Title: Synthetic and polymerization mechanism studies of unsaturated quaternary ammonium salts
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Permanent Link: http://ufdc.ufl.edu/UF00098030/00001
 Material Information
Title: Synthetic and polymerization mechanism studies of unsaturated quaternary ammonium salts
Physical Description: 111 leaves. : ; 28 cm.
Language: English
Creator: Angelo, Rudolph John, 1930-
Publication Date: 1955
Copyright Date: 1955
Subject: Ammonium salts   ( lcsh )
Polymers and polymerization   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Thesis: Dissertation (Ph.D.) -- University of Florida, 1955.
Bibliography: Bibliography: leaves 107-110.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00098030
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000551165
oclc - 13301719
notis - ACX5629


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Synthetic and Polymerization Mechanism Studies

of Unsaturated Quaternary Ammonium Salts



June, 1955


The author wishes to express his sincerest

appreciation to Dr. George B. Butler whose tcochinC and

direction have greatly contributed to the completion of

this work. The author is indebted to Dr. A. H. Gropp

for his oncouragmonent, enthusiasm and criticism tlhough-

out this course of study. The advice and suggsctions

offered by the author's Supervisory Cormittce and by his

student associates is Gratefully acknowledged. The author

especially wishes to thank Mr. G. D. Price for carefully

proof-reading the manuscript, Mr. B. A. Parkin for the

benefit of stimulating discussions, and irs. Mlary Joy

Breton for typing the manuscript.

The author is indebted to the Atomic Energy

Commission for the support of this work.




LIST 0.' ?I'I ....S




A. Tetraallylethylene diamine

B. Tetraallyltrjizathyle ne dianine

C. Totraally!hexamrcthyl-no diamine

D. Tetraallylheptanothylene diaxmino
E. Tetr-.allyloctamnthylcne dianine

F, Tetraallylnonamethylene diamino

G. Tetraallyldecamethylane diamirDe
III. P ,;PJiJ I.'IOC OF 1,4 AN D 1,5 Tlr, IA.TY DIA.'I.. S

A. Ui-s.ccecsful Attempts to Prepare 1,4
and 1,5 Tertiary Diamiiies

B. 'rcpar:~-tion of 1,4 and 1,5 Tertiary

C. Discussion of Results and Proposed
ilo clcni sm
















A. Preparation of the IHezaallyl
B. Preparation of the Dimethyltetraallyl
A. General Discussion of Method
B. Experimental Results
A. ilethod of Analysis
B. Surimary of Experimental Results of
Capacity Doterminctions
C. Disc:asion of Capacity Determinations

VII, POLYiESiI. ATI0:T ILiC -:iIr.i S. UDt1S
A. Monomror Syntheese
B. Polyme:-ization Products and Results
C, Discussion of Results












I. Ilfrared Spectral Analysis 24

II. Smunnry of Physical Properties of l,n Tertiary
Diaminos 32

III. Proporties of Hexaallyl Diammnonium Dibromide
Derivatives 45

IV. Properties of Dimethyltetraallyl Dianmmonium
oibromido Jerivativas 46

V. Polymne ization Results 53

VI. SLummary of Ca.pacity Determinations 60

VII. Azo Initiated Polymerization of Hoxaallyylethlene
Diaamoniuw Dibromide 88

VIII. Azo Initiatod Poly-erization of Diallyldiethyl
Ajmmoniu n Bromide 89

IX* Analysis of Poly-diallyldiothyl Anmonium Bromide 91

X. Hydror-enation of Poly-diallyldiethyl Ammonium
Bromi de 93

XI. Comparison of Polymerizations Open to Atmosphere
and under Nitrogen 94

';II. Approximation of the Derroo of Polymerization 97


Figure Page
1. Equilibrium Exchange Capacity 57

2. Hexaallyl Derivatives 64

3. Dimethyltetraallyl Derivatives 64


Previous work1-6) in this laboratory has shown

that insolul:le resins of the poly-quaternary ammonium

type possess anion exci.ance properties. Fuoss and Cathers(7)

have made similar observations with the quaternized deriva-

tives of polyvinylpyridine. With this property in mind, it

was decided to prepare a series of unsaturated quaternary

derivatives of diamines and study the anion exchange

characteristics of the resultant resins.

The main objectives in this investigation were as


(1) To provide a successful synthetic route to

the bis-quaternary derivatives of unsaturated l,n tertiary


(2) a. To study a different approach to the

preparation of the 1,lj and 1,5 tertiary diamines and their

corresponding quate!rnry derivatives, since some p-elimi-

nary i:ork(5) involvin:- their preparation had proved un-


b. To propose a mechanism to explain the

failure, and the various side reactions, of the previous

attempts to prepare tlie 1,4 anld 1,$ tertiary diamines.

(3) To correlate the effect, if any, of the



degree of cross-linking and the swelling coefficient on the

capacity and possible ion-screeninC effect of the resins.

(4) To study the effect of variable distance
between quaternary ammonium exciharcie coiters on the proper-

ties of the resin, especially in regard to selectivity of

ions of various size and charge.

(5) To study the mechanism of the polymerization

of this type of unsaturated quaternary ammonium monoamers,

since they appear rather unique in their property of

yielding a soluble and, consequently, noncross-linked resin

from a monomer possessing two unsaturated groups. ()

II P;: P J Tli; OF 1,n TERTIJ/Y DIliIInS

In attempting to peopcre l,n tertlury diami:.es,

the reaction of the appropriate dihaloalk-ne or di(aryl-

sulfonoxy)calk.ine with diallyl arinoi proved very successful

except in the cases of the 1,4 mend 1,5 derivatives. The

successful method of obtcininT the 1,4 a-d 1,5 derivatives

follow in Section III.

The yields of the l,n tel-tiary diamines were 70-

954 in all cases except for the hexamothylene derivative
wlich was obtaL-.e in 21.75 yield. All temperatures are

listed as de-rees centigrade and are uncorrected.

The carbon, hydrogen and nitro-on analyses were

carried oft by Peninsular Chemroscarch, Inc* and Clark

Microanalytical Laboratory. The bromide analyses were

determined by the Volhard method as riven by Pierce and


The following section deals with the preparation

and purification of the l,n tertiary diaml.es except for

the 1,4 and 1,5 derivatives*

A. Tetraallylethylene diamine

(CHe=CHICHs) al (CHO) ai (CHaCH=CH )

This product was prepared in a manner similar to

that reported by Angelo. ( Three moles (291 g.) of

diallyl amine was added to a paste of 168 g. (2.0 M) of
NaiICO0 and 100 ml. of water. The mixture was heated to a

gentle reflux and 187.8 g. (1.0 M) of ethylene dibromide
was added slowly. Reflux conditions were maintci:ied for
seven and one-half hours after the addition. The mixture
was cooled, filtered and the solution treated with an
excess of 40% iJaOH solution until a distinct separation
occurred. The oil was separated, dried over solid IaOCI
and distilled at reduced pressure. One hundred and fifty-
seven crams (71.14 yield) of clear liquid boili.ig at 72-3e/
0.3 mm, and having4 nD 1.4705 was obtained. The compound
was previously reported as boiling at 790/0.5 mm. and having
nD 1.4702.

B. Tctltaallyltrimethylone diamirne

(C2,,=.Lli i)2:. (Cu2)a (L-A2C-;*=C^-1)8

The product used in this work was that prepared by

Angelo;(9) the procedure was that of Laakso and Reynolds(10)

involving the reaction of diallyl amine with 1,3-di(p-toluene-
sulfonoxy) propane. The yield was 80.~'; boiling point
88-90/0.5 rm.; nD 1.4711. Analysis calculated for

C,5HeN8O: N, 11.95%. Found: i., 11.57%.

C. Tetraall ylhexarnethylene diamine

(C i}e=CiIC 1;a )aN; (CHis), N(CHe CH=CaII ) B

The product used in this work was thct prepared by
Angelo; the procedure involved the reaction of allyl
bromide with hexamethylene diamine mixed with a paste of
ila2CO3 aad water. The yield was 21*75; boiling point

124*/0.8 mm.; n6- 1.4701. Analysis calculated for

CaIsiaiQ: 2, 10.13. Found: h, 10.21J.

D. Tetraallylheptamethylene diamine

(CH2=C;J C. ,) (C:Ia) 7. (C:12--=CIHa)

1. 1,5-dibro:nop :.itaE, e
Four hundrod and seventy-two grams of concentrated

H1SO0 was adJi. with cooli.-; to 1610 .. (9.57 M) of 43L
HBr solution. To this mixture was added 137 g. (1.595 .,)
of tetrahyd2ropDr3an. Tho mixtur-o was allowed to reflux
gently for threo- and a half hours, waz cooled and separated.

The bottom layer was filteird, :as 'ed with water and driod
over XgCO3. 'Thl dark liquid lua distilled -id 237 g. (72.3%

yield) of 1,5-dlbronoo.reitie oboilin,:: at 88-900/6-7 mm. was

2. Pimelic nitrile
Two hundred and twenty grama (i.5 NI) of uaCI was
added to 300 ml, of water and the mixture heated gently
until the 'iaCU dissolved. Pour hundred and six grams

(1,76 M) of 1,5-dibromopentane dissolved in 1 liter of
95% ethyl alcohol was added carefully to this hot solution
until a vigorous reaction occurred. The remainder of the
bromide solution was added as fast as the reaction would

permit. The mixture was allowed to reflux for forty-two

hours after the addition. The ethyl alcohol was distilled

at reduced pressure and the residue cooled a'd filtered.
The filtrate was extracted twice with ethyl acetate

(300 ml. portion and 100 ml. portion). The ethyl acetate
was removed from the extract by distillation and the residue

was distilled at reduced pressure. One hundred and fifty-

seven grams (73.0% yield) of product boilinG at 153-6*/
3-3.5 am. was obtained. Pimelic nitrile is reported
as boiling at 175-60/14 mm.

3. Esters of piLmlic acid
a) ';iethyl pimelate was prepPred in a nenner

sililrf. to the method -iven by Pdms aand arvel.(13)

Five hundred 'Frr's of concentrated H2SO4 was added, with

cooling and stirrin-, to 500 r. of 95 ethyl alcohol. One
hundred and fifty-seven grars (1.29 M) of pimelic nitrile

was added -;d the mixture was allowed to reflux for ten
hours. The mixture was then cooled, poured into an equal

volume of ice water, separated and the top layer dried

over CaCla. The liquid was distilled at reduced pressure
through a Claisen apparatus and 202 g. (72.7% yield)

of diethyl pimolate boiling at 1),9-SL0/19-20 amm. was

obtal.ned. Diethyl pimelate(1) is reported as boiling

at )16-52*/22 mm.

b) Dibutyl pinelate was obtained in a 9C0J yield

by the following gonersl procedure: Two moles of pi.Aclic

acid was adCod to ol ht moles of n-butanol in an equal

volume of toluene and 2 g. of co-'3cettrated :.i':04c was added

as a catalyst. The solution was refl;-xed with stir:-lig

while the water of reaction- was roroved as the azeotrope

and collected in a water separator. The acid was neutra-

lized wCith an excess of "3aCOs while the solution was still

warm. After Ciltrati.n, the tolucne and butanol were

removeJ by distillation. The dibutyl pi~r.clte was fi.-all;

obtaine,0 by distillotion at reduced prs.Lure.

