weight was calculated from the yercent reaction by the
use of the following formula which was developed by Csrothers:

9:2;‘1.
f f:

Whore P is the percent polymerisation, X is the number of units
in the chain end F is the functionslity per molecule of monomer.
Both of the monomers are considered to have s functionality of 2
since the double bond of the mslsio anhydride does not take part
in the esterifioetion reaction. substituting 91.6€% (or .9154)
for P’snd 3 for the sales or 1, the squstion becomes:

.9154 3 l ’i.“ .9164»: 3 .1. This gives 3 s also of 11.82
'uhioh.shen.nnltiplied by the weight per each two functional
groups (71 5) gives the moleculsr weight of the polymer'es 839.

The graph of the reciprocal neutralisstion.milliequivslents
vs. time shows test the estcrificeticn of seleio anhydride and
ethylene 513001 is a second order reaction. The values of k st
both temperatures were determined from the strsight sections of
the curve only. since the rate decreases considerably after seversl
hours or reaction. This 1. due to the reverse reaction (hydrolysis)
which takes plsoe in oil esteririostion reactions or this type.
Although enter use removed by distillation during the reaction,

considerable quantities of water ere probably held by the viscous

25

 

FIGURE g2
GRAPH 0F RECIPRGCAL
EILLIEQUDIME-ZTS PLO’I‘TED
AGAIEEST TIE-E I}? MIZQ'UTES
— — -— Temperature 190 C

Temperature 205 C

.7.

05.

.5.

1/ (tax)

.4-

.3 « /

02‘

 

A ; A A n A A L
j '—

o 100 200 300 400 500 660
‘ Time in minutes

26

 

mixture resulting in the hydrolysis reaction.

Min-g; the discussion it has been hemmed that eeterificetim
like the only motion taking place. However, it should be mentimed
that there ere several other ooureoe which the reaction could have
followed. these helm; A-polymerixetion of the acid. polyethor
tometlon and polyumydrlde (oration. A-pclymeriution end
polyenlu'dride formation Ironic! both result in cmpmmde which
should omtain only 2,: hydrocen, e value much lower than. the
percent. hydrogen round. The A-polymr would show no unenturotion
end 7would not. add any or the reagents which wore added. The poly-
anhydride should not be formed since the hell! ester would tend to
prevent it. Although polyethor fonmticm usually requires higher
tapereturoe and e doE-q'drotion utalyet, 1‘. could conceivably ”be
formed during the motion. However. the polyether would not be
hydrolysed by the week elkell eolutione need, there would be no
difference in the noutreliution and eepmlfioetlou equlnlonta.
and e greater percentage of hydrogen would be present in the poly-
ether. The oer-boa: hydrogen dotemlmtione were in very close
egreenont with the theoretloel for eateririoetion.

The edditlone or various reagente never exceeded 953-5. which
night be due to enell amounts of isolated oroeellnhgee through
double bonds. although in nest cases the remaining meatumtion
eee accounted for by double bond titratione.

Eatorificetlm would produce 15 polyester which could home 0.
ellin 01’ my me of three forms depending; upon the terminating
group» The terminating groupe of the molecule might be 8 hydroxyl
groupe. 2 urboxyl groups or 1 oer'ooxyl and 1 hyclroaqlo The half

27

 

ester theory would support the loot etruoture, but since free
gylool and free eold ere known to be present, any 01‘ the three
.typee of molooulee could be ranted. A cyclic structure for the
polmr in rather improbable “me e ring or more than eight
newer! mld have to be fame-d and no neutralieation equlvelent
would be shown.

