SXBTBB818 OF POLYAHEHYD1S

APPROVED!

fcjjor P r o f e s s o r

W P i w e s i o r

D i ^ e c t ^ ^ o ^ t h e * I3#p©3^

VCcrtrt^J^\ / Dtam of tl i« Graduate School

SYJJTHBSIS Of mTAIEEHTBES

THESIS

Precented to the Graduate Cornell of the %

Iforth Texas Stat® tJniYeraity in Partial

Fulfillment of the Hequixements

Por the Degree of

MASTER Of SCIEKCE

%

Hubert Bonald O'Neal, B# S<

Danton, Texas

June, 1964

PREFACE

Tha polymerisation of aldahydaa has toon a racant and

intar««ting davalopnant In tha fiald of polymar aynthaeaa.

Thaea davalopiaanta hara includad tha polyuiriaation of both

monoaldehydes and dialdahyias to high aolaemlar weight

poly»ers •

Part one of thia tha sis ooneama tha polyaariaafcility

of aome oc9/9 -unsaturated monoaldehydes and also ralataa tha

synthesis of soma new poly aldehydes whieh harra not haan ra~

portad in tha literature*

Part two ooneama tha polymerization of glyoxal, the

simplest dialdehyde, ^ d tha structure elucidation of thia

new polysar*

iii

TABLE Of C0HTEH2S

Bftgt

MST Of TABLES , . . . •

LIST Of ILUtJSTBATIOKS r i

mm i CfflLPTSR

I , UfTBOKJCTIOF . . . . . 1

nf f i f t n i f i i AT »y # JSJLIr(ItAXUpli X & Ju • • # + • • # + • * # # * • # (

I I I . KSS0LTS AND COHCLUSIOIfS . . . . . 12

PART I I

CHAPTBfi

I , IHTBOHJCTIOlf . 1 5

ii* mmxmAL to I I I . HISUXffS AID C0RCLDSI0H3 25

APKBJTDIX . . 32

BIBLIOGHAPHT . . 36

I t

LIS? OF 2ABLE2

fabl® tag®

X« RtsuXta of Polymerisation Attempt®. • * « *12

usi of ihmmmnms

figure

t« Polj-glyoxal o . . . . . . . . 33

2* AolU SytateA Boljrglyoxsl . . . . . . . . # 34

3- Ac«tyX*ttd Polyglyoxal « * * # » • # « * . 35

Ti

Ml® 1

CHAPTER I

xifsowcficm

formaldehyde h u been encountered la a pelyaerio form,

ever ainee it® earliest preparation by Batltm in 1859 (3)«

The typical formaldehy&t polymers are low molecular weight

substances which decompose when heated* The structure of

the polyf ormaldehy des remained obscure until the very

thorough and skillful investigations of Staudinger (10)*

Staudinger established that the polymers are comprised of

sieleeuXar chains of polyexyaethyleite units* Alio, Staudinger

was able to prepare formaldehyde polymer® with molecular

weights that exceeded the typical by a considerable degree.

This was accomplished by allowing purified liquid formal-

dehyde to pclymeriss© in bulk at -80° C. The end groups

of the polymer® were shown t© be predominantly hydroxyl

thue having the general structure shown below.

10-{GH2-0-)aCHg-0H

Inyestigations by E. X. dm Pont de Keaours & Co. re-

searchers over the last twenty-three years have led to the

discovery of ways to polymerise formaldehyde to a high

molecular weight polymer having high thermal stability.

The success of the stabilisation involved acylation of the

unstable hemlacetal end groups (9).

1

?he polyformaldehyde currently produced fey B* I* 4u

Pont 4# lemour© & Co. is ac®tylat®d polyforiaiiiaehydt and

is sold rnidsr th® trad© name of "SeXrin". Selanea® also

produe«e a polyformaldehyde which is sold und#r the trade

tt»«o »c®loon*« This polyforualdehyd© is stabilised hy

c®polyj®®ri®atioa with a email a&ount of a cyclic ®th®r

such m ethylene oxide (2).

Polymerisation of aliehyit® hightr than formaldehyde

to high molecular weight crystalline polymers wa® r®port®d

in 1960 by Yogi, Satta* «»* fvantoum (it* 8» 4)*

polyald®hyd®« w®r® prepared ®wploylns an orga»o*®t®llie

catalyst at -78° C* in an in®rt hydrocarbon «©lT«at* fh®

polymerisations wer® carried out und®r strictly aoafegrtoott*

conditions. Solid polymers wer® obtained which wer©

highly crystalline and thermally unstable* fhie type of

polymer Is in contrast te the predion®, typical polyners

which art lower in »ol®cular w®t§ht aai ar® anorphoua*

Th® high molecular weight crystalline polyacetaldehyd® 1®

insoluble in all th® cosaaon organic solvent® and is tough

and fiexlbi®, llatta ha® «®tahU®h®d that th®»® poly*®r»

ar® ieotaotio wh®n prepared at low temperature and in th®

pr®®®nc® of st®r®o«p®clfio cataly®ts (7)* Th® atruotur®

of th® hi«h®r polyaldehydes can b® represented by th®

following repeating unit. _

i R

latta (6) to# proposed a mechanism for the anionic

polymerisation of aldehydes which is illustrated with

acetaldehyd© ©ad an aluminum trialkyl •

I H

CH--C.0 4- Al-H J \

a.

H 1

CH,~C*0 •> A1~R 3 \

a

H i

a CB~-»e~£KAl 3 i i

i a

H i

H

H

CH.-CaO

1

i a

C H , - C » G - A l <7*

1 a

H i

•OwCWCH^ •—••">

CH.-C*"»0**CU" 0"*A1 3 i i i a ea, a

ch.-C»O H H

3 i i a ch.