4. hieptanethylene glycol

a) The general procedure(15) as -iven in "Organic

Reactions," Vol. VI for the reduction of esters using

LiAlH4 was followed. Nineteen and five-tenths grains

(0.513 H; a 10% excess) of LiAlH4 was added to 500 ml.
of dry ether in a five liter flask. The slurry was cooled

by an ice-salt bath; stirring~ was maintai.ied with an

induction-typo motor; all possible precautions to exclude

noisturo were taken. A solution of 100 g. (0.368 A) of

di-n-butyl pimelato and 250 ml. of dry ether was added

very slowly to the well-stirred slurry of hydride. After
adding for one hour, the stirring became difficult and
500 ml. of dry ether was added to the reaction mixture.
The temperature was maintained at -3o to 0 during the
addition period of two hours. Two hundred milliliters of
ether-ethyl alcohol solution (50% by volume) was added
slowly to destroy the excess hydride. After all the excess
hydride had been destroyed, 1100 ml. of 10 HSO4 solution
was added until two clear layers were obtained. The layers
were separated; the ether layer saved and the water layer
extracted four times with 100 ml. portions of ethyl acetate.
The combined ether layer and extracts were dried over

Drierite. The solvent was removed and finally 40 g.

(32.5% yield) of heptamethylene glycol boiling at 140-
145/8-10 mm. was obtained. heptamethylene glycol(16)

is reported as boiling at 146-49/l0 mm.
b) The previous experiment was repeated using
20.0 C. (0.525 M) of LiAlI4 and 100 g. (0.368 M) of di-
n-butyl pimelate. Forty-five and one-tenth grams (92.7%
yield) of hoptamethylene glycol boiling at 145-488/8 mm.
was obtained.

5. IIeptamethylene dibromide
The general procedure(17) given in "Organic
Syntheses," Coll. Vol. II, for the preparation of bromides
from alcohols was employed. Sixty-six grams (0.5 M) of

heptamethylene glycol was placed into a flask equipped with

a gas inlet tube, magnetic stirrer and condenser leading to
a tared trap of -IaOH solution. Dry HBr gas from a cylinder

was introduced into the flask while the temperature was
maintai-ed at 100-200. The addition of HBr took three and

one-half hours, at which time the trap contai.-i:g NaOH

solution boran to increase in weight rapidly. The layers

were separated and tho bromide layer was treated with one-

third its volume of concentrated Hl20&. Water was added to

this emulsion until a distinct separation occurred. The
mixture was separated and washed with water-methanol solution

(50 by volume) until the product was neutral to litmus.
The pro.hiuct was dried over CaCI2, distilled at reduced
pressure and 65.0 r. (50.3w yield) of clear liquid boiling

at 125-260/8 mm. was obtained. Mullr and Vane(18) report

the boiling point of heptancthylene dibromide as 1230/11 nmm

6. Tetraallylhoptamethylene diamine

To a slurry of 242 g. (2.5 M) of diallyl amine,

126 g. (1.50 M) of .aiiCO3 and 75 ml. of water, heated to a
gentle reflux and stirred vigorously, 65.0 g. (0.252 M)

of heptamethylene dibrcnide was added slowly for one and

one-half ho:rs. The mixture was cooled, treated with an

excess of LC4 NaOH solution, separated and the amine layer
dried over NaOH pellets. The excess diallyl amine was

distilled and the residue was distilled at reduced pressure
through a Claisen apparatus. Sixty-four groans (87. yield)
of light yellow liquid boiling at 124-26*/0.1 rmn. and having
an n 1.4719 was obtained. Analysis calculatod for

Ce114 s: C, 78.6 H, .8; ,, 11 ; i 9.6o5. Found: C, 78.51 ,

H, 11.50o; ;i, 9.51.*

E. Tetraallyloctanethylene diamine

(C i,=CHCi ); (C Ha)I ; (CHGCJ =C Ia) ,

1. Suberic nitrile
This preparation was carried out exactly as
described in the previous preparation of piiolic nitrile.
One hundred and ninety-seven grams (0.82 M) of hoxanethylene
dibromide dissolved in 500 ml. of 950 ethyl alcohol was
added to 100 g. (2.05 M) of NaCI; dissolved in 150 ml. of
water. After the hexawiethylene dibromide was treated in
the same rmnnvor as the previous nitrile preparation, the
mixture yielded 96 g. (87.1% yield) of clear liquid boiling

at l75-78*/10 a. Deutsch and v. Braunn(19) report the
boiling point of suberic nitrile as 176-8/11 mm.

2. Diethyl suberate
This preparation was carried out exactly like the
previous preparation of diethyl pimelate. Ninety-six
Crams (0.705 M) of suberic nitrile was allowed to reflux
fifteen hours with a mixture of 400 C. of concentrated

IiSO20 and 40C ml. of 95. ethyl alcohol. After the stberic

nitrile was treated in the sa:no irmnner as tVie previous
nitrile hrydolysis, the mixture yielded 119 g. (73.5% yield)
of clear liquid boiling at lO-L,'O/8 mrm. and having an
n8 1,4324. Karvonen(20) reports the followilt constants

for diethyl suberate: boiling point, 136-80/8 mn. and
n, 1.43278.

3. Octarethylene rlycol
The reduction of diethyl suberate was carried out
in the scje manner as the previous reduction of di-n-butyl
pimelate. One hundred and nineteen rrams (0.517 1i) of
diothyl suberate dissolved in 250 ml. of dry ether was
carefully added to a cooled slurry of 25.0 g. (0.66 M) of
LiAIi4 in 500 il. of dry etheo. The reaction mixture
yielded 73.5 r. (97.4* yiold) of a clear liquid boiling at
158-60*/9-10 nam. The boili.g; point of octamethylone glycol
is reported(21) as 160-620/9*5 am.

4. Octar~ithylene dibror-ide
Octamethylene dibromide was prepared in the sane
nanner as the previous prepLration of hoptamethylene di-
bromide. ieventy-three aid five-tenths grams (0.503 M)

of octamethylene -lycol was treated with Gaseous iir at
100-20* for two hours. After being treated in the same
manner as the previous bromination, 86.5 g. (63.2% yield)

of clear liquid boiling at 170-1*/33-34 mm. was obtained.
Dionneau(22) reports the boiling point of octamethylene

dibromido as 173*/35 mm.

5. 2etraallylocta-methylone diamine
To a slurry of 303 g. (3.18 II) of diallyl aniLe,
168 g. (2.0 M) of .aHCICO and 120 ml. of water, heated to a
eontle reflux and stirred vigorously, 8,.5 g. (0.318 M)
of octamothylone dibromide was added slowly for forty
minutes. Afte, the addition, the mixture was allowed to
reflux for an additional eight and one-half hours. The
mixture was then cooled, treated with an excess of LO' .aOli
solution, separated and the aminc later dried over iaoH
pellets. The excess diallyl amine was distilled an-d the
residue was distilled at reduced pressu-re thiro,'h a Claisen
appa-atus. The prodAuct frothed very badly; class wool and
paraffin were added to relievo the foaming. Eishty-three
and five tent'.s grams of light yellow liquid boiling at

133-40*/0.l mm. was obtained. This liquid was fractionated
sad 73.0 r- (75.5` yield) of light yellow liquid boiling at

134-80/0,09-0.1 mrn. ind having: an nS 1.4651 was obtained.
Analysis calculated for CloHal3a: C, 78.9,; 'I, 11.-32;

i., 9.2%. Found: C, 78.81/; H, 11.755; N, 9.15C.

F. TetraallTlnonamethylono dianine
(CHIi=CHCsii )2N(C1H, ), (CH, l=CLal )

1. v'rom tile disulfonate
The preparation of 1,9-di(p-toluenesulfonoxy)nonane
was accomplish. od in accordance with the procedure of Laakso
and lHeynolds.(lo) Eirhty-six and two-tenths grra:s (0.54 M)

Oj. noinam.ethylone Cl:rcol dissolved in 10 ml. of dry pyridine
was treated with 206 g. (1.08 A:) of p-toluene sulfonyl
chloride dissolved in 280 ml. of dry pyridine. Folloiuiin
the method cited, 217 r. (85.5 yLold) of pro.i:.ct was
obtc.i-ed. Lieltini point after third recrystallization from
absolute alcohol was 75-70. Analysis calculated for

CaaliaSs0e: C, 5).95 ; H, 6.j:>. Found: C, 56.87,;
:, 6.o9;.

-.noty-o:e grams (-.195 M) of 1,9-di(p-toluone-
sulfonoxy) no:a:le was refluxed and stirred for fort,-eiLiht
hours '.ith 33 g. (4.0 M) of diallyl amine in accorda.ice
with the procedure of Laakso and Remnolds.(10) Afte working:
up the reaction r:.iture, 42.5 g. (68.3; yield) of liuiht

yellow liquid boiling at 11i8-52/0.06-0..1 m. mrnd having
an n52- 1.4710 was obtaoined.

2. From the dibromide
To a slurry of 170 g. (1.75 M) of diallyl Laine,

84 g. (1.0 M) of ':aHCO3 and 50 ml. of water, heated to a
-cotle reflux and stirred vigoro.:sly, 50 g. (0.175 M) of
nonanothylene dibromide was added over a two and on---.alf

hour period. The mixture was allowed to reflux an addi-
tiaoal sevon aod one-half hou-s. The mixtju.o was thon
cooled, treated with an excess of 40' MaO0i solution,
separated and the amine laTyer dried over s0'Hi pellets.
The excess diallyl amine was distilled and the residue was
distilled at red-iced presoFre. ?ifty-two gra-s (9m4.5

yield) of li-ht yellow liquid boiling at 146-8/0.06-0.07 mm.
and hrvin.- an nDi 1.4723 was obta.i ed. Analysis calculated
for Cs,Ha38,: C, 79.3/; ri, 11.93. Fo'-nd: C, 79.8-5;

i, 12. 01.

G. 'otraallyldecaWr3tnilen1e dimline

(GHC=C:ICHs2 )a (CH2) eol( CH;G=C=GH2 ) 2

1. From t-e disulfonate
he preparration of 1,10-di(bo .zoenesulfonoxy) docame
wrs accomplisrhed in accor-dance with t~ prococd.-re of Laakso
and Rernolds. (10) One hundred and one gram-s (0.58 M) of
docrenethyl-no glycol (n.p. 70-1) dissolved in 200 ml. of

dry pr:-idln- :.s treated with 205 g. (1.16 M) of ben:cne
sulfor-yl chloride. Follow!:- the method cited, 226 g.

(35.65 yield) of product was obtained. -lelting point after
third recrystallization from absolute alcohol was 46-308
/Aialysis calculated fcr CmaHa oSgO: C, 50.14'; i, 6.66u.
F'ouLd: C, 57.6T/; H, 6.79?.

One hundred and thirty-six Crmis (0.3 M) of
1,10-di(benzenesulfonoxy) decane was refluxed for forty-

oi.rht hours 'with 3uU ;. (5.15 ') of diallyl amine in accor-

dance with the proced-ire of Lackso and Reynolds.(0 The

reaction ni::ture yielded 82 g. (u2.2J yield) of a dark

liquid, boili..- at 155-6C0/05 rm. This was fractionated
and 72 g. of a li ht yellow liquid boilij:! at 154-5/
0.1-0.2 --i. and havlin an nD 1.4701 was obti: .ed. Analy-

sis calculated for CG22I1402: -43:. found 2, 8.27,.

2. -.ro i tV dibro:-ido
To a sl-:r'r of 162 -. (1.66 :) of diallyl ami.-o,

84 (. (1,0 M) of !;a:iCO3 arn .50 nl. of water, heated to a
?-tle reflux nid stirred viGorousl-, 50 -. (0.166 M) of
decamethylone dilb omido was added over a period of one and

threo-fourths hours. The rmi-.ti, u was efl''.xed for an
additional fivq hours, cooled, treated with an e::c.ss of
IC" U'r:0Hi s< l't.io., separated and driod over 'iaOi pellets.

The excess dicll-jl v&ine was to]:en off and the residue
distilled at reduced pressure. Thirty-nine graC1s (70.5-

yield) of a lirht, v--llow liquid boili: at 152-6*/0.07 mm.
v id havi:- an ini- 1.725 was obtrl.-ed.