The reactivity of polyeuxylene glycol uleete tooerd halogens
em! hydrogen halides 1e 1n the order Brzélgflflécl elthmagh the
difference in the reactivltlee of 3 Cl end 831' 1e ought. Bromine
reeote very elowly end the mum my be either eu‘oetitution or
eddltlon. Chlorine route more eoeuyend to e greater extent then
bromine but the. product tamed 1e tumble toward beet. From the
meet-gee of blagen premt. 2m end a 01 odd to the double
bond nearly quentltetleelyq Blane neither of theee reegente ere
eepeble of eubvetltotion, the peroent helogen ghee e good indict»-
tim of the maturetion present in the polyeetere Le eee eat-n
peotod. none of the helide dorlvetlvee could be oheolned for no-
eeturetion by the bromide-bran“ method. the brmidoohroute
mthod depende upon the eddition or bromine to the double bond
end in tho presence of et leeet three (too oerbonyle end one or
more Maseru) wrongly electronogetlu group" edditlon would be
greetly inhibited while lubetitutlon would be may enhenoede

The edditlon of em“ to polyethylene glycol mleete reeulted
in two entirely different products. Frau the rel-tire mutate of
the produete prodmecl. it an be concluded thet the winery reeotlon
product to the minted polyeetor. while the eeoondary reaction
product to nleemlde. There ere probebly other produote romeo
in the hectic: nlxtm‘e chloh were not leoletede With both

28

reeotione taking plece elmltenemely eon-e dienide or upertic
eoid should be formed. Eoeever. eince the resin ue precipiteted
Ira e enter solution the eepertio acid derivative would be lost
in thin step. The percent nitrogen or the nelelmide (22.67%) In
louver then. the theoreticel eelue end all mute of neleenic
ecid ere probably present in the eolid. Shoe these products
were the results of ranting en excess (for eddition) or enmonie
to polyethylene glycol mate. it would be interesting to deter-r
line whet producte mild be formed by reacting the two in an equal
molar retlce me or the other or the reeotion ooureee might be
elimineted by running the reaction et e different temperature-

l'he eddition of Murine. which should enoe ebont the eene
reeetivity ee commie. eee only 65% caplet“ Thie 1e probebly
m due to the reectlvitiee of the tee bonde involved but my be
due to the eteric hinderence of lerge urboeyl end Maurine
group“ The eddltlm product wee eeeily oxidized by Wu
wick mld indicate the presence of e pendent EH: pump. Verioue
eminee eculd probably edd to the double band of polyethylene
glycol neleete but they would be reetricted by etefle tectore to
than or the mller groups.

’1in Wide adds nearly qmntitetlvely and might be
used for the m'vlmtrlo determination or the double bond. The
eolid product ie not crymline end epperently ie not too eteble
to beet eince eon 530‘ me given or: at tmpenturee elightly
higher then thou need to mporete the eclvent. lie explanation
can be given for the differences chem between the percent 152%
addition end the titretion of the mining maturation. The
etructm'e of thin derivltire cmld be e a: - 1:3 :- or-'C\ - i'f— e

01*! R0 031' (£50
29 2 2 2

The atmoturo is preferred since the addition or two electromagn-
tivo nitro group: to ‘10 symmetrical band should be as difficult
on brmimtion or chlorination.

Thu ottmpt to m nitrooyl chloride to the double bond ro-
mltod in the Iona-Mon of moat-lo mid. and no addition no do-
‘oootad. Although tho tmponturo no loop: of; 6°C, hydrolysis in
an aqueous told ”lotion on not unexpected. Sm. tendency to odd
or counts tho bond 1- indicated by tho conversion or the about.
to {mar-10 Cold. and tho addition would probably inks place under
condition. unfavorable to hydrolysia.

rho mum at cum: mmorm. with polyotm'lm glycol
mint. took phoo coolly at temperatures bola-r 100°C. Tho new
rout-.1111 tint took plan. could not be octet-mined tines tho polymer
at 113.011.1131. 111 :11 001mm“ Honour. doc to its moolubluty.
tho promo or o. cross-link“! structure an inflated. This to-
aoum would be ninth:- to the vulcanization of rubber and the
atmturovmldbo-gi-vg-én nndrymgofttnpolymrtor
awn). any: with mic; alga-tom to determine whothor or not
the reaction product no that proposed above or hydntod sulfur.
81m. tho alt-tinny no not door-and to any great extent tho
product could not how been the latter.