H i

CH

E i

•AJL

1

In order to substantiate hie proposed ateehaniam

latta conducted 8<®m experiments employing labeled ethyl

groups In the organoaetallic catalyst. It was reported

that in the synthesis of isotactie polyaldehydes with

Al(CgH^)g<0C2H^) as catalyst, radioactive polymers were

obtained only if the ethoxlde group contained labeled

carbon atoms. Konradloactive p#ly®@rs were ©htained with

the use of labeled trlalkylalusdnum m catalyst • These

reported results certainly agree with the above proposed

mechanism involving an aUsoxid# transfer#

fmrukftwa has proposed a slallar mechanism whereby

the active species la the polymerisation of am aldehyde

by an organo*etallic compound It the corresponding

metal' alkoxide (4) *

1 i 1**C«0 + B*Kt

1 R-C-.<>»Ke I 1*

1 B»C»Q

H 1 i i

BWCW O»C*»0»»Me I I B' H

H i

i 1*

E H.*"* O**** 0* *0**» 0~M©

i H

I i

r H ac

This mechanism is substantiated by the fact that

some metal alkoxides were found to fear# catalytic activity

for the polymerisat ion of aldehydes.

At the time this work was initiated, only a limited

number of aldehydes hafi been reported aa being polymeria-

able to high molecular weight crystalline polymers. Shese

aldehyde® in elude the normal aldehydes through octanal m

well as trichloroacetaldehyde» phenylacetaldehyde , iso-

butyraldehyde, and. 3~ethoxypropsnal* Share is m noticeable

lack of m aldehyde containing conjugated unsaturation such

aa bensaldehyde, crotonaldehyde, furfuraldehyde, or clnnamal-

dehyde, Also, a cyclic aldehyde had not been reported as

being polymeriaable» A review of the developments in the

field of poly aldehydes has recently been made by Bevington (1).

The polymerization ef unsaturated .aldehydes is mentioned in

this review and it is indicated that such aldehydes poly-

merise , but generally the reactions involve the ethylenic

double bond rather than the carbonyl bond* Alao, Koral

has r%mmtly reported the polymerisation of crotonal-

dehyde by Means of certain tertiary phoaphinea to a

Tinyl-type polymer (55*

flier® were two ob^ectivea to thia project. The firat

objective was to determine if the carbonyl functionality

of m aldehyde containing <x ,/s -uaaaturation could be

polymerised by an organoiaetallio catalyat, auch aa alu*im*a

triethyl wider the usual conditions t© a high molecular

weight cryetalline pely*er. The aeoond objective was to

synthesize new polyaldehydes that had not been reported

in the literature*

fiie following aldehyde a were selected bic am®# they

were readily available and they would be expected to

fulfill the above described objectives! srotosaldehyie,

furfuraldehyde * einnaaaldehyde, hydro ciimaaeldehyde,

bensaldehyde* oyolohezaneearboxaldehyde, and >-oyclehexene-1«

carboxaldehyde •

CHAPTER BIBUO&HAPH*

1.* Btvlfigtom# "Polyatrs ftnra Aldahjraee.," British ?la»tloa. XXXV (f.touwy 1962)., 75-79.

2. B r i t i s h J a t » n t 9 0 3 , 6 6 1 , C « 1 k m m C o r j o r m t i o a of I v r t e s (1 §§§).#•

3* Btrfclarov, A . , wm>*ar ©In ig®,Der iva t« A * * Jo<UaetlMrl«n8,s

AffililJtt J i £ , O W t f r (Mty t85&)». 242-252 ,

4* Fujikawa,* J » r S&eguaa, T . f H« r Kawasaki , A , , J a a i * H*f and F a ^ l i , Y# >

ttCry©taXXime Po lya lA thyAaa , "

M k Sttomtoh a x r a (April 1960),

5* K o r a l , J. S*:f "Crotonaldthydt Polymerisation,M J o t m r n l

M M m K M f M f > « X {0ei©lMir 1§62) f S 3 7 - S l l r

6, Natta, &.f "3t«r*o»p»cifie M l y m r ± m t i m & §& <

Polymer SelincAk XIVII I (S»e«Brt>«r 1960) # 21!

8* Hatta, <*,, Ma**aati# a., Corradinit IV, ana fiae»lf I, f # "I»otaetie •- ' " ~f - * - -

• ® .

iKBailTijLf Ur* | uOXTAQtMS&f JfcVf &2ia l * 6 8 i # X« W#

X X X « r ( I ^ 4 ? 9 l o ) , P 1 5 n 5 l : " ^ , W o t i w ? ' « m w a ® 4 4 '

Schwtit8arf C* S*« Kaeltonald, 1* l i f aai ftmifwem.* #. 0«, jfraaiiJL M imMfi, .Batottr Scl»no«. 1 (1959)» 15&* ' "

1 0 # • o r « m i 8 c h a n I t e t e S a a s B #

11. T«cl, 0,, "Th« PsXywrlaatisn of AX4«iqr<«(," Jmi rnu l of 3cl«nc«. JXVI (3«pt*sb*r I960), 261-86?.

CHAPTER II

WWHtlWffiAf

fhe aldehydes to be studied were commercially avail-

able but it wa® necessary to distill them *1© obtain a, high

degree of parity* The hydrocarbon solvent * n»h#xane t wa® .

eosaaereially available hat it was rigorously purified he-

fore use# Aluminum triethyl v u selected at the catalyst

for this study and it ma purchased from Texas Alkyls as

a 25 per cent solution in n~hexane*

Infrared data were obtained hy a Parkin-Elmer Model

S3? Grating Infrared Spectrophotometer* The samples were

prepared as f&Jol lulls and ran with tedium chloride discs

at a slit setting of 800, X-ray diffraction studies to

determine the crystallinity of the polymers were obtained

with a Phillips Electronic Instruments X~Hay Diffraction

Unit using a 114*6 am. camera.