Attempts to prepare tetraallyltetramethylcne

diamine and tetraallylpentamnethylene diamine by the

previously successful reactions of the 1,4 and the 1,5

dihalo- or di-(arylsulfonoxy)alkanes vith diallyl a.ine

were unsuccessful. (23) In the reaction with the dihalo-

alkanes, the products were diallyl pyrrolidinium bromide

and diallyl piperidinium bromide. In the reaction with the

di-(arylsulfonoxy)alkancs in the presence of a larr'e excess

of diallyl ainne, the products were allyl p.'rrolidine and

triallyl amine from tihe 1,4 derivatives, and allyl piperi-

dine and triallyl amine from the 1,5 derivatives. The

products of the reaction can be explai.ied on the basis of

an intramolecular cyclization to the five and six ::embered

cyclic quaternary ammonium salt, followed by an allylation

of the excess diallyl amino by the quaternary ammoniun salt

to produce triallyl aminc and the appropriate allyl substi-

tuted hetrocyclic amine.

This section deals with the isolation and identi-

fication of th'e products of the above reactions, an ex-

planation of the course of the reaction and, finally, the

successful method of preparation of the desired 1,4 and

1,5 tertiary diaminos.

A, Unsuccessful Attempts to Prepare
1.4 and 1.5 Tertiary Diamin-s

1. Reactio:i of 1,4-dibromobutane with diallylamine

a) A mixture of 44 5 g. (0.206 M) of 1,4 dibrono-

butane, 60 .. (0.618 Mi) of diallyl amino, 34.6 g. of IaliC03,

and 20 ml. of water was reflu :ed for seven hours. After

filtration and addition of 2iaOH to the filtrate, the organic

layer was distilled; however, no material was obtained

boiling in the expected ranre for tetraallyltetramethylene


Several other experiie-nts were perfor.;ed varying

the ratio of dihalide to amine, cha.n-gin solvents and

chagrin the base, but in all cases none of the desired

product was isolated.

b) To four milliters of 1,.-dibromobutane was

addod twelve milliliters of diallyl amine at a temperature

of 35. While the liquid was beirn- stirred, the temperature
rose to 1000. After standing overnight, the crystalline

product was collected, washed i ilth aceto.ne and recrystal-

lized from hot acetone and a small amount of absolute

alcohol. The product started to decompose at 205* and

melted completely at 315-220 with decomposition. A

bromide analysis of the product showed 34.77Z bromine.


The calculated Br percentage for the dihydrobromide,

(CHI2=CCIIC a)aI(CII )4N(C!aC=Clsi)2, is 38.951. The calculated
+ +
Dr" Br"

Dr percentago for diallyl pyrrolldiniun bromide,
I \+ iGCE=Caii

CHaCH=CHI,, is 34.49%.

Since diallyl pyrrolidinium bromide has not been

reported in the literature, a method for its preparation


N-allyl pyrrolidine was prepared by treatinT

pyrrolidine with allyl bromide in the presence of NaHiCO3,

The boiling point was 129-30* and n8.- 1.II086. Analysis

calculated for Cyia U: C, 75.64; H, 11.71;; N, 12.61".

Found: C, 75.35,; H, 11.87%; N, 12.,1%.

To a cold mixture of 21,0 g. (0.19 M) of ;-allyl

pyrrolidine and 75 ml. of acetone was carefully added

25.0 c. (0.207 M) of allyl bromide with cooling. The

hygroscopic salt which precipitated was washed with

acetone and dried in a vacuum desiccator. Thirty-nine

grans (90.5% yield) of product was obtained. After re-

crystallization from hot acetone with a small amount of

absolute alcohol, the product started to decompose at

2020 and melted completely with decomposition at 315-20,.

A mixed melting point with the reaction product from above


showed decomposition starting at 198o; the mixture melted

completely with decomposition at 314-220.

2. ieactioi, of 1,5-dibromopentane Uith diallyl amine

A mixture of 4 ml. of 1,5-dibromopontane and

12 ml. oi dicllyl amine was allowed to stand overnight.

The hygrioscopic crystals were collected, washed with

acetone and dried in a vacuum desiccator. After recrystal-

lization from hot acetone i.ith a small amount of absolute

alcohol, the product gave a flash melting point of 194-60.

Upon slow continuous heating the product started to de-

compose at 209 and melted completely at 297-302 t:ith

docomposition. A bromide analysis of the product showed

32.318 bromine. The calculated Dr perce-.tare for the

(CiS=C3,LHa) (i'I)6:i(ciihi.*u=ic)as is 37.66%.
+ +
Br" Dr"

Tio calculated Br content for diallyl piporidinium bromide,


\C;CU=G;ig, is 32.o'. Diallyl piporidinium

bromide is roported(l) to Ilavo a flaai inoltiLg, point of 190.

3. ioaction of l,4-di(p-toluoGiesulfonoxy)butane with diallyl-

Aftor a number of unsuccessful attempts to obtain

totraallyltotra-iethyleno diaminine by the method of Laakso

and Reynolds,(10) the following modification was adopted:
Two hundred and twenty-eight Crams (0.577 1) of 1,4-di(p-
toluenesulfonoxy)butane and 632 g. (6.5 M) of diallyl amine
were rofluxed for seventy-two hours. The mixture was
allowed to cool and the layers separated. The lower layer
was treated with an excess of 40 0 iaOH solution, allowed
to stand overnight and filtered. Fran the filtrate, 3 g.
of a yellow liquid boiling at 100-1101/0.3-0.5 mm. and
having an nD 1,4721 was obtained. The original upper

layer was distilled and 180 g. of diallyl amine was re-
covered. The residue was distilled at reduced pressure

and 11.5 c. of a light yellow liquid boiling at 100-110o at

0.3-0.5 mm. and having an n$4- 1.4720 was obtained. A
nitrogen analysis showed 9.33,. The calculated nitrogen
percentage for tetraallyltetranethylene diamine (C eHa8Ia)

is 11.27.
These fractions appear to be impure tetraallyl-
tetramethylene diamine because this compound was prepared
by another method and found to have a boiling point of
96-8o/0.1 mm. and an ns- 1.4716. All attempts to purify
the fractions failed; the attempts to prepare derivatives
for identification purposes also proved unsuccessful.
Considering the total of 14.5 g. of crude product as
tetraallyltetramethylene diamine, the yield would be 1015.

howeverr, during the distillation of the above
reaidue at reduced pressure, a large amount of material
was collected in the cold trap. This material was
fractionated r~d a small amount of diallyl amine was
recovered. This was followed by 20 g. boiling in the
ratire 111-147, and 21 r. boilingJ at 147-?149 and having
an ne- 1.44 89. With allyl bronide, this latter fraction

(147-49*) 7ave tetraallyl3 ari.onium bromide molting at
183-40. A mii;xe meltinG point with an authentic sample
of tetraallyl aunonium bromide was 182-83*. The reported
constants for triallyl arrine are: Boiling point 143-90;

2n'- 1.4502.
The intornediate fraction (111-47) should contain

allyl piyrolidine (bp, 129-30) if the previously cited
disproportionation rnochanism is correct. However, allyl
p rrolidilo was not isolated front the fraction at that time.

4. Reaction of diallyl pyrrolidinium bromido with
In order to support the above proposed course for
the reaction, 36.0 r. (0.155 ') o' diallyl pyrrolldinium
bromide and 120.0 g. (1.24 M) of diallyl amine were re-
flu::od for thirty-six hours. Turin;~ this time, the liquid

ti-'pe.-ature remained at 1090, the boiling point of dic.llyl
amine. After thiE time, the salt became viscous, the color
changed to a licht -ed and teo temperature rose to 120o.

Refluxinc was continued for an additional twelve hours.
The mi:.ture was cooled, filtered and the dark red solution

fractionated to yield: Diallyl arino, 68 g.; boilijC

point, 110-13,; n1f- 1.4397; all-l pyrrolidino, 7 C. ;
boiling point, 130-1i0*; n25- 1.,1471; acd ttiallyl ani.e,

4.5 r.; boiling point, 146-90; n~ 1.lU99.
Treatiicut of t.e allyl p.rrolcidlne fraction with

allyl bromide gave the quaternar- ammoniiun salt melting

at 313-20 with decomposition. mixedd molting point with
an authentic sample of diallyl pyrrolidiniui bromide was

314-210 with decomposition.
Treatment of the triallyl anine fraction with

allyl bromide gave the quatornar-;' amoniIu salt melting

at l84-5". Mixed melti:ig point with an anthontic sr-e mple
of tetreallyl annonilm bromide was 184-5*.

5. i;oaction of 1,5-di(benzonesulfo..oxy)pont e9- with
diallyl amine

As in t'ie case of the 1,4 derivative, a nnumbe" of
unsuccoszsful attempts to pr-eoare tetrea llylpentamethyleno

diamine by the method of Laakso and Reynolds(10) were made

and the following modificaticn was adopted. 'Tw1o h'. .drod
and seventy-nine gra-,s (0.727 M) of 1,5-di(benzenesulfE..oxy)-

pontane and 776 r. (8.0 M) of diallyl amine were refluxed
with stirring for forty-eight hours. The product was

separated as described above, and 501 g. of excess diallyl

amine removed b: distillation. Following! the diallyl
amine, l5 g. of a colorless liquid boiling at 1I7M-9*
was obt.aled, a !d 40 o, o.f a dark yellow liq~3i boiling
at 60-100 at 0.05 is. iAftor refracticnration of the
fraction boiling at 147-1:90, a prod-ict boilin.- at 1l8.-503
a.d having an nD I.l4539 was obtained. On the basis of

the above proposed mechLanmis for the reaction this
product sho Id be a mi.:tu-c of triallyl amino (b.p. 1.3-

50, nD 1.1502) asd allyl piporidine (b.p. 14'- ,o

nD 1.4577).
Since it was ir'possible to separate t;ese com-
pounds by distillation, an iifrsar:i analysis was node
"sl."i a Porkin ULei double-boam infrared spectrop`.oto-

meter with a cell thic lnss of 0,025 mr:. Various mixtures
of pure nacmol.s of triallyl aonine and allyl piporidine
were a~de in an attempt to match the index of refraction
of the reaction rIlixtu-o. A min-ture contain. C 51e by
we-it of triallyl amine hsd a -;DL" 1.4533 compared to

the nl'- 1.4539 of the reaction Tni:tu e. The infrared

spectral anal-yis .'-rve tile folloi.in-r results:



Sample nas Absorption band (mici-ons)
Sample n D


Allyl pipori-



(51, by wt. 1.4533

Product 1.4539

3.30 sh

3.38 sh


---- W

7,23 7.70 8.33



7.22 7.70 0.33

7.22 7.70 8.33

'these results show conclusively the presence of

both triallyl amine and allyl piperidine in the reaction

product mixture, and the refractive indices indicate

approxinately equal molar quantities of tihe two compounds.

B. Preparation of 1,L aoid 1,. Tertiary Diariinos

1. Tetraallyltetramethylene diamine

(Cea=ChCH )NI;(CH)4N (CiiaCli=0iis)a
a) Preparation of L,.i,1'.1,'--tetraallyl suc-

cinamide.--To a well-stirred solution of 211 g. (2,168 i0) of

diallyl amine in 200 ml. of dry benzene was added a solution

of 84 g. (0,542 M) of succinyl chloride (bp. 87-9/18 mm.)




---- I

in 100 ml. of dry benzono while t:h tempornture was nmin-

tailod ,-t 10-20', titrrfL: i was co:tinl'.od at this tempera-

ture for one hor afto:-- addition w conrileted. The Solu-

tion was filter?' ar.d the Ciallyl amidI hydrochloride

crystals were washed with Jr-y benzc:-s. The wcshinirs were

added to the ori "'inal filtrate and the bensene removed.