The polyothylm glycol mun;- ohomd I «11‘ addition to-
totim when heated to approthtoly 90°C with bonsoyl poroocido or
ditertiory bu‘syl peroxide. tho convoraion with tho httertoatalyot
being muoh‘ hater.

Tho maturation dotomimtim by moot of the outbox-33 were
mutinhotory. Tho presence of certain group: on the hind causod
oxidation with psmngamto to be no complete an tint of the

30

polyootor itself. Tho oxidation of tho hydrazine oddition product
woo om grootor than tho polyester. i‘hio may homo resulted in
tho omidotim of tho pendent KHz group to I302 or 3203. However.
no hmoo ooro detected. .

Tho uoo of morourio oeototo for tho determination 5mm ros-
produooblo rooulto when liioo omditiono ooro rigidly mintoinod
but tho wt of maturation no for below tho thoorotioal.
Aloe. tho unootorotim of tho mar odditiou product on {mud to
bo mh grootorthon thot of tho polyootor won thio mothod no
o-ployod, Tho ootim of tho morio mototo dopondo upon tho
oddition or maria ooototo to tho doublo bond tolloood by
titrotion of tho liborotod oootio ooid. (ho theory propoood for
tho otrootmro fox-nod from tho odditim of urourio ooototo to tho

doublo bond 1. 4;- o . m oddition of methyl

.‘ g “S A a
(,9- oOa-ng-L-Cg
oloohol than hydrolyooo tho polymer ooototo to oootio mid ond tho
nothyl otbor of tho polymor. Tho difficulty of forming ouch o
otruoturo oo that proPOood obovo in tho prooonoo of the too
olootronogotito carbonyl groupo io evident-

Tho loo too-alto of tho porbonooio ooid titrationo might be
oxpaotod oinco thio motion depends upon tho addition or on
mgon otm in tho tom of on opoxido linkage. From the otmoturo.
. (:0:- Cbo/C .. 002-, it con bo ooon tint tho tmdornoy to form tho
opoxido mid bo wry slight in tho promo of tho ootor group“

Tho oddition or groupo with no olootronogotivo oinrootor woo
triod in tho hydroaonotion upormonto. Tho rooulto govo fairly
good wt with maturation found from tho poroontogo or

olomto ond tho braaido-broczoto titration“ The method could not

31

used oinoo tho ooozmoy of tho gouge mdingo for tho atoll armt
or pronoun drop no very poor and o constant mammtwo could
not ho mint-mod.

Tho bromido-brmto titmtim in tho prooomo of oir no mien
lower than tho thowotioal. In tho abaomo or air and by mplq'ing
tho 19 We hootizq; period. results near tho thoorotiool for
addition «to obtain“. km. it would to noted that the
promo of a mbatitution motion in not inpoooiblo duo to tho
hot that tho utility of tho hydrogon atoms on tim doublo bond
wound bo inoroasod by host. The ootion or the mercuric “into
io- not thoroughly mdorotood but opparmtly its action in duo to
m typo of coordimtim of tho mic ion with tho froo bromine.

most or the mtimo carried out proceeded to o 3mtfl' om-
tmt than hos boon found tam of polybumdimo. Polg'butadimo
ohms only o substitution motim with brmino and o‘nlorino out!
tho oxtmt of subotitutim io-zmoh grootor than that which ooouro
in tho illogonotim o! polynotwlono glycol mlooto. 11:31 Ind Iii}?
odd to pottinztodiom but tho motion of tho tamer requiroo 16
loom-o at 85°C it no catalyst is mod. Polyimtudiono roocto with
3:203 but the «summit of the roootim 10 not known and both of the
901mm" will moot with 83!.12. Tho roooticuo of polfimtodiono
and positive odditi groom io very difficult. Tho addition of
mi: to polybutudimo under a prooouro of 2100 lbsq’otp mo at
433°C in tho pronoun of o Codio catalyst ozumod only very mint
troooo or nitrofiogx.