Typical Polymerisation Procedure

The aldehyde monomer was distilled under a nitrogen

atmosphere on a 30~plate Oldershaw distillation column

into a 300 ml., three-necked» round bottom flasks About

15 ml* were collected in the polymerisation vessel. The

flask was equipped with a stirrer and a nitrogen inlet

and outlet# A 100 ml. portion of n»hexane» which had

been refluxed over sodium wire for eighteen to twenty

7

hour® and then dietilled m a 30-plate Olderahaw colusa,

was addtd to the no nomer# I ha aldehyde eolation was cooled

with stirring to ~73° C* by iumersi&g the flaak 4m a dry

ioe-»aeetone feath. A 1*5 al* (0*00236 sola) portion of

aluminum triethyl (25 par cent isolation in n-hexane) wme

added to the cold eolution % maims of a hypodermic ayringe*

All operationa were conducted under a dry nitrogen atmou-

phara. If polymerisation occurred, it generally did so "

within fire to tea minutes as' evidenced "by an increase in

riaooaity and eventual gelation. ' If there was no evidence

of polymerisation in thirty minutes, another afnal oatalyat

charge•was added and the stirring continued in the ©Old for

two to three hours# In those runa wher© polymerisation did

not scour, a control rm was aada eaploying isotoutyraldafcyAe

to check th® parity of the eolvant*

Polymtrii&tion of Bydroeinna®aiaehydt

A 16 al» <16*35 g*§ 0*122 sole) portion of hydro-

cinnaaaaldehyde was vacuum distilled, h*p* 114® C. at 15

ma* pressure, on the 30-plate Olderahaw coluim into a

300 al*, three-necked reaction flask* A 100 al* portion

of dry n-hescane w m traneferred to the flaak under a

nitrogen ataoaphere and with agitation tha mixture cooled

to -70® C, in m dry ice-acetone hath* The monomer froze

creating an agitation problem* fhe mixture wm® allowed to

warm until a haterogeneoua slush waa obtained* At thia

point 2*0 al* (0.00315 sola®) of 25 par cant aluftitiua

triethyl in i ^ s m i were added % means of a hypoderaio

syringe* After seven to ten minutes, polymerisation was

evident due to the fonaatieii ef a hard gel in the bottom

©f the flMdu A 75 *!• portion of 5 per @*ot aeetylacetone

in bmtaael was added to destroy any residual catalyst asad

ale# to idS la the removal of the catalyst* The polymer-

was isolated fey filtration and then washed with acetone

in an exploeioa proof Waring Header sad filtered* This

was repeated three tiaes and then the pelymer was dried in

a vacuum oven at 60° C, for twenty to twenty-four hour®. •

5here was obtained 5.9 g* of a whit# solid, this eerre-

sponds t© a 36 pea? cent conversion. An infrared spectrtw

shewed aeetal absorption in the 900 cm,""1 to 1200 esu~1

range and the absence of earbonyl absorption at 1730 em.~1.

X-ray diffraction data indicated the polymer to he crystal-

line.

Polymerization of

3-»Cyclohexene~ 1-Carboxaldehyde

A 13 a&« (12.4 g»t 0#113 wile) portion of >-oyelo~

hi'xene- l«*carboxaldehy de was vacuum distilled> b.p, C,

at 17 ®m» pressure, en a 30-plate Oldemhaw e t a and

transferred under nitrogen to a 300 ®1. reaction flagfe*

4 1©0 s&» alifttot of dry a-hexane was transferred to the

flask and with agitation under a nitrogen atmosphere# the

mixture was cooled te -78® C» in a dry iee-acetone hath*

fhe catalyst, 1.25 al. (0.00190 stoles) of 25 per eent

10

aluminum triithyl in n-hexane» was then added hy a*ane of

a hypodermic eyringe. Gelation occurred after eeven to ton

aliurta* but the reactioB was continued at low temperature

for two hour*. 2h* polymerisation wae t«ndaatt.& hy th«

addition of 75 «1» of 5 per cent acetylaeetone in butanol.

fh« polymer wae filtered, washed four timee with acetone,

and dried in the vacrn oven for eighteen to twenty hours

at 60° C*

A yield ©f 3.8 g. of dry polymer- mm obtained. This

corresponds to a 31' per cent conversion "based on the mono- •

MBT weight. Infrared data showed acetal absorption* and

the alaaenee of oarbonyl absorption# X-ray diffraction

etudiee showed the polymer to be crystalline.

Polymerization of

Oyclohexanecarboxaldehyde

An 1$ ml. portion (17*© g*j 0.161 moles) of eyelo*-

h«x»»eearbexaldehyde «is vacuum distilled® b*p. 75° 0, at

20 m * pra»«eres on the 30-plate Olderehaw colusm into a

300 a£U reaction flask, A 100 ml. portion- of toy n-hexane

was trs&*£erred to the fjasfc and under a nitrogen tftao**

phere the mixture was celled with agitation to -78° C4

in a dry ice-acetone bath. A 1,25 »1* (0.00190 mole) portion

of 25 per cent aluminum triathyl in n-hexane was then added

lay means of a hypodermic syringe# • ©elation occurred in

seven to ten minutes but stirring under nitrogen in the

oold was continued for two hours* The polymerisation was

11

terminated % the addition of 75 »!• of § par oant aeetyl-

acaten# i n butanol# ' She f t lywi r wan f i l t t r t d , wMfcti thraa .

tines with and dried in si Taemm ovati at 60® 0*

for twenty-two feoura#

ffatra was obtained 6#9 g. ©f dry pely&ar eerrtfiipemding

te a 41 p#r ©tut eonrarsion. la f rar td data stewed aoatal

absorption and tha abaance of carbooyl absorption* X*»ray

dif fract ion stmdlta indicated tha ptly&tr; to ba axjatdXftaft*

e i & i f l i i l l

R E S U L T S A I D G O R C L U S I O H S

f l i # a l d e h y d e s * s e l e c t e d f o r t h i s s t u d y w « r # a u % j « e t « d

t o t h # p o X y m r i a a t l o a p r o c e d u r e d « s c r l b « d l a t & © e x p e r i -

m e n t a l s s c t l o x u T a b l * 1 s h o w s tim r t s u X t s o f t h e s e

p o l y m t r i z a t i o n a t t e m p t s .