Tieo rveadno wfs distilled at re'd- ed nress-'ro to obtain

100 g. (80o,6; yield) of liquid boililn: at 160-2/0. 1 "n.,

having an n, 1.5925 and d4 1.0060. The infrared

spectral- showed absorntlon bacds for aliide carbonyl a-:d

carbon-c'r','o dc:ble bo:d. Anclyslis calculated for

C.e:40s: C, 69.:,; H, 8,38;; 1T, 10.13., Fo~nd:

C, 69. C'; 9.11 ; -;, 9.7 "T: calc-'letd.: 81.86.
IL-D fo'd: 81.15.

b) :,dJ ctio-.. of :1,: '--tetrnallyl s c-

ci:l;,ide.--To 16 g. (0.h2 H) of LiA1H4 as a sl'-rry in

300 ml. of td,- ethLor, was added during one anid throo-
fourths hx-.., 62 p.* (0,22 IT) of tetrc-llyl s-.ccina-ide

dissolved in 2CC ml, of dry ethe'r, A tihre-neck five

liter flask equi::e" Milth ice water condenser, thermometer,

droppi:ri f-Tunol, sealed stirrer, and cooled by an ice-solt

bath wrs omplo~ed. The tempe-"ature of the reaction ml1:ture

was nrii-itrui-ed below 15* durir- the addition:. After reflu;zing

fifty hers, a mixture of ethanol and water was added to

destroy tho excess hydride. The mixture was then treated

with 800 ml. of 10% NaOH solution and solid "8aOH pellets
until a distinct separation occurred. The ethor layer was
separated and the water layer was extracted twice with
200 ml. portions of ether. The combined ether layers were
dried over solid NaOH, and the ether removed. The residue
was distilled at reduced pressure to give 27.5 g. (49.3%
yield) of clear liquid boiling at 96-8*/0.1 mm. and having

an nD 1.4716. The infrared spectrum of the compound
showed the absence of the carbonyl bond and the presence
of the carbon-carbon double bond absorption. Analysis
calculated for C,eIlleeNI C, 77.4l%; H, 11.3,; hI, 11.2,.
Found: C, 77.50; H, 11.3N; 1, 10.7". The dihydrobromide

was prepared by treatment of a dry benzene solution of the
above amine with dry HBr gas. The compound melted at 107-8.
Analysis calculated for C,1ois3aoBra: Br, 38.95r. Found:

Br, 38.621.

2. Tetraallylpentamethylene diamine
(CHa=CiiCH2 ) 3;(CHB),N(CHaCH=CHja)a

a) Preparation of -I;J.11'.Ii'--tetraallyl rlutar-
aaido.--UsinG 64 g. (1.64 M) of diallyl amine and 72 g.

(0.425 M) of glutoryl chloride (b.p. 1000/10 mm.), and
following the procedure above for the preparation of
tetraallyl succinamide, 113 g. (91.7 yield) of totraallyl
glutaramide was obtained boiling at 165-7*/0.03 mm, and
having an nia- 1.5020. Analysis calculated for C,7HSOeiHs:

c, 70*3/; H, 8.86"; i, 9.t65. Found: C, 69.9c; H, 8.366;
i, 9.26%. The infrared spectrum showed absorption for
amide carbonyl and carbon-carbon double bond.
b) Induction of li.il.U'..I'--tot.,ually7l lutar-
saido.--Usinr 21 r. (0.553 I) of LiAlH4 and 87 r. (0.30 1)

of tetraallyl rlutaramide, and following the procedure
described above for the reduction of tetraallyl succinamide,
e::copt that this solution was allowed to reflu-< for four

hours instead of fifty hours, 53 g* (63.[L yield) of a
clear liquid was obtained. This product boiled at 96-70/
0.02 n2i. and had an nr- 1.4743. The infrared spectrum

showo'e the absence of the carbonyl bond and the presence
of a stronC terminal carbon-carbon double bond. Analysis
calculated for C71Ho1- : C, 77.8'; H, 11.4.6 ; I, 10.68;.
Found: C, 77.3oj; H, 11.2LI; N, 10.33T. The dihydrobromide
was pre)ared by treatment of a dry benzene solution of the
above amin:e with dry IIHr ras. The compound molted at 115-

7. Analysis circulated for C,7i1haiBrs2: Br, 37.66'.
Found: Br, 37.58%.

C. Discussion of Rosults andl Proposed IMechanism

In the reaction of l,,L and 1,5 dihaloalkenos with
diallyl zrline, it appears likely that the first attack
would result in the formation of the 4 or 5-bromoalkyl
diallyl amnino hydiobromide. In the presence of an excess
of diallyl amine, the free bromoalkyl diallyl amino should

be liberated, since it should be the weaker base. The second
step probably involves the formation of a cyclic quaternary
ammonium salt. It has been pointed out that aliphatic
bases containinC amine and halogen in the 1,4 position
exist only as salts and on liberation of the bases condense
to pyrrole derivatives. It has also been shoun(25) that
azin.-s of the type x(CHs)nNRa yield (CHe)nNRax" when n

has a value of 4, 5 or 6. It appears, therefore, that the
mechanism of reaction of 1,4 and 1,5 dihaloalktans with
diallyl amine is as follo~.s:

Br(CH,)4, Br HIfl(CHICIH=C:I)- Br(C 4 I)a'(e2CIl=C=g),

Hi (CHaC T=CII2 )a

( C)C =T(C:2C I"I 0:a )12 Br (CHs) e ( H( C2CIi=CH2 ) I

Although disproportio.'ation was not observed in the
reaction of diallyl amino, eith-r with 1,4-dibromobutane or
1,5-dibronopcntano (probably since a large excess of diallyl
amino was not .seod), heon diallyl pyrrolidinium bromide was
heated with a large excess of diallyl amine, both allyl
pyrrolidine and triallyl amine were isolated and identified.
It appen.as that the reaction is as follows:
\+ l3HaCIICHs
+< C=C + 2HN1(CH1ChCH) reflux in
1\CW=CHU s larGe excess of
+Br- HN(CHaCH= CHCa)
Iahl(CH2CiH=CIia)s + N(CIIHCI=CI[a)3 + D .CHSaCH-=CHS


This would appear very likely in view of the work of Zliel

&ad Pecklam(26) involving the migration of the furfuryl

group in the disproportionation of fur'uryl quaternary

anronium derivatives. These authors havo shown the

followii g:

I -(Ch) ) + reflux r (Cis)3l +

(0.05 M) (0.6 M) s +

+4 llg
(W3' yield)

Thic tTpe of disproportionation also occurred in

attempting to use the nothod of preparation involving the

di(aryl-3ulfonoxy) alkanes in the presence of a large excess

of diallyl amine. It appears that in this case the reaction

involves first an intramolecular cyclization, as shown

before, followed by a disproportionation involving migration

of an allyl -roup, as shown above. This would be indicated

as follows:

(lihere A is an arylsulfonate group)

reflu.x in A CH=
A(CHg)4 GA excess (

i- i (CO IaC =C IT= )a CC.ia- CH=Ca

2 (Cg(...=CJ i)a <+ ILa(C.lCi=C~Ha) + (3) i CIIeClI=CHe

Although Laakso and ieynolds(0) reported a yield

of 77.5, in the preparation of 1,l-bu s(dibutylamino)butane,
and 66.5 in the preparation of 2,5-bis(dimorpholino)hexane,

the yield was only 10% in the preparation of 1,5-bis(di-

benzylamino)pentane. It has been shown by von i3aaun, Kahi,
and Goll(27) that the relative firiness of attachment of

hydrocarbon residues to hetrocyclic nitrogen in quaternary
aAmnonium salts increases in the follo':in- order: allyl,
benzyl, methyl, ethyl, propel, etc. These authors also

point out that rethyl groups were lost, in the presence of
primary or secondary amines, from quaternary ammonium salts

of hetrocyclic nitrogen compounds (even piperazine, the
least stable hetrocyclic compound studied) without rupture

of the hetrocyclic ring.

Allyl or benzyl groups are lost in preference to
alkyl groups because of the resona-.ce stabilized ions forced.

The weakness of the carbon-nitrogen bond caused by the

formation of such ions accounts for the allyl migration
shown in this study and for the poor yield of 1,5-bio(di-

benzylamino)pontane. () This would also tend to support
the theory of a carbonium ion(26) as an iitoermdiate in

the disproportionation reaction.

The fact that furfuryl trimethyl ammonium iodide
reacts with piperidine(26) to give a 48% yield of N-fur-

furyl piperidine is evidence that the relative firmness

of attach-eont, as discusseJ by von draun, Ku=n, and

Gloll,(2 of furf-r:-- is less than that of methyl. This

would uynp'-ar quite reasonable since the .'urfuryl group

contains Lhe allylic structure. The fact t"it this

reaction o2oce:ided to :S completion in three hours

duri-i: rrflux at appro-inmitoly 1300, while diallyl pyr-

rolidinirLm b.-oinide, after thirty-six ho rz at 1090, had

shown no sirns of reaction, would indicate that the furfuryl-

nitrocon bond in frrfuryl trimethyl aiiionizuci iodide has a

lesser doaree of attachraent and a greater degree of ionic

character than the allyl-nitrogcn bond in diallyl pyrroli-

dinium bromide. This view is also supported by the fact

that the j.li'uryl carbonium ion has a greater number of

stoailir-in; resonance structures than the allyl carbonium


H Wsr

r-t 3 0e r- SS 9
fr r 0 *

H00 HI4
+)4. r4 43 f
I C-4 CA











H 0 40




at S





e ,o 00

E-4 E-




0 0
o o
C 0

0 0

0 0
0 0

0 0
r-H H
o 0


0 0
-O O-

> o
i- r

0 a

A, (X
(8 r

1A C i.
*rl * * *
CO l^ s0 0m '0 "-

r0 r1 1 F4

0 V\ r~\4
f-i '"\ co-

a *
0 0

%-4 CC ) CO
4A 3 -
*** I


-4 H H -4

H 60 6,-I o i
0 * I
4 0 c0 Co

0- C'- C'- i

r a H
0 Hr- H HD q

o %4 (s F, C
fr I r-I -I ,-I <

S- 1 4 Ccd
$ *0 C 4 o
u 43 -1 03 Q


) leP 0r 0 0r
E-4 H H-4 H

B o E e *
c a '

',o C
0 -0

-4 r- i b s
O H5,4 els cr-4 r-40

? 4 (.30 D ? s
-4 4#$ 0 +O 4
*. 0 ra

C'T0 Cd O

H E-0 0 e
0 -s.0 I4~C u.L;, su 0
U 4-CU~r 4.)'r4 ~ d -G~t*
02 0I 2
~E4 -( r


The bis-quaternary ammonium salts prepared in this

work were made by adding the appropriate halide to the

unsaturated tertiary diamine dissolved in acetone or aceto-

phonone. In the preparation of the hexallyl derivatives,

two moles of allyl bromide were added per mole of diamine.

In the preparation of the tetraallyldimethyl derivatives,

dry gaseous methyl bromide was added in an excess which was

collected in a cold trap.

All of the hexaallyl derivatives were formed quite

readily by gentle heating on a steam bath. The tetra-

allyldimethyl derivatives were prepared at the temperature

of an ice bath, using a magnetic stirrer and allowing the

excess methyl bromide to escape into a cold trap while

the mixture remained at room temperature ovornirht.

In most cases the salts obtained were extremely

hygroscopic and extreme care had to be taken in the puri-

fication of these compounds. In all cases the product

from the reaction mixture was quickly filtered and then

washed with cold dry acetone and dry eth-r several times.

The salt was then quickly placed in a vacuum desiccator

and allowed to remain at room temperature at less than

05 mm. from six hours to one week. The salts were then

recrystallizod from hot acetone with addition of absolute


ethanol until solution occurred. Only in some cases could

absolute ethanol or higher alcohols be used for recrystal-

lization, since this usually resulted in a solution from

which a crystalline product could not again be precipitated.