Tho oi't‘oot of the olootrmoL-otivo om:- gown on tho dmfizlo
bond 13o boa readily ohm by tho motions. carriod out. kp-
memtaflmmndl ortho olootrmoommd

32

the double bond toward themselves which action results in two
labilo hydrogen stuns and a double bond which in wry mrenotiw
to other olootmogntiw group. ouch u bromine ond ohlofino.
Positive groups such on H32 and 11 met rather readily. Outer
when)... ouch n Hflr and BC). canton: one pout-.170 ond mo
manta” group and probably odd through the initial ottocment
or the hydmgan ion tollmd by 3 shift in the double bond
Olootrms tmrd the hydrogen Imd the f 11151 attachment of the
halide group. £11 or the other simple molecules which added to
tho dmblo bond form two groups which have different electro-
mgttivitiooo Tho approach or the two groups probably muses a
slight shift or the pi electrons in one direction. destroying the
W of the electronic structure ”Jonah; addition to taint

91m mm «:3. 1y.

COZ'ICW S I (31:5

1. Ethylene glycol and 331019 onhydrido react to yield o

“coma. light ctnmclorod ruin. polothylono glycol minute.

0 EH 0 H n
flthoprobobloatruoturo1\mitof (0-0 .00 -c-o-c .6).
a a

2. The cmrlflcotion proooodo by I second order reaction which
In. a rat. or .0009 moo/min. at 190°C. and a. rut. of .0012 Wain.
M: 205°C.

3. The) any or counties: to:- the motion in 18.760 ooh/mole.

4o Polyethylene glycol moot. will met with Win, hydmino.
' hydrl‘bo. nitrogen tctroxldo, calm: monochlcrido, hydrogen. bromino.

chlorine. hydrogen chloride, om! hydrogen bromine.

6. The double bond or pclyothylcm glycol mint. 1- counted
by tho m carbonyl group: omjugo’ood to it.

1.
2.
3.

4.

amuwmmr
B.r:.11n.. ”Rapport Ann.'. 260, (1347)
c. 3. 1,098,775
a. 3. 1,103,329

Cox-other... E. 11., Arvin, J. A" 'J. Am. Chem. Soc.', §_1_

2560.70, (1929)

5-
59
7.-
39
99
1°?
11.
12.
13.
14.

15.

Vanndor. 'Ann.". 280. 167. (1894)

r.uzuk1. r.. 'Bull, Chan. Soc. Joptn'.4;9, 17-26. (1935)
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Hbrrox, 0.. “Trans. Flroday Soc.'. 55. 570.1. (1937)
Rtnlnuohi..L., '2, Elootroohan.'. 43. 156-7. (1937)
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noun, 1.. 'J. Am. Chem. 8...“. 63. 3681-6. (1941)
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u. a. 3.393.552 .na U. 8. 2,404,105

Price, C. 6., Veaver, 8.. 'J. kn. Chem. 306... 61. 3360-1.

(1939)

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39 a
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1270-6. (1939)

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19. hut-110. J. J., Protective and Ducal-nun Coatings, John

Wiley a: Son: 1110.. in York. 1941. Vol. 1. p. 427.

an.

Ibido p413.

210 U. 3. 2,115,070

220 MIN. '0 3.. .Jo Chm. Soc-"g 1950. 1059.63

35

 

23. luau. H. J.. Presmn. D... 'Ind. Eng. Chem. Anal. £41.".

21. 3043013.}. 9.. 11022111. 1-. 'J. Am. Chem. 300.“. 68. 1495-

15042. (1946)

26. c. 1. 41. 4103. (1947)

25. Uhlrig. L. and Levin. R. "Ind- Eng. Chem. Anal. 88.“. 13,

90-6. (1941)

27. c. 1. 42.921. (1948) _

28. c. A. 42. 1515. (1948)

29. Jun. Lanna Keenan. Wu. J. Research'.. 258. 272-82. (1947)

80. c. 4. 42.. 201. (1948)

.11. mayo. 1.. nu. I... 'J. Am. Chem. 800.“. 89. 1339-48, (1947)

52. my... 2.. Smy, 4.. ‘J. Am. Chem. Soc.". 69. 1348-51. (1947)

33. c. A. 41.4186. (1947)