T A B L E 2

b e s o m o f mmmmuTim A f $ s ® $ s

Mmwmr S i r a t t u r t $ CmYemim

C r o t © m . a l d « b y i «

K H W & ' I I !! u

H - C - C - C - C - H

i H

c t f — ct f

0

f m r f u r i l d t l i y d © o =

/3

l

o

y

iT"'

O

0

g* W <mm j k fotto. jfflWtj ^ ult 41* tiihMi ijfldttfi'' aft Jfrti QjJM-o 0

% d r o c i » n a s i a 3 . d s h y d t Q - h l U 5 «

2 » » i S i * X d # l j y d ® Q - X . 0

C y c l o h t x a n e -

e a r b e x a l d o l i y d e a -

4 1

3 ~ e y c l o h t x « n * « » T »

e s r t o © x i & . d < s . t o y d ® o - u 3 1

12

13

fhree • of •lit® aldehydes studied were polymerissable

under the conditions describe<1 In the experimental ehapter.

The infrared spectra of poly hydro cinnaisaldehyde f polyeyclo-

hexanecarboxaldehyde, and poly C 3h»cycl0hexene~t~carb©»~

aldehyde) showed the absence of carbecyl abaox^tion at

173© em,*"1 and. strong absorption in the acetal **$&»& ;

between 900 as."*1 and 1200 cm. *"**• Bear® data indicate

that polymerisation involving th® carbonyl functionality

ha® occurred. X-ray diff inaction pat tarns indicated the

polymers to be crystalline* , .

The polymer* were insoluble in all the m m m n organic

solvents, thus indicating the molecular weights were rela^

tively high and that they were crystalline. Molecular

weight determinations were not attempted due to the extreme

insolubilities of the materials.

The first objective of this project was to determine

if the carbonyl functionality of an aldehyde containing

o( f/-?-uasatmrati@a could be polymerized under the <m>*»

ditions described in the experimental chapter. She result®

of this study indicate that such aldehydes cannot be p@ly»

iserlKed under these conditions* these data indicate that

wasaturmtion conjugated with the carbonyl group is datrtaejttal

to polymerisation reactions involving: the carbonyl group,

fhi® is evident from the ease of polymerisation of the

corresponding saturated aldehyde® as compared t@ the laek

of polymerisation of the U,/? -unsaturated aldehydes.

14

Pmrthtimore, nonxtonjugatad iraaaturation appaara to h&vt •

a# tffact on polymerieaMlity as tyidenead hy tha formation

of polyCB eyelohtxome l-e&rTaaxaldtl d®) * It ia prahabl,#

that coordination with. tha catalyat occur®, as daaorihad

la tha mechanism hy Hatta, but that tha #3#etr@pM2.lt

character of the cartoon atom ef the carfconyl group Is 4a*

eraaaad to euoh an extant, in tha «<t/? -unaaturated alde-

hydes atuAled» that transfer of tha alcoholate doaa not

occur*

2?ha second objective of this pro5®et was to syntheaize

new polyaldehydes that had net heen reported ia th©

litiratmre. This objective was completed a® thrt# new

polyaldehydes ware prepared. Also, tha reault® of this

study contain the ftrat polymerisation of a cyclic aldehyde

to a high pelyaer and tha firat high molecular weight

crystalline polyatr imTolviag tha carbosyl M M of an

unsaturated aldehyde* tha result® of this project have

been published in tha Journal of felyaer Science*,

•Brady, f* T» and O'Heal, H* B», *3?olyaldehydee", Journal JJSC M k MJSSJb I. <**. »•), (1963), 437-438.

¥ABX I I

fOItUffiUZAflOI Of OrlYOXAL

CHAPTEB I

IKTKODUCTIOW

The polymerisation of aldehydes 'to high nolecular weight

polymers has been an interesting and recent development in

the field of polymer syntheses (2, 6, 10)# tonoaldehydee

have been converted into high polymer* whereby successive

addition to the carbonyl functionality occurred. The

products are substituted linear polyoxymethylenes having the

following repeating unit:

I i C ** 0 ** I E

The nature of R depends upon the monoaeric monoaldehyde*

These polymers are thermally unstable and revert to the

monomer unless stabilized.

There are scattered reports in the literature of low

molecular weight polyaers of dialdehydee. Horrish has re-

ported that if the pure dry vapor of glyoxal, OHC-CHO, is

exposed to ultra-violet light, a glassy skin is slowly de-

posited on the walls of the containing vessel (7)« Similar

observations have been made for certain dialdehydes of the

general formula?

0HC(CH2)nCH0

15

16

However, no detailed examinations of the etructuree and prop-

erties hare been reported# ill of these polymer* depolymerise

when heated.

Until recently, the polymerization of aldehydes to

high molecular weight compound® has primarily concerned

monoaldehydes. Overberger and Jffoyer have both reported the

polymerisation of glutaraldefayde to a high molecular weight

crystalline polymer by en intra-intermolecular mechanism (9# 5}*

<f" . O

V r %U

k 2 /iH2-C H2

o f ,0J"

=*2 A

OIL

H 0

E C

H

^ / C H2 \ *

CHg

JL

H x[OHC—(CHg) -CHOJ y0 v " 0 H / ~ V / v w » h c c

I I c c

°*2 / H 4

CB? C H2

E \ cr

(Gig)

CHO ' n

»>n | m+n*x

Koral hae reported the polymerisation of euberaldehyde

to yield a polymer of the following structure (3).

-CI -

(CH2)

CHO

0

6

m

/ ° \ /°N CH

s CHj,

yCH

f a OHg

OHj -CH, n

1?

It Is baliavad that formation of tha nina-mambarad ring la

anargatically unfavorable said therefore » ifi xoich larger

than n.