Totraallyldimethylmeth ethylene diammonium dibromide, which

was extremely hygroscopic, was the only salt which could

not be recrystallized.

The salts usually melted over a one or two degree

rcice and in sone cases decomposed slightly.

A. Preparation of tho Hexaallyl -Derivatives

1. Hexaallyletyllonediammoniumr dibromide
+Br- +Br-
(CiHi=C HCIIa)3 aE(H) a(CHaCI=CHa))a

Sixty and five-tcnths grarns (0.5 M) of allyl bromide
was added to a stirred solution of 50 g. (0.227 M) of tetra-

allylethylene diamine dissolved in 100 ml. of acetone, This

mixture was allowed to heat rently on a steam bath for five

and a half hours. The product was then quickly filtered,

washed with cold acetone and dry ether and placed in a
vacuum desiccator. Seventy-six grams (72.83 yield) of

white crystalline product was obtained i.hich melted at

1119-500 after recrystallization. The product was previously

reported(28) as melting at 147-8*.

2a iexaallyltrimethylenediamnonium dibromide
Br- Br"
(Ca=C HCHa ) l' (CHsa)a :(C HCIi=C )

The same ge:seral procedure was followed; eirht
and eirht-tenths grains (0.0724 M) of allyl bromide was
added to 8.5 g. (0.0362 M) of tetraallyltrimethylene
diamine dissolved in 20 ml. of acetophenone. The raixtu-e
was allowed to heat gently on a steam bath for one-half
hour. Fifteen end eighty-five hundrodtis gra-s (91.7%
yield) of product melting at 185-6* (with slight decom-
position) was obtained. The product was previously
reported(28) as melting at 185-7* (with decomposition).

3. iexaallyltetramethylenediaramonium dibromide
+Br- +,Br-
(CH32=CHICIa) ai (CHeB),4 (C(Ai=CiiC ls)a8

Usini the sane general proce-ure, 14.5 g. (0.12 M)
of allyl bromide was added to 15 g. (0.06 M) of tetra-
allyltetramethyleno diamine dissolved in 30 ml. of aceto-
phonone. The mixture was allowed to heat for one hour.
Twenty-seven grins (91*7, yield) of product melting at

130-41* was obtained. This was recrystallized from acetone,
ethanol, and ethyl acetate mixture. The product meltoL at

168-70*. Analysis calculated for C2He38iiHaira Br, 32.59%.
Found: Br, 31.70, 31.7h%.

4. ilexaallylpentamethylonediammonium dibromide
+B" .+Br

Usili the same general procedure, 13.5 g. (O.154 li)
of allyl bromido was added to 20.0 ,. (0.076 '-) of tetra-
allylpon:tanothylene diamino dissolved in 25 ml. of acetone.
IIeatin,' was continued for fifteen minutes and after the
resulting viscous liquid crystallized, 35.5 g. (92.2,: yield)
of product melting at 153-5@ was obtained. Analysis
calculated for C23i140s3rs: Br, 31.695. Found: Br,

31.70, 31.75,.

5. ioxaallylhexamethylenedia: morniLun dibroinide
3r" Br-
+ +
(CIHa=CIICH) aN (CI)CC.) iOCI!=CHa) a

The product used in this work was some of that
preporod by Angelo(28) in previous work. The compound was

made by addi;~g 28.2 g. (0,23 M) of allyl bronide to a
solution of 27.6 g. (0.1 2) of tetranllylhoxariothylene
diarLiAc and 25 ml. of acetophenone. Forty-seven and three-
tontlhs (rc.os (91.5 yield) of product melting at 179-800
(with sli-:ht decomposition) vcs obtaliod. Analysis
calculated for Cai, 2at2r:. Br, 30.83". Found: Br,


6. Hexaallylheptamethylenediarmmonium dibromide
+Br" +r"
(Ciia=CCi:e)aW (Ca)7 H(Cial.=Ciia2 )

Using the same general procedure, 25.4 g. (0.21 M)
of allyl bromide was added to 30.0 g. (0.10l4 4) of tetra-
allylhoptamothylene diamine dissolved in 60 ml. of acetone.
The mixture was heated for ten to fifteen minutes. rorty-
threo gri:s (77.81 yield) of product meltiia at 192-30
(with slight decomposition) was obtained. Analysis cal-
culated for C2a,141B3ra: ITr, 30.02%. Found: Br, 29.94,


7. He=nallyloctamnethylenediammonium dibromide
+3r" +Br"
(CH,=CHCHa)a i. (CliS) N(Cli LCH=CH)am

Usinr the same Coneral procedure, 16,5 g. (0.136 M)
of allyl bromide was added to 20.0 g. (0.068 4) of tetra-
allyloctamethylene diamine dissolved in 25 ml. of acetone.
The mixture was heated for ten to fifteen minutes on a
steam bath, whereupon a viscous liquid separated. This
was placed in a refrigerator overnight and 15 g. (40.5'
yield) of product melting at 195-7* (with decomposition)
was obtained. Analysis calculated for C2eH4,NsBri:
Br, 29.214. Found: Br, 28.57, 28.518.

8. ie.xa lylnon:amthylnediar- rionium dibronide
+. +ar-
(CI!=C [iC. )a.iJ( i [i )9:. (CHaC if=ClI )

Usin- the saoe general proce.-ure, 18.2 g. (0.15 N)
of allyl bromide was added to 16 g, (0,05 M) of tetra-
allylnonamethylene diisine dissolved in 40 ml, of aceto-
nhenone. The mixture was heated for fifteen minutes,
Twenty-three and six-tenths grams (8L, yield) of product
meltinr at 201-2o was obtained. Analysis calculated
for C27ii4Sii2Brq: Br, 28.26%. Found: Br, 28.41, 28.52/.

9. ie -aallyldocamenthylcned;omia noniium dibro.iide
+B"r +Br"
(CH=Cic.;)3 ;;a (C),o(CHaCiI=CHa)

Usiri: the same -eneral prc-cedure, 24 '. (0. M)

of allyl bzrondide was rLddod to 30 g. (0. 09 I) of tetra-
allyldecanIothylone diamino dissolved in 50 ml. of aceto-
phenone. The mixture was heated for thirty minutes. Forty-
three rre-is (83' yield) of crudo product was obtaiiLed. This
was recr'ystallized fror. n-anmy alcohol. With the bath
previously- heated to 180o, the product melts at 185-6
(with decomposition). Analysis calculated for Cgaoliiao:Bra:

Br, 27.'d2. Found: Br, 27.76, 27.71.

B. Preparation of tho DLmetlhyltetraallyl Derivativos

1. Dimeiethyltetraallylethylonediammoniuun dibromide
+TBr +Br-

CbT CIe T2

The product used in this work was some of that

prepared by Anigelo'(2 in previous work. To illustrate

the ge.ieral procedure, the preparation will be given.

Dry methyl bromide was allowed to bubble through a gas

inlet tube of capillary size into a mixture of 28 *-.

(0.127 M) of tetraallylethylcnc diamine and 50 ml. of

acetone. The mixture was stirred with a magnetic stirr-er;

cooled by an ice bath; excess C.:aBr vapors were collected

in a cold trap inr-.rsed in a mixture of dry ice and acetone.

Precautions to exclude moisture were tkl:en. The addition

of methyl bromide was discontinued after six hou:s and the

excess CIG3r was allowed to evaporate into the cold trap

as the mixture romalaed at room temperature overnight.

The mixture was filtered, washed with cold acetone and dry

ether, and placed in a vacuum desiccator. Fifty grans

(96.2/ yield) of product iielting at 191-2 (with slight

decomposition) was obtained. Analysis calculated for

CGeH3oNaBra: Br, 38.97%. Found: Br, 38.86".

2. DimethyltetraallyltrLnimthyljnediamEronium dibromide
+i Br'
I(, \ ,,

710 pa cuct used in tills worL u~a prepared(28)

previously Iusi. the above pi'oce'.ure. Thirty-ei;ht gtrt -s

(89.*6; yiold) of product nmoltin- at 1.,9-11 (closed
capillary) un; obtalioed. !LilyciZs calculLt-jd for

C, 7nI3a...-rs: -r, 37.67,. .ouid: 3r, 37.63, 37.924.

3. DiLiethyltetraallyltetra)iethiyl-onelae -.onium dibromide
+J3r- +-r"
(CHesC:Cne) :(CHe)s"(CHC.-c=Ce:=),

*.sii.: t::c sa:'o general procedJre, rnothyl bromide
was L-ced to 16 g. (0.064 I) of totr-aallyltetral-ethyl-ne

diamino disXsolved in 1C00 ml. o- acetone. Twenty-four

grc- .. (38,' yicld) of p: :duct m3tti-. at 163-5 (with

deco: iorition) was c-btcil.d. Analysis calculated for

Ce i'4-i'-. 2: -2, 36.47- I:''-d 1Lx, 36.' 5, 36.36L .

4. Dirie thy:ltetraallylpoe:- ta.nethylond lammoniumi dibrormide
+Dr- +.r

Usin the c-ar. general procedure, methyl bromide
:as added to 20 g. (0.0763 ;I) of totraallylpentamethylone

diamine dissolved in 100 ml. of acetone. Thirty grar-s

(87.3 yield) of product melting at 133-5* was obtain-d.
Analysis: calculated for C9,sineil~Bra: rr, 35.2 Found:

Br, 35.36, 35.26,.

5. Dimnethyltetraalllylhixajmerthyl lned irr.ron-iu dibromide
+Br" +Br

The product used in this work was prepared(26)

previously usii:V thle samer procedure. Porty-ai.-Iht iram'-.
(quantitative yield) of prod-ict meltinr at 202-3 (with
decomposition) was obtained. Analysi- calculated for

CeoliaNa3Bre: Br, 3h.28-. Pound: Br, 3U.284

6. Dimothyltetraallylhepta--.ethll;-nedi i Lr.o:luru dib. oride

+(H= +jr"
(CH=C):(CH (HgC;=C

'-sin~ the so- r.-" .rcl ?;ace auzro, r"ot.1rl brol..o.ide
was dc'3i1 to 20 C. (0.069 ) o tetaallylhpt.othy
diamni- dsloled in 100 nl. of aceto so. -'t,:;ty-el ht
a.;:i five-tonths gcrp's (86.2- yi-1d) of pr-od-uct .elting

at 193-"., (with docomposition) was obtained. Analysis
calculated for Csj1olaS13r2a 3r, 33.27%. Found: Br,

33.36, 33.32 .

7, Dimethyltetraallyloctamethylenediammonium dibromide
+Br- +Br"
(CHC; -:=C;i ) ( CHa ) (CH, C i=Ci )

Usiin the somc general procedure, methyl bromide
was added to 20 g. (0.068 M) of tetraallyloctamethylone
diamine dissolved in 100 ml. of acetone. Nineteen and
sevon-tonths grcas (58.7% yield) of product melting at

178-80* was obtained. Analysis calculated for Ci-4aisaBrs2
Br, 32.33,. Found: Br, 32.37, 32.4L0..

8. Dime thylt etraallylnonamethyloned iemmonium dibromide
+Br" +Br"
(CH=iCtlCla) (CHa)9 (CHCCHCH)
-sing the same general procedure, methyl bromide
was added to 22 g. (0.069 M) of tetraallylnonamethylene
diamine dissolved in 100 ml. of acetone. Twenty-oight
grams (80% yield) of product melting at 187-90 (with
decomposition) was obtai;ind. Analysis c-lculvtod for

C3aHa441:Brs: Br, 31,45. FomLd: 3r, 31.23, 31.25!.