34. U. s. 2.434.808

as. c. A. 42. 923. (1948)

as. U. 8. 2.419.188

37. U. 8. 2.422.859

:8. Scum. 'J. Lu. Chen. 5...". 69. 1892-8. (1947)

59. c. A. 41. 3815. (1947)

40. U. s. 2.424.653

41. U. 3. 2,426,647 and U. 8. 2,426,848

42. Snow and Frey, 'J. Am. Chem. 8043.3, 55.. 2417-8. (1913)

$3. Turner, R. A... Connor. 11.. 'J. Am. Chem. Soc.“ 69. 1009-12.

(1947)

44. U. s. 2.419.500

45. Holman. Ho. Imlhshirlo. 8.. Salary, A" Bargmnn. F...

'J. Am. Ch». Soo.'. 69.2589. (1947)

48. Kill-loch. 11.. Johann. c.. um, i... ”Sch". 102. 128 (1945)
36

47. U. 3. 2.426.017

48. Band. G. 2.. fiAnn1. Chem.', 19. 390-2. (1947)

49. 84.1.. 31. Hormnn. 9.. Band. 9.. 91nn1. Chom.'. 19. 971-5. (1947)
so. Levy. 1.. Scaifo. c. w.. '4. Chem. Soc.'. 1999-1104. (1946)

516 U. 3. 2.417.675

52. Coleman. .nd Howell. ”J. Am. Chem. s...‘. 45. 8084. (1923)

53. Ford. J.'H.. Duo. 1... Gainer. F... “J. Am. Chem. 3008'. 69
844-6. (1947)

54'. U. 3'. 2.581.709 U. S. 2.381.4704-6, U. S. 2.417.470, U. 3. 2.417.
892-5. U. 8." 2,418,562

55. C. A. 41. 5718, (1917)

56. c. A. 41. 8890. (1947)

57. Guile. R. I... Huston. R. 0.. 'A Wood Laboratory fianuol of
Synthetic Plastics and 3031mm: Katerina". Hichigon State College.
East Inning. Mich». 1944. p68.

58. Heron and Siegel. ”J. Am. Chem. 5...”. 68. 1494. (1947)

59. )hrk. 3.. ond Whitby. G. 3.. 'High Polymers“. Intomionoo
pubnohorc. 1110., For York. 1940. V01. 1. p. 415

60'. Gotta-.11. F" and Daniels. 17.. 'Outlinel of Phyllool Chemistry“.
John Wiley 1: Sana. 1119.. low York. 1943. 2nd. 9. 350

61. M1912. 3.. Mathews. J.. Ind Williams. J... 'Exporimttl
Phyoicol Chantry'. KcGrov-nflill Book: Company. 1119.. Her York.
1941. 3rd. p. 158-9

62. mcmbottun. I. J” “Reactions of Organic Canpmmds".
Langmna. Green and Coupony. Haw York. 1938. p. 22

63. Ibid. 9. 21

64. Fisher. R. 1... l'Inboratory biannual of Organic Chemistry“.
John‘W1loy 2 Sana. Ino.. NaI'Iork. 1938. pp. 293-327

37

65. Ibid. pp. 386-7

664» Willard. 11. IL. md Bin-.1111. 13. 11.. "Elementary Quantitative
Amlysio'. D. Van Rostrum! Company. Inc. . Her York. 1940. 3rd.
pp. 185-6

87. Ibid. pp. 157-60

68. hhinarsn Jo. fitters Thesis. 1948-. p. 11

694 Gilmnyb. md Bhtt. A. 3.. “Org-.1116 Synthesis”. John
Kiloyrk Sons. Eat York. 1941. Coll. V01. 11. 2nd. 9. 566

70. Sarina-h. 3nd Johnson. Bo Lo. 'Inéo Eng. 0118111.”. 40.
558-42. (1948)

71. 61111311. 3.. and Bhtt. A. ii... 'Orgmio Synthesis“. John

Wiley & 30118. E" York. 1941. 0011. val-t I. 2116.. Pp. 431';

38

 

 

 

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