Berington haa recently Bade a review of tha developmenta

in tha fiald of aldehyde poly*eri«ation (1). In thia rariiw,

ha predicted that ainoe glyoxal, tha aiapleat dialdehyde# la

iaoalaotronic with butadiene, aeveral repeating unit® ara

possible *

E *0 O** H . 0— ' \ / \ /

-C-.0-. c « c c « c ! / \ / \ CHO H H -0 H

(a) (b) (o)

However, it was auggeeted that it ia improbable that polyaera

of glyoxal would contain appreciable aaounte of adjacent mon-

omer unite of typaa (b) and (c) ainca thaaa would eorraapond

to paroxida linkagee in tha main chain. If tha polyner ooi

elated largely of tha repeating unit (a), tha unraactad

carbonyl groups might hecom® involved in growth raaction©

thua giving riaa to branching and croaalinking.

Okaarura and lorlaoto have raportad the polymerisation of

glyoxal to an inaolubla amorphous white solid by irradiation

but no atructure waa propoaed for tha material. Tha infrarad

data raportadly showed acatal abaOrption and tha abaanc© of

oarbonyl abaorption (8, 4 ) ,

1S

As a result of Berington*s prediction# and the reports

by Okamura and Morimotot glyoxal seemed to "be a very inter-

esting dieldebyde to study sinoe it is the first member of

the ©trie® and might polymerise in a number of different

ways* Also a detailed study of this polymer should yield

information that would apply to higher dlaldehydes such as

malonaldehyde and perhaps succinaldehyde* It was anticipated

that if glyoxal could be polymerised as Bevington predicted,

that a ladder polymer might result from an intramolecular

oyclisation*

H H

I I C *• 0 * 0 - 0

c / \\

1 0"' I

B j

1 j 1

C [

I

1 5 *&* 0 * j

, - ^ A

H 0 ' H > 0

H A 1 A

c c B A 1 a

i i

h i

At the time this project was initiated* glutaraldehyde

and suberaldehyde were the only dialdehydes which had been

reported as being polymerisable at low temperatures employing

organo-metallic catalysts. The objectives of this research

problem were to study the polymerisation of glyoxal and

secondly to determine the structure of the polymer as well

as determine the properties of this new polyaldehyde*

mumm mmwmAim

1* B t v i g w t w f t f C « t " P o l y * a r a f r o * A14afayf iaa # * B r i t l a h Elas t i c s . XXX? <Vttawx7 1962), 75-79. '

2. Furukawa, Saagusa, f*y P a j i i , fi»t Kawasaki, A«f X a a i , H« f and t i j i i , T«, "DryetB^liae ft^a3LA#tey4t®|B

H t fiinx Ufjpi i i9«o), i4t^i5f#

3* Start* i* I , and S»olin, I

4* Moriaeto, §«, Kawasrara, H., m& Yoafaie, Y.» Hitroon JCagalca. 3asshi, l i m i 1464,

5# Moytr, f* W* Ir# and trav# B. A., "Maiar PoXyglutaraldafayde,' ~ ffolsmar Science# 1 P a r t B (SaptamMr 1 9 6 3 ) ,

6* K a t t a , $ * t Mmmmt1, §*# Corradial, P « t ana B&gsi, I . " l B o t a c 1 : l o A l 4 » b y d » m y m t r e , • ^ j B t a B B l i l S S i a E I Ghm1M* XXXfXX I April. 1H0)» 1f

I@3Ffl.ili, 1* t« W. aad Gr i f f i t h s , J . &• A«f Journal M ^ 9 , 4 teittef (Saptambar 1932), 2 8 2 9 / ™ ™

0kam**» 3*« Hayasiii, E»» «*4 Merit Bead at ioth Akamai taatimg ©f Society High Pelyntr #apan, Mqrftt May 1f€i» |A§ eit iA W f w c v k m , J . j m € Jmmmri $##

M AjM&Mfa ibbI Qacldof« ?ol« XII of P03$®tr Eaviawa, a l i t a d lay 1., l a r k ©ScTI* 1* Iuacrgut, i volwosi Saw T@rkf

.Jolm Wilay and 8oaoy 1§63«

Orarbargar, C. f # , lehida, S«, ami Singadorf, S#, " In t ra -Xnttyvoltertar Polymariaation @f ilmtaraldtfeydt,n Journal M. M a B iSl«IS6i m i

{ A p r i l Sf-Sf*

10. Yogi. 0*1 "fh* Polyatr i ra t ion of AX4ofydo*»" J partial ©£ Seiaaoa* XOT (SeptmUr 19601, 2lt*§S4*

19

CHAPTER II

f T W t T i f i f 4 T.

MfllAIef 4 MM

Infrared data was obtained by a Perkin-Elmer Modal 21

Infrared Spectrophotoaeter. The samples ware prepared as

Kajol Hulla and ran with sodium chloride diaca. A programmed

allt opening was employed. X-ray diffraction pattarna wara

obtained with a Phillips Electronics X-Hay Diffraction Unit

employing a 114.6 «a. cmsera.

Preparation of Monomeric Glyoxal

A commerlcally available 30 par cant aqueous solution

of glyoxal was vacuum distilled at 1-2 cm. pressure until

no mora watar distilled over* The hard and brittle residue

was pulverised and dried in a vacuum oven at 60° 0. for

120 hours. Upon pyrolysis of this residue, which is believed

to he a triaeric for® of glyoxal* the characteristic green

vapor of monomeric glyoxal was obtained (2). This vapor

v m passed, under nitrogen pressure» through a 14 in# drying

column containing 8 mesh anhydrous CaClg. The vapor was then

passed directly into the polymerisation flask containing

the solvent and catalyst at -7S° C.

Purification of Solvent

Technical grade tetrahydrcfuran (THP) was purified by

refluxing over sodium wire for eighteen to twenty hours and

20

21

•fcfetn distilling under an inert atmosphere on a 30~plate

Oldershaw eolinaa.

Preparation of Catalyst

Sodiuia naphthalene* found to fee an attive catalyst for

the polyaerissation of gLyoxal» was prepared fey the »eth©& of

Scott (4)* Into a 100 xtl* three~neoked flask mm charged

2«05 g# {©§01$ uole) of naphthaleiii ami SO WQL* of dasy THf.

the flask was equipped with a rfcirrer ant a nitrogen inltt

and outlet. $he solution was cooled to 10-20° 0* and with

•tirring 0#|f §• (0*016 aele) of eodiuB wir# wa» added# The

reaction was complete after o m hornr end resulted in a dark

green solution of sodium naphthalene.