9. Dimothyltetraallyldecanothylenedianmmonium dibromide
+Br" +3r"
(CII,=C;lC, [,)21(CHia) o'(CGHC:i=CHa1)a

s13 C1a3
*sinr the same general procedure, methyl bromide
was added to 16 g. (0.06[15 M) of tetraallyldecamethylene

diamine dissolved in 100 ml. of acetone. Twenty-four grams
(8.% yield) of product melting at 163-50 (with decomposition)
was obtained. Analysis calculated for C,2li4il4Brs:a Br,
30*59. Fo-unid: Br, 30.61, 30. .

r CO ,- Cr- N IUA CO lA1 0 O
0 * * * 0 *
N r-I H r-N H 0 -:r (n
( E- 01c- c 0 o t'- -,t o co

1 t 0 1^1A C- r0 co Nc i 0 _:t
aa C- I a% *o\ v tr\ _t i\ a- F--
o ar< 8 8 I * a* * * * *
S0 I rI 1 r- 0 0. Co cO C:O --
.n n (n ( n f r\m\ c j ) (v m cm CU C\j
H H~
4 S

0% f N 4 1 0 N
S I \D CoO N Ns co
a r P * * *
S I I rN r c 0 C0

S0 I I- tM N N- N
* -
P3 0 N

0 0 0 0
O O O C0
H U'1 0 C,- nIl o r C 4 F.

S r- r- r-I H t r rH r-' C

Q 41 0 at 0 ca
a M
O a 0 In 0 00 C

0 0 gto V t 0 0
So df o e o t- e

0 0 0 0 0 0 0 0

o r-0 0 r-0 0 0 0 k
ca 3 0s r-I H 0T CT w o
E-4 r-I ,- P,
4o l 0 0 0- c 0
4) 04

S40rt 4z c 0 0 r 0

c -P 0 0 0 Q 00
B S r-i H i A Hs .

0 H H 0 H 0 0 H
o4 .> o 0 SI 0 g

0 00 0 Cd 0 0
r-1 H H H H H4 H "

O- It r- r -l (- I il

N ( o 0 on C N E- 0 0
o0 0% 0 cO 0 V\o
w 0 0 CO CO cO c 0 Co co

to-- :1 Bo r'oN ms sUO Co CC 0 r-o, No m -0
01> %0 0 0 (n C-\ f (MN N e i-; j NC\j 10 -t
H G2 ** * * *9* ** 9 * *
E-40 P- CO c -t' -0- ,.O,0 1A \ -I tn C N H -I-! 00

f- *


- 0 0 0 0
odo i r4 r c3 0 0
(r n cF"-nco C- m CH

C% ao 3 C0 A o t v (D 0

#-4 0 r ri Hr t
* * *I I
S0 0 P 0 0 0

0 C.

0 o a C c 1 0 H
o 0 0 0 0
H E 0 0 e 0 O o i

H HaH ct H H

0 40
Q m f -4l 4q 4-I r 4 =;
;Hi a I H a 0 eI


P-H rl r0-i |A z H-i 0- A r-i H0 r-l I

W' 0 H H H Hd (D rH C cH H H0H
ro oo fr fr or o oo

2cs 0 0 H 0 0

4) 0 (0D 04c 0 0 00 0 0 00


00 00 00 00 00


A, General Jiscussion of Method

In an attempt to prepare the rosins in a rather uni-

form size ond shape, and to allow for dissipation of the

heat of reaction which could causo decomposition of the

quaternary ammonium derivatives, the suspension polymeri-

zation technique was a-ployed.

Using this method a number of difficulties are

encountoered. Constant high speed stirring must be main-

tained; the proper shape stirrer must be employed a:d the

proper carrier solvent must be used. An attempt to solve

these difficulties was tradee by carrying out various sus-

pension polymerizations usi-in tetraallyl ammonium bromide

as the mononer.

The stirring problem was finally resolved in the

folloriri, manner: A Palo Myers' motor, controlled by a

variable voltage rer-ulator, was employed at very high

stirri-IG rates. The voltage setti-ng for the high speed

varied froia 45 to 60 volts. This was due to slight

differences in the binding of the stirring sleeve. After

experimonting with various stirring sleeves, a heavy-

walled piece of glass tubing inserted in a rubber stopper

was used. This compensated for slight vibrations at very



high speeds. The stirrer was made of -lass and was shaped

like a cork screw. The stirrer and stirrer sle:ve were

fitted as tightly as possible. Any initial binding was

compensated for by allowing the stirring device to proceed

at high speeds, usi-g- graphite and niA- ral oil as lubricants.

This was done previous to each experirLent and resulted in

more uniform stirring. The stirring sleeve and the stirrer

wore excessively and had to be replaced quite often.

Further, this wear caused the deposition of a fine lass

powder in the reaction flask.

The most difficult phase encountered in trying to

obtain uniform bead particles was the sticky period, which

caused merging of individual dispersed particles into


Hohenstein and Mark(29) indicate that polymerization

in a heterogeneous suspension in which the monomer is

mechanically dispersed in a liquid not a solvent for it

or for any species of polymer molecules, and in which the

initiator is soluble in the monomer or monomer phase,

results in a polymer bead or pearl. In such cases the

polyr;erization takes place in each monomer- lobule and

converts it gradually into a polymer bead or pearl; the

liquid plays only the role of a carrier, which favors

heat transfer and aritation, but does not interfere with

the reaction.

However, after a period of tire, the globules, which

now represent a rather concentrated solution of polymer in

monomer, become 1usmmy and upon mutual contact in the s:et.am

stick together and form agClomerations which cannot easily

be broker up into individual lobules of the original size

or shnpe. It frequently happens t:-i t upon continued stir-

ring the ar-lonerations do not disintegrate, but coalesce

into laroe:r units. 'Te authors(29) describe several ways

of brin.ii.gL the system over the sticky period without

mergi ,- of the individual particles:

(1) Suspension stabilizers can be used that can

cover the s'.rfaces of the -lobule with thin layo s of

inorrt nic or organic substances which do not interfere

with the rEction, but prevent or diminish tho toredency

of thv globulos to stick together during the gunnmy period.

(2) The intorfacial tension between the carrier

solvent aCnd t'-o mo..onorr phase can be increased by dis-

solvi-r electrolytes in the carrier solvent if it is water

(3) The density of the carrier liquid can be

adjusted to the doesity of the globules during the cgmy

state. In doi-.- so, the tendency of the stick-y Clobules

to accumuleto either on the surface or at the bottom of

the suspeosio:i is removed.

(!I) The viscosity of tho carrier liquid can be

increased and thereby moko it more difficult for the dis-

persed globules to collide vigorously enot h to mere.

In this respect, many experiments wlore car'rice

out with tetrEallyl arimonrlimn bromide as the noiromcr;

the p:'cedi.43 su-.rcstions were ecnplo.-od until the bost

conditions wer found. Durin.- these e:oerimrints stabili-

zers 3such as bentonite and talc were used; carrier solvents

s ch as ethyl benzeae, chlorobenzene and toluone wore used;

increased viscosity of tihe carrier liquid was investigated

- various additions of mineral oil; since the cnrrilor

liquid in this particular poly-jrrization was not water,

adjustment of the interfocial tension by the addition of

electrolytes was not employed.

The best conditions for carryi;: out this particu-

lar polymerization were as follcw;i: A stirring rate ad-

justed to l0-60 volts as indicated previously, a tempera-

tuie level of 600, a carrier solvent co.nsistinr, of 150 ml.

of mineral oil anrd 50 ml. of ethyl boa.zone, a modiomer

phase consisti-irn of a half a milliliter of water per Lrar

of quaternary salt, and an initiator co-:centration of two

drops (approximatel- 0.012 g./drop) of 6G~ t-butylh: dro-

peroxide solution per gram of quaternary salt. In all

cnses, using totraallyl aimioniuTr bromide as the rLonoi;mer,

90-1lC.- yield of i-solub.-li resin was obtained. However,

in no case were any wAll-shaped boads forced. The product

approached a spherical sliape, but had much random shape dis-

tribution. Iuch of the size distribution of the particles

obtained was in the desired 15-60 mesh region.

The stirri-g at 600 was continued for forty-eight

hours after which the product was filtered and washed

succeesively w-ith heptrne, acotor.e, L 1cohol and other,

The p-.oduct was then so:':old for apprlo:-iately one hour

in hot hontan~ and thon filtered and washed as before.

The product was thon dried for two;ity-four hours in an

oven at 60o. This proccdu:s i.isured the removal of the

film of nincr.al oil* At this time the swolli,,-- cooeficient

of the rczin was dot;e i:ned. The ratio of the wet bromide

volume to the dry bromide volume of the rosin is the

swellinii: coefficient. It was zaeasur-ed by allowing the

dry broriid foio of the ro ain to settle in a r,-aduated

cylinder and detormini--,t the volume. The wet volume was

deterlaiied by allowing the stne rosin sriplo to soak in

distilled water until no further chaae in volume vas


This ,-eneral p:.ocedlure was applied to the polymeri-

zation of the quaate:.nary derivatives of the diamiAiles des-

critod previo, sly. In al. cas2s, except for te: he::aallyl-

d .ec ethylenene end the diI.athyltotruallylhe:mr.ethylene

di-crnmonliuri dibro.rde derivatives, tLe. rocin product vWs

not perfectly bhad sI-ool. In :ost cases t'ip p.-oduct was

of rmido:n slhpo, but usually in the desired 1"-6' nosh

reG' ioe. o. risi-i particles of t:.iso two dc:-ivatives

ijore perfectly bead shaped; only the docamethylone

derivative retai.ied its board shapo th.roivhoat all operations,

such as washi:lg, exchanCg or recycll.i

The poly..er-ization of th.; quatcrnary derivatives

of txo pot Iotlylm-e an'. oct.:intLhylone dcrivativos dif-

fered fro:. the -enoral prccadure describcd abcvo. T>ese

pol7~oriPizatio.js wore carried out in the bulT prise ;sriSg

t'.e sac.ie mo:ionecr, initiator c.d uater ratio, 'ile resulting

resi.is were ground to the desired 15-60 raesh size alid

treated s:-nilarly.

B. Ti!perirm.ntal liesults

The following table gives a sur.m.iary of the results

of the polymerization of the quaternary derivatives of the

preceding diamiines. It is believed that any yield over

10e0 is caused by glass particles deposited from the

stirring mechanism. In this section the resins will be

given the following notation: CaH = polymer of hexa-

allylothylenediammoniur dibromide, CUDT = polymer of

dimethyltetraallylethylene disamonium dibroride, etc.

2 L. -.:i V

Total wt. Wt. obt:inod Swell.
asin OLtaLi. ed ( ..) in 15-60 .;e1sh (c.) Yield coeffr
.. -_ ? - -__ l~ l- ] l l l l l ll l I. . ,, .... !,, l - -







































- II "---- I~


A, Method of Analysis

The method of determiininC the capacities of the

resins in this investigation was essentially a titration

procedure similar to a neutralization titration of a

strong base and a strong acid, A known quantity of the

poly-quaternary ammonium bromide form of a resin was

quantitatively converted to the poly-quaternary ammonium

hydroxide form of the resin. An excess (compared to the

theoretical number of milliequivalents of poly-quaternary

ammonium bromide) of a salt of a strong mineral acid was

added to the poly-quaternary ammonium hydroxide. An ex-

change took place and hydroxyl ions were released into

solution. Suitable titration of the hydroxyl ion content

by a strong mineral acid then determined the exchange

capacity of the resin in terms of milliequivalents of

hydroxyl ion exchanged per gram of dry bromide form of


This method is essentially that described by

Butler and Bunch, (1) and Butler and Ingloy,(2) in which

the actual titration was carried out using a Beckman pH

meter, adding 1.0 ml. increments of standard acid at

3.0 minute intervals and measuring the pH of the solution


at the end of each three minute interval. This routine

was continued until the titration was complete. The pH

was plotted against milliliters of acid added and the

capacity was obtained from the amount of acid required to

cause a sharp break in the curve. However, the capacity

of the resin measured by this method never approached the

theoretical capacity of the resin, and the break in the

titration curve usually showed a shoulder which was

interpreted at the time as amine capacity. (3)
Ilusa(6) developed an "equilibrium" titration

method for detenrining the capacity of this type of anion

exchan-o resin. His method consisted of preparing equal

samples of resin in the bromide form, quantitatively con-

vorting each sample to the hydroxide form, and adding

various known quantities of standard KBr solution and HBr

solution. The pH of each sample was measured initially

and at various intervals, extending to 420 hours in some

cases. A plot of pH versus milliliters of standard HBr

originally present gave a titration curve which appeared

very similar to a standard acid-base titration and from

which a relatively accurate determination of capacity could

be obtained. The advantage of this type of titration is

that the measured capacity is the capacity attainable after

the system has reached equilibrium. The disadvantage of

this method is the prolonged period of time involved and

the number of samples measured.

The equilibrium capacities, measured by Husa, (6)
often approached the theoretical values and were much
higher than the values determined by the rapid titration

method. Differences in equilibrium time, pH of solution,

and ionic strength were suggested as factors causing

variation of the results given by the rapid method and
the equilibrium method. The equilibrium titration

curves showed no amine capacity, as was suggested pre-
viously, but gave a smooth curve with a sharp break.

As an illustration, the equilibrium titration curve for

the resin of hexaallyldecamethylene diansnoiium dibromide

follows, This curve appears by the courtesy of W. J.
Husa(31) from his Ph.D. Dissertation, University of

Florida, 1953, P. 82.

The following procedure was used to determine the

capacity of the bis-quaternary ammonium resins obtained

in this work. A weighed quantity of resin (approximately

0.2000 g.) was placed in a sintered glass filteriig funnel

(medium). The funnel was stoppered and the resin soaked
in ten milliliters of 14 UaOl solution; the resin sample

was filtered, washed and soaked every day for 10-12 days.

After this time, the turbidity test for bromide ion,

precipitated as silver bromide, was less than ten parts

per million. The resin was then washed free of any

hydroxyl ion by using distilled water and checking the

filtrate with phenolphthaleini



r r-< I *


S0 6y
''^i f-: l -

3 I

0 -C
r- _^ r1

.'o "' 0-
F: t

0 '-C

in 0- =

< ,. C

0 C

s- C-; i-
;\ --f **
i. r t -

c, I'.
W U(
^ ^^

fal ri
^ *f-l
W 4i


The resin was placed in a 250 m2l. beaker with 75 ml.

of distilled water. To this mixture was added 50 ml. of

0.20 i KBr solution (ten milliequivalents of bromide ion).

After standing for five minutes, the mixture was titrated

with 0.0195 1N HDr solution by using a Beckman Model K

automatic titrator. The endpoint was set at pH 7 by

adjustment with a standard buffer solution, and the

anticipation rate was set at 7. 'he first 15-20 ml of

standard acid was titrated rapidly, but thereafter the

titration proceeded rather slowly until the end of the

allotted one hour period. There was still so.o exchange

takii-,q place at the end of one hoi.r, as was observed when

somie samples were allowed to titrate further. This type

of asymptotic approach to complete neutralization was to be

expected from tho data of (usa.3

The theoretical number of rilliequivalants was

calculated for each resin based on monomer units. The

actual number of milliequivalents exchsaned per hour was

calculated and was expressed as the fraction of theoretical

exchange per hour.

B. Summary of Experimental Results
of Capacity Determinations

The capacity determinations of the bis-quaternary

ammonium resins were carried out in the manner described.

A summary of the data obtained follows in Table VI. In

this table thie zoAosll.-s are -ivan th-o same notation as before,

whero 0C21= res1n of hoxaa.llyletbAyar3 nndia monium dibromide,

CaDT = resin of

dibronide, atc.





I o




.0 CO CO C ooz CO
0 O0 N00 0o
oo L- E- sO 0
'.o c- co a'. r o IA '.0
* * * * *
0 0 0 0 0 0 0 0

'\ U\ r- O' 0 lC- 'O t

* * * 9 *

o, H,- H rn 0 1UN 0 0
0 0 0 0 0 0 0 0
c rt O \0

0 C O NO c CO (D 0-

o Noo oD -
('n ^ r< r, r`- CND(l

0 00 0 0 0 0
* * * *

o N c H m -- 0
o H (O H C'- !\- 0
0 0 0 0 0 0 0 0

o c ; 0* 0 < 0

L tS- co o01 - C
-r A -O t '0 C"j t-
* 0 0 0 9 9 0 *

S 0 4 U 0 a E- E-

I0 o (n
O H or
* *

I\CO (co

* *


0 0 0

c Cm C\J

cr- r-
* *

0 4\ .O
m 0 0
* 9

* *



"qa 0 0
,, N O NO ,0 ,O t.
S 0 0 0 0 0 0 0

COm r- O3% 0 H
rit rH r- -H 4 H %3
O rI A' t\ IAJ U\ -.;
0 0C 0 000 0

r: H N o ( N c


: H O NC CO O E r- C-
S E * * *
CT C 0 0 c 0 0 0
MH ! al N W cM cN cuN

H 0 -4- \I.C 0 r-f r 0% 0 X
6 p o o 00 o o o
-C0 0 0 0 0 0 0

*I r* * *

09 0 9 0 6
-a .ti s < -^ r.. l? cy 0, 0 0

I N H H- r-I H


0 0 0 0 0 0
0 0 0 0 0 0 0

C, Discussion of Capacity Determinations

The type of rapid titration determination which was

carried out in this work proved to be quite adequate. The

time and number of samples were kept at a minimum. The

Beckman Iodel K automatic titrator proved to be satisfac-

tory in measuring the fraction of theoretical exchange per

hour. It is believed that suitable experimental techniques

could be developed, involving the automatic titrator, to

differentiate between the initial stage of exchange,

apparently due predominately to a mass action effect, and

a latter equilibrium stage of exchange, apparently due to a

diffusion rate factor. It is conceivable that relative

diffusion rates of various ions could be determined and

differentiated from total exchange rates, which were

probably measured in this work.

It is believed that an equal milliequivalent basis

would be more reliable than an equal weight basis of com-

parison of the resin exchange rates. In the previous

determinations it should be noted that the theoretical

number of milliequivalents of the resins ranged from

0.707 to 0.977. However, the adequate excess of initial
bromide ion should compensate for differences in mass action

effect due to the unequal unit milliequivalent basis; the

initial quantity of bromide ion consisted of 10.0 milliequi-


The most interesting effect, as seen from the

exchange capacity data, is the definite indication of a

maximum exchange per unit time of the pentarnethylene

derivatives. This effect is shown in Figures 2 and 3.

It could be merely a coincidental factor dependent upon

some non-uniform polymerization technique. Although every

polymerization was carried out as uniformly as possible,

there were, in many cases, noticeable differences in the

induction period, the globule size during the polymeri-

zation, and the final particle size and shape. However,

the effect of maximum exchange of the pentamethylene

derivatives is a factor that could be considered from the

basis of differences in the unit structure of the polymer.

A suggestion as to the uniqueness of the struc-

tural configuration of the pentamethylene derivatives is

the possibility that uniform linear chain growth through

the allyl double bond would result in a polymer with five

carbon atoms between each exchange center. This type of

linear growth would cause only the pontamethylene deriva-

tives to have equal numbers of carbon atoms between suc-

cessive nitrogen atoms. This is illustrated in the

following scheme:

Fir'-urc 2


~ 9

0. 8




6 7 8 9 10

Figure 3

2 3 4 5 6 7 8 9 10
Number of Carbon Atoms in Methylene Chain

2 3 4 5

Hexaallyl Derivatives

0O 0





= i f i

Ra Ra
\+ +/ "n
CH,=CHCH2I- (CH) 6-1a-C 1,CH"=C H C+Z*
Initiation with free radical Z-

\+ + H H
CH9=C;C: .i(C;i a)5l-CIIC--C : Z
PropaCation with monomer molecule


Cja=CIC1\1(CHa)e"-C3C-sC-C-CJiaLl-(CH) BGi-CHsCBH=C1a

Ca C4, > C t etc.
Since there has been no definite proof of structure

of these derivatives, this suggestion is to be considered

as a possible course only,

The capacity data of Table VI seems to show no

definite correlation bctwc-n the swelling coefficient

relatedd to the apparent degree of cross-linking) and the

e :chanco capacity of the resins. It was expected that

replacement of one allyl Croup of a quaternary anmonium

derivative by a methyl group should give a resin having

less cross-linking and higher swelling, there being fewer

allyl double bonds available for cross-linking. Conse-
quently, the methyl quaternary resins should have higher

excha.re values if we consider a low degree of cross-linking

to allow easier ion movement in a less tangled network. How-

ever, the data in Table VI does not bear out this contention


and, contrary to expectations, the methyl derivatives have

less exchalce capacity per tuuit time tl.in the correspo-iding

allyl derivatives in practically every case.

There was no expo~imental evidence obtai.Lud to show

a connection between the ex:cr-;go capacity of the recias,

particulac-rly ac rogards their selectivity towards ions of

different size and charge and their respective swelling

coefficients, apparent decrees of cross-linking or

variable distances between quatom ar7 ammonium centers.
However, some work32) is presently being carried out in

this laboratory by L. G. Kulkarni, relative to the possible

selective exchange properties of these resins.

VII 2CLY ..IATIO CiAiI2:: z:,r: .

Previous work(1-5) carried out in this laboratory

pertainiir to the free radical initiated polymerization

of allyl or substituted allyl quaternary ammonium deriva-

tives gave infusible and water-insoluble polymers only

when derived from monomers containing three or more allyl

groups. The product resulting from the attempted polymeri-

zation of a monomer containing one or two allyl groups

either was not polymerized or was assumed to be non-

crossed linked, since it was completely soluble in water.

These results are contrary to the accepted views

that mon omers containing one double bond result in a

linear chain type product possessing some degree of solu-

bility; monomers contahing two or more double bonds result

in a t-Lre:-dimonsio:al, cross-linked product possessing

little or no solubility. Since the products of the polymer-

ization of allyl quaternary ammonium salts have appeared

somei~rint abnormal in their properties, it was decided

to investigate the mechanism of this type of free radical

initiated polymerization.

A piperidine ring structure for.ied by an alter-

natinr intramolecular-intermolocular chain reaction was


oonsider3d as a possibility which coo-ld preve'; cross
linking in the polymerization of q~.,atornary ~umnoni,

derivatives containing only two allyl do-ble boiuds.

Simpson, ::olt and ZCite(33 have indicatC frc.,i the

corrolatio.l of data on ti:e polz:iorlzation of diallyl

phthalate that at the Cel point m.uch fc' the cazrboo"-ca&-bo:;

double bond, suppocosly free to crose link after; tie

Efel point, is tied up as a cylic structure due to intra-
moleculr polynorization.

It umas decided to approach this subject fro,!, the

aspects of suitable stnthetic adaption of mononer struc-

ture, der.radation studies, infrared anal-ses and molecular

weight determinations.

A. Monomer S.itheses

1. Preparation of diethyldiallylarrrionium bromide
+ Br-
(Ca1Gcd) aN(CHci1=CH= ),

Sixty and five-tenths grams (Q.5 M) of allyl

bromide was added to 50.0 g. (0.44 M) of diethylallyl amine

dissolved in 100 ml. of acetone; the diethylallyl amine
had a boiling point of 110 and n 1.4198; Libermann

and Paal 1 report the boiling point as 110-13o. Upon

addition of the bromide, the mixture became cloudy and

crystals began to form. The product was washed and

decanted several tL.ies with cold acetone, filtered and
dried LiL a vacuLiu doeiccUtor. i.A. -hy-seven grans (804.1
yield) of white, hygroscopic crystals, melting at 1550
(closod capillary) we-e obtained. .aecrytallizatlon from
hot acetone and a miLall iam1-nt of absolute etimanol gave
the saXe1 -..eltlI; point.