Polyne risat ion of Glyoxal

A 170 *!• portion of dry ®Bf was plaotd in a 500 id*

thre*-&«ck«d reaction flask with a atirrer and a

nitrogen inlet and outlet. fM solvent was then ooolii to

~?8° 0# fey iaaaersing the flask in a dry iee~aeetone feath,

A 10 ml* (0*5® g«$0#0037 mole) portion of s©di«® naphthalene

in fSF was addtd fey means of a hypodermic syriage and the pure

dry vapor of saonomeric glyoxal then passed into the reaction

vessel# Polymerisation occurred within five to ten wimttt*

as evidenced fey an increase in viscosity and eventual gelation.

Stirring in the oold was continued for thirty minutes and the

polymer isolated fey filtration# 2? he polymer wa« initially

washed with SHI ami finally with two acetone washing® in an

22

explosion proof faring Blendor. The solid m e dried twenty-

four hours in a vacuum oven at 60° C. The polymer was stable

at room temperature but decomposed on heating to 150° C.

An infrared spectrum of this polymer is shown in figure

1>p*£* 33* X-ray diffraction patterns indicated the polymer .

to he amorphous*

At room temperature, the polymer was very soluble in

dilute sodium hydroxide solution and slightly soluble In water

and also in ethanol• A positive .end test was obtained when

an aqueous solution of the polymer was'treated with bromine

and potassium iodide (1).

Treatment of the polymer with dilute hydrochloric aold

gave a residue whose infrared spectram differed from that

of the original polymer# The spectrum is shown in Figure 2,

page 34.

Acetylation of Polyglyoxal

' A 2*00 g* sample of polyglyoxal was placed in a flask

containing 400 mg* of sodium acetate* A 75 ml. portion of

acetic anhydride was added to the flask and with agitation

the mixture heated to reflux and held for three hours* A

darkening in color was noted after ten to twenty minutes of

refluxing. After cooling to room temperature and filtering,

1.13 §» ®f material was isolated. This material was washed

repeatedly with acetone» water, acetone, and finally anhydrous

ether. The solid was then dried in a vacuum oven at 60° C.

This polymer decomposed upon heating to 290° 0.

23

The infrared spectrum of this material is shown in

figure 3* Page 35'* The acetylated polymer was slightly

soluble in dilute sodimm hydroxide solution at room temperature

and insoluble in water. The acetylated material was slightly

soluble in water at 100° 0. The enol teat on the aqueous

solution was positire,

This acetylation procedure is similar to that reported

by Schweitzer (3)» -

i.

cmmm wwxo§m$M

Veiglt F.# Spot .teats ig .(fagttqjd Analysis. ftw Torkj mseTi«r .^3sJi0HS| foslaS^ lf^7 '

2* Harriee, 0* end tisane* I»€# "TTber JBonoaolekularte m i

Sehw*it»»r, 0. S,f KaoDonald, H, S., ul.PondtrMa, J, 0 A m m ! of Annllaa folyatr Sci«ao«. I (1959), Iji. • f

4# Scott, I# ®*# Walktr, J# wad Hanaley, V» L,t "Sediua Naphthalene, 1# A lew Hetho* for the Preparation of Addition Co^pounde of Alkali Metals asd Boly^y^li©

t s s : » < » « « ^

24

CHUPTER H I

HB8UXE3 AITD C0HCKJ3I0irs

The preparation of antoydrome monomoric glyoxal m i m

extremely critical step im the synthesis of polyglyoxal.

Several attempts were made to obtain the dry monomeric glyoxal

vapor before a eatiafactory procedure was developed. Harriot

reported tho preparation of monomeric glyoxal by the selenium

dioxide oxidation of ethylene (2). This prooadure was em-

ployed but tho yield waa very Xow and storage of the monomer

was diffiouXt• freeze-drying of the monomer from afueou©

solution was unsuccessful due to the extremely dilute solutions

required. An attempt to aseotrope the water with bensene

from the aqueous solution of glyoxal resulted in a rubbery

likt Material which gave no indioation of forming the graen

vapor of monomeric glyoxal upon pyrolyais.

The method aeleoted has been very eueoeaaful and ia

described in the experimental section in detail. However,

it waa found that if the solid isolated from the vacuum dis-

tillation waa not finely pulverised and carefully dried the

polymerisation would not occur*

She solubility of glyoxal was found to be a limiting factor

in the selection of a suitable solvent for the polymerisation.

The solvents normally employed in low temperature polymeri-

zations of aldehydes are hydrocarbons. However, glyoxal is not

appreciably soluble in hydrocarbon solvents at the low 25

26

temperature necessary for polymerisation• T#trafeytewfariii

(J®) was found to b« a good solvent for glyoxal at -?S° C*

It was neeesaary "to rigorously purify THP prior to us® as a

polymerisation solvent«

Sodium naphthalene was found to tot an active caialysi

for the polymerisation of glyoxal in r"BF at -78° C# Aluialnma

triethyl, a 00am® catalyst in low temperature polymerizations

of aldehydes* forms an etherate with ffHf bat this etherate was

not an astir® oatalyst for this polyaerisation# Other catae*

lysts that were studied inolmded a-butyl lithim mi boron

trifluoride etherate* 2 lies# were also found to be inactive

for this palyasriftation• The sodium naphthalene was freshly

prepared before eaoh polynerisation run*

The infrared speotrssi of polyglyoxal {figure 1, page 33)

showed strong hydroxyl absorption at 3300 em* , a strong ab-

sorption at 1595 strong acetal absorption in th# 1100-

950 cm#**-- region, and the mb«#aet of oarboayl absorption at

the usual 1729 oiu~1. The data obtained' frost this spectra®

do not agree with any of the predicted strwteres dasoribed-

in the Introduction. ' • ,

It was noted that if glyoxal polymerized as levington

pre dieted, an alpha hydrogen would be available for enolisatien*

An enolio structure would thus account for the strong hydroxy1

absorption at 3300 oau~\ the acetal absorption, and the

senee of earboayl absorption* However, the strong absorption

at 1595 0*#*" would re»ain va&ssigntd* fhe pr#»«ne® of ®»

enolio structure was ooafiraed by an enol spot test ( 1 ) .

m

$h* polymar h i vsry solubls in diluts eodiua hydroxida

solution and slightly solubla in vatar and also in atfcaaol,

fhsaa solubility data further substantiate the enolle struc-

ture «im% mmlB *r# slightly atidle. She slight solubility

la water would also be expeoted because of the «a*H« hyiroxyl

groups#

Aeetylaeetonef known to exist.in an enoXte f«»t m e

seleoted m a bo del eeapound for studying the structure of

poXygXyowa# A atroag absolution at 1595 cm."*1 has been

reporttd for aeetylaoetone ant is attributed to hydrogen

bonding between m enelio hydroxyl group and a earbtayl

oxygon (3)* this results in a shift of th# ©arbawyX abBorptioE

fr@» the usual 1f25 em"1 to 1595 e®*"1* *hie absorption is

known to be an extremely strong absorption m & is about 100

timm stronger than th© noraal oarbonyl absorption, Since

there 1® a strong absorption at 1595 em."1 fm polyglyoxal,

it has baan proposed that thara is hydrogen bending between

an anolic hydroxyl group ani a, earbonyl oxygen,

OonsetuantXy an the basis of the infrared data, the «»&*

ability data, and tha pesitlre anol teet, tha fallowing

structure was proposea for polyglyoxali

\ .o"

it C / V H S0^H a _

-0 it JO.

f xO-H--0^

?/0-? c.

H

20

I t was halle-rad that acid easditiema w o l d met f » w

hydrogen bonding in tha ©nolle form, fhtr#f®rt f when a

portion of polygiyoxal was treated with dUmta hydraehlarla

aalft, a residue was ohtainad which had m i n f r a red aptstwia

(at#' l lgttrt 2, page 34) different f w m that of the ©riglaal

polpatr# * & U tytetowft shows strong hydrosyl ttlwefptlmi at

3300 cm, % tha abaanaa of atwarption at 1595 a sl ight

aaatarayl abaorptian at 1785 cm#"1, m& a alight 1625 a®/"1

abaorptlan* Thaaa data indieata tha abaanaa of tha hydrogan

bamdad a t w a t e a , pregane# of a snail asoimt of fraa

aarbaayl, from t ha ohalatad portion of tha original j*3jr*»r«

an# ©arba&^aarbaia a t 1625 om.^1 freu tha anal,

fh* msa tmra t i am abaorption had **#* aavtrad by tha ahlftad

carbonyl abaorptlan on tha polygljoaciil apartmm* The a l i g h t

increase in carbonyl absorptita Indioatid t h a mmwit a# ahalatad

e t raa tmra wa® ralat iyaly a&all, Conaatntntly, la tha proposad

struetura, m l a eomsidarably lmrg«r than n»

than a par i l tm af palyglyoacal waa aaatylatad with aaa t l a

anhydrlda# a tramamdom® daeraiwia In hydroicyl absorption wa®

apparent m avidancad by the Infrarad spaetrs® of . tha aoaty-

latad polyraar (aaa WLgara 3» page 35). - Tha aptatrwi alms

i n d l e a t a d am aatar carbonyl absorption a t 1760 a alight

absorption at 1625 cm."*1, tha abaanca of 1595 «#"*1 abaai^tian,

and atrang aeatal mbaarption. Tha 1*25 ea."1 abaarptlon la

aaalgaad t© a a rb t»*«»b tm nnceturatlon, Tha raanlta ©f this

spaetrua ar« axactly aa w#mld l a axpaotad f a r t ha aaatylation

of a polymar with t h t proposed anolla atruatura.

m

Aaetylaeetone was also aub^ected to the aaetylation

procedure and tha apectrua of the aoatylatad material waa

In good agreement with tha literature (3)« Of particular

importance wa® tha fact that tha hydrogan bonded carbonyl mm A

abaorption at 1595 cm. had disappeared indicating acetylation

of tha enolic hydroxyl group had occurred.

Tha reeulta of tha acetylation of both polyglyoxal and

aeatylaeaton# «?# in good agrtaaant with th# proposed moll®

atraoture for tha polyner.

Tha aoatylatad polymer waa found to be slightly aoluble

in diluta acdltua hydroxide aolution# iasolmbli in water at

room tesrperature, and only slightly soluble in water at 100° C.

Tha alight solubility in sodium hydroxida aolution ia apparently

due to tha residual hydroxyl groupa present in tha aoatylatad

polymer aa evidenced by tha infrarad apeetruau ' It is expected

that a longer reaction time in tha acatylation procadura would

produce complete acetylation. Consequently > it would seam

that tha aolubility can ba controlled by tha degree of aeety*-

laticn.

Iha ob^ectivea @f thie research problem mm to study

and to determine tha atructurt

• Tha polymerisation of glyeacal

haa baan' conducted in tha preaence of aodium naphthalana in

tetrahydrofursn at -7$° C. fh« polyglyoxal dacoiposad at 150® C,

and waa slightly aoluble in water and alcohol. Tha polyaar

waa raadily aoatylatad with acetic anhydrida to yield a

the polymerisation of glyosal

and properties of the polymer

••30

a a t a r i a l w h i c h f ® e © 3 ^ © e t i a t a b o u t 2 9 # C , S t r m c t u r © a l u -

c i d a t i o n o f t h e g l y o x a X p o l y m e r i n d i c a t e d t h a t i t h a d a

y o X s w M f r t a l t y p a a t r u c t u r ® c o n t a i n i n g p a n d a n t i m o X ' g r w p * a n d

a l e ® a c y c l i o © h a l a t M a t r u c t u r e I m o ' l r t u g h y d r o g e n h e a d i n g

h m m m m © n o l l e h y d r o x y l g r o u p a n d a p e n d a n t « « M > a i y l ' g r o u p «

$ to e f c j a o t J v a a o # t h i a r e a e a r c h p r o g r a m w a r ® t h u a o b t a i n * 6

a n d t t o p * * X i n i n a y y ' r e s e a t s h a i r # b « a » s u l r a l t t a d a n d a c c e p t e d

f o r p u b l i c a t i o n i n t h * J o u r n a l o f P o l y m e r . B * 4 * n e . i * * « 4 4 4 *

t a i l e d d e s c r i p t i o n o f t h a t # r t m a l t s w i l l b * j r o b l i e h e d s h o r t l y

i n t h e a n s a # J o u r n a l *

* B r a d y , W* T « a n d 0 4 S t e a l , H * & « , " P o l y m e r i z a t i o n o f © l y o x a l , * feurnal o f P e l a r m e r S c i e n c e * I I P a r t B ( I n P r e a a ) *

CHAPTER BmtOGHAMT

i . Fe ig l j P . , EXeerier J5 I i t

'MasiM AH 2ami£jaalwka> »•* J o r t , ©hing Company, 19W.

f . Harr ies , 0, sM teame, !».» "ITber ae&o&olelenlare* m l tri-^ jsoletoalares ©1 joxaX $8 Itetttaehe Cheriscbe B ^ S b l S . a (January

3# B&eaussen, R. S , ^ ' I m m i e l i f f , 3>« B#». and Brat ta in," 1, S . , *•*# * < ^ U I I l A ^ v 4 4 » i 4 . i 4 / « J#A * . WLXiM JmewSkb WmJLM m fi

"Infrared aa t filtraviolet Spectroscopic Studies on Ketones*" J* ' " " *" - *• '• * ~ * • M l («*rcfa

. American OMMeal Society* 107 2*

31

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Book®

Peigl, y., Spot Testa iii o A&ftlza&ft* K e w T o r k» Elsevier Publishing Company, I960.

Okamura? S«f Hayashi, K., and l®rif I., teal at 10th Annual Meeting of Society High Polymer Jaya*, Tokyo, lay 1961, (As oited by Furukawa, J. and Saegusa, J*, MpfSftllflUffl of Aldehydes and Oxides, Vol. Ill of Polymer Heviewl, etited by I. f S k a M l . H. lasiergut, 6 volumes. New York, John Wiley and Son®, 1963*

Staadin«er, E., M e Hochaolelmlfereii Ij^MaSiBSSai Berlin, Springer~¥erlsg7t§ ®0.

Articles

Bevington, J, C M "Polymers From Aldehydes," M M f l l IiilftillSif TXT? (yebrmary 1962), 75-79.

Brady* W. 5. end 0»Keal, H. E., "PolyaMeto-des," M. Polymer Scicnce, I Part B (tagftst 1963)t 437*4387

Brady, ¥• T. and 0#l@alf 1. 1.y "Polymerisation of Glyoxal," Journal of Polymer Sclanee. II Bert B (In trees)*

Batlerov, A., »Uber einig® Berivate dee Jod*ethylen»,n M n A m Per Cfaemle. 0X1 (May 18S9)* 242-252»

Xlt&Jli H« §

Barries, C, and fesme, P., "Tiber monoaolekulares u»d tri-molskalares Glyoxal," Deutsche Chftmieche Gesellgehafct Bericbte, XJ» (January 1907), 165-172*

Koral, J* H., "Crotenaldefayde lyaeriaation," isumti Jl£ Polymer Science. 151 (October 1962), S3f~Sj§;

Koral, J* !• and Bmolin, 1. K», "Shg Prepara*i©» and Poly-merisation of Suberaldebyde,«'W & M ^ t f 1 Part A (August 1963), 2831-2W-

36

3?

Horimoto, 0., Kawa^ra, H,, and Yoehie, Y M E £ ® m iMSfe Zaaahi. m i l l (1961), 1464,

Jfoyert W, W. Jr. and Grev, £• A« , "Linear Polyglutaraldehyde,1

~ 1 *»** B (September 1963% -St#

latta, §*• "Stereospecific Bolm&rigiationa.M Journal of Polymer Science. XLYIII {December 1960), 219-239. '

ffetta, $., Corradltd., P., and Baeei, I* W., "Structure of I sot actio Polyal&ehydes," Journal yf Polymer Science» II (June 1961), 505-525. ' ' "

JJatta, §.f Masaanti, §*4 Corradini, P», and Basel, I. *Xsotftetlo Aldehyde Polymers,® M e lateoaeletelare Cheaie. XTOII (April 1960), 156-159. '

lorrishj R. 6. W* and Griffith#, J• G» A., Journal of Chemical Society. (September 1932), •

Overberger, C, Iehida, S*, and Ringsdorf, H., "Intra?-Interaolecular Polymerization of OiutaraXdehyde»H & m m £ L M l t e M i S S g i (April 1 9 6 2 ) , S1-S2.

Basnaseen, B« S., Tunnicliff, D* D«, and Brattain, R» 8#. •Infrared end Ultraviolet Spectroscopic Studies on Ketone®«* ,€|SP|LM $ M M m i s m SMmLs^L M M M M * (®»eh 1949)s 1068-10727

Schweitzer, C. E M StecDonald, E* and Pundereon, J# 0*, i s m t i M i W U M S 2 S B E . M s m # 1 c 1959) / 15S,

Scottt K. D*, Walker, J. F., and Haneley, V. L., "Sodium Naphthalene, I. A lew Method for the Preparation of Addition Coiapounde of Alkali Metals and Polycyclic Aromatic Srarooerboiis,'1 Journal o| the Aaerteaai. Chemical Society* IvIII (Beceaber 193HT S441-2444.

Vogl, 0#, BDlmnerlB&tlen of Aldehyde®,M Journal of Polmer Science. X&YX (September 1960), 261-264. '

Patents

British Patent 903,668, Celanese Corporation of Aaerioa, 1962*