2. Preparation of triethylallylarmonium bromide
+ Br
( 3C T~ ) z r (CHnC' IC=Cl )
.LiIrty-sis and t:-i.L.-tenths grams (0.3 :) of
allyl ~ibroc i.i was added to 30.0 r. (0.293 I) o' triothyl
aiinc. '2h1 sane -roc-d'-e was followed and 60.5 g.
(92.1"J yield) of uhite hygroscopic crystals was obtai..od.
The product :.ialted at 229-31* (with deccrposition; closed

3. Preparation of 1,1l-bis(diethlylallarrnonium)butene-
2 dibronilde
+Br- +r-
+ +

CIIa=C_'C Ci =C;Iz
The intermediate dianine, 1,4--bis(diethylamino)butene-2,
was prepared in a 31.83 yield by the procedure of Amundsen. (35
One hundred and sovonty-eicht grams of light yellow liquid
boiling at 118*/20 mmr and having an n2'- 1.4573 was ob-

tai.ied. Amu-ndsen reports a boiling point of 115-16/20 mm.
and an nD'. 1.4532. The product rapidly decolorizes when
allowed to remain in a sealed container at room temperature.

Twenty gr'sa (0.10 ") of l,13-bi((diethlamino)
butene-2 dissolved in 50 ml. of acetone ;oas allowed to
react wIth 26.6 c. (0.22 ;7) o-' allyl jromide in the same
manner as bL.JiAro. The cr-ue prn:d:ct waz rocr-ystalliz d
froi hiot acotone aind absolut h o thanol; 26.5 rg (59 ryielrl)
of white, powLeri product .: ltiA, at 185.-6 (uitlh de-
composition) was obta-ioed. Co-t- (36) repc-rt the meltiIg

polnt of this pr-oDct t ;it'out rocyst3allization as 172-3o.

4. Preparation of diallyltetraothyldocanothylenodia~r.oniuni
+Br- +Br-
C:i3Che) a-(Clio) ,oe-'(CICIieH)8

heo intermediate diamine, tetraothyldecanethylone
diamine, was prepared in the sane manner as tetraallyl-
decariethylene diir.ine in Section II. One hundred and
twenty-six gra':s (1.73 M) of diethyl anino in a slurry
of 81: r. (0.5 A) of ..aHICO aeid 50 ml. of water, was
allowed to reflu.: with 52 g. (0.173 ::) of decamethylene
dibromide for ten hours. Thirty-nine gra-!s (79.5$ yield)
of light yollIo liquid boili at 120-Co/0.02-0.0.5 ;.
and having an nD'- 1.4493 was obtained. Analysis cal-
culated for COa84o:0: C, 76.2,; :~ 14l..1; N, 9 .86.
Found: C, 75.97*; H, 14.Gb8; ;, 9.,2-.
Fifteen Grams (0.053 M) of tetraethyldecamiethylane
diamine, dissolved in 50 ml. of acetone, was allowed to

react t:thi 13.3 g. (0.11 ) of nlll ..ro-idc. After being
treato... i tLho U ai- i.rL.1 as Lioore, 17.0 g. (61.2

i-eld) of ::2le, vor, y-'ocopic salt minl.tlC. at 2$-70
(,it, dico.:.position; cluodu capilla.y) was obtai.icd.

5. Attempted preparation of quaternary salts of 4-diethyl-
zLihi.oj c..-t,.i s-1

The intermediate amine, 4-diethylaminobutene-1,

was prepared by roflu:din for ei-hteon hours a mixture of

190 r. (2.6 M) of diethyl amino, 84 g. (0.9 M) of NJa;;CO,

50 ml. of watei and 30.0 g. (0.33 H) of 14-chlorobuteno-1.
(The l-chlorobutene-l was rcdistilled and the portion

boiling at 75.0-75.5* anid having ann nu 1.4238 was used;
Juvala reports the boiling point as 75.0* and the
nD as 1.*233). Aftar separation and purification, 15.L g.
(36.6.J yiold) of clear liquid boilinL at 134-5* and having
an nD 1.4250 was obtained. An infrared spectrum indi-

cated the characteristic terminal double bond absorption
ihilch was deslled in this preparation.

Attempts to prepare quaternary ammonium derivatives

of 4-diethylaminobutenel- did not prove very successful.
Only in the case of the allyl quaternary was a crystalline
product obtaoi.ed. The reaction of equlmolar portions of

allyl bromide and 4-dlothylaminobutcue-1 dissolved in

acetone, gave a white, hygroscopic product which melted at
208-100 (with decomposition).
The reaction of equimolar portions of 5-bromo-
pentene-I and 4-diethylaminobutone-1 dissolved in acetone

gave an oil, which, after many recrystallization attempts,
gave a very hygroscopic semi-solid. This semi-solid was
obtained by careful washing, decanting with cold acetone
and allowing the residue to remain in a vacuum desiccator
at leas than one millimeter for several days.
The mixtures of 4-chlorobutene-l or 6-bromohexene-l
with equimolar portions of 4-diethylaminobutene-1 dissolved
in acetone showed no signs of reaction after gentle heating
and after remaining at room temperature for six months.

6. Attempted preparation of quaternary salts of 1-
di(pentene-4)amino butane
+ X"
(CHp=CIICHC,;mGCilgC) al' C IC aCHaClla

The intermediate amine, l-di(pentene-l)amnno butane,
was prepared by refluxing for three days a mixture of 21.9 g.

(0.30 M) of n-butyl amine, 87.0 g. (0,7 M) of iHaCO3*HO,
100 ml. of water ard 100 g. (0.67 1) of l-bromopentene-4
(b.p.-53-4L*/51-2 mm. and nD 1.4636; Juvala37) reports

the b.p. as 56*/75 mm.). After separation and purification,

41.5 go (66.2% yield) of light yellow liquid boiling at
228-37 was obtained. This was redlstilled and a light
yellow liquid boiling at 114-160/9-4 rm. and having

an nD 1.4525 was obtained. An infrared spectrum gave the
characteristic terminal double bond absorption desired in
this preparation. Analysis calculated for C,4HaTNI
C, 80.3,; H, 13.9j 1N, 6.7,. Found: C, 80.41 ; H,
12.60,; N, 6.73/.
All attempts to prepare crystalline derivatives
of l-di(pentone-h)amino butane were unsuccessful. The
amino was reacted with methyl bromide, methyl iodide,
allyl bromide, benzyl chloride, hydrogen chloride and
hydroron bromide in various solvents, but no crystalline
product was obtained.

7. Attempted preparation of quaternary salts of
1-di(hexene-5)amino butane
(CH,-=C..C IsCiCI4 ) 81 (CiC8i iCiIl )
The 1-bromohexene-5, used to prepare the inter-
mediate amine, was made by treating at 0-3* a dry pyridine
solution of 5-hexene-l-ol with phosphorous tribromide.
Seventy-two and one-tonth grams (Qi4.2- yield) of 1-bromo-
hexeno-5 boiling at 78-800/61 rm. and hEvvi~ an na~- 1.4676
was obtained. Price(38) reports the boiling point as

75-80/61-2 mri. and the na as 1.4620.
The intermediate amine, l-di(hexene-5)amino
butane, was prepared in the same manner as before.
Fourteen and five-tenths grams (0.20 M) of n-butyl amine,

82.5 g. (O.0o M) of K4GOa1 1/2(H0o), 2.o g. of copper
powder, 100 ml. of water and 70.1 g. (0.43 M) of 1-bromo-
hexene-5 were refluxed for three days. After separation
and purification, 29 g. (61.1 ; yield) of a light yellow

liquid boiling at 175-840/64 mm. and having an nD 1.h51:6
was obtained. An infrared spectrum gave the characteristic
terminal double bond absorption desired in this prepara+i? f .
Analysis calculated for C,8Hsi3,,: C, 80.93"; H, 13.17;'

N, 5.90. Found: C, 80.41W; iH, 12.8r. ; N, 5.98:.
All attempts to prepare crystalline derivatives

of l-di(hexene-5)amino butane were unsuccessful. The amine
was reacted with methyl bromide, methyl iodide, allyl
bromide, benzyl chloride, hydrogen chloride, and hydror-en
bromide in various solvents, but no crystalline product
was obtained.

B. Polymerization Products and Results

In an attempt to explain the water soluble property
(apparent lack of c:oss-linking) of resins obtained from
the polymerization of quaternary ammonium derivatives con-
taining two allyl groups, an alternating intramolecular-
intermolecular chain reaction forming a piperidine ring

structure, which could cause a non-cross linked type of
chain growth, was proposed. The following scheme il-
lustrates the possible mechanism. (Z'= initiator, R

saturated group).

+ sCIIa=Cilh
(1) Z-+ fH1
-7,C -=C]1 =

(2) 1II


+ Cli C-C-Z
(3) R2l

R/ \p"
Rp Ili



+ CHaC-0-Z

H 2


lar Growth

+i IiaCH=Ci

CaC Bgl

lar Growth

C112=C *-. I


(tI) 1n2i(


etc. 4

As a possible approach to the structure of those

poly-allylquaternary ammonium derivatives, a study of the

reactions of suitable monomors and the degradation of the

polymers was attempted.

1I Degradation of poly-tetraallylammonium bromide

A decomposition of the poly-quaternary ammonium

hydroxide, leading to simpler products which could be

identified and possibly associated with a ring type struc-

ture, was carried out. Since a quantity of poly-tetraallyl

amn-onium bromide was on hand from the previous suspension

polymerization trials, this product was converted to the

hydroxide form and degraded,

Seventy-eight grams of poly-totraallyl ammonium

bromide was soaked in 250 ml. of 1' 1aOH solution, filtered,

and washed with distilled water. This process was carried

out once a day for 28 da-s until the test for bromide ion

was less than 10 parts per million. The product was

washed free of hydroxyl ions and filtered as dry as

possible before it was paced in a vacuum desiccator. The

product remained in the vacuum desiccator at a pressure

less than 1 mm. until it reached a constant weight. This

took one day and the product weighed 62.5 g.; the calcu-

lated weight of hydroxide form should be 60.2 g. from the

initial 78 go of bromide formn

The converted product was placed in a distilling

pot connected to a receiver immersed in a Dewar flask

containin:1 Dry Ice and acetone, A second trap cooled in

a similar manner was connected in series. The product was

heated at 300-500 for four hours while e the pressure was

maintaieod at 10 nm. Tho contents of the flask b-came a

tarry residue. A total of 14*0 ml. of a two layer product

was obtained. IFurther heating for an hour at 3500 and

less then 1 mmn. ave no further product,

A total of 12,8 :. (14.0 ml.) of product was

obteaied; 5.0 ml. of a blach upper layer and 9.0 ml. of

a light yellow layer. The black upper layer was re-

distilled; 1.1 ml. of liquid boiling at 60-80O/760 mm.

and having an n3l- 1.4620 was obtained; 1.5 ml. of very

dark liquid boiliAir at 60-110/0.05 ru;. anu having an
nD 1.51 was obtained (the liquid was too opaque to give

an accurate nI"); some tarry residue was left in the distil-

ling pot. Both fractions turned darker upon standing and

the higher boiling fraction became quite tarry. Both

fractions gave a positive test for nitr'ogeon. An infrared

spectrum was obtained for each fraction, but no clues to

structural features were evident. Attempts to prepare

derivatives of these fractions failed.

A quantity of tle residue left in the original

distillil. pot was extracted with ethanol in a Soxhlet

extractor for one day and the alcohol solution evaporated.

A residue was obtained which upon f-rth.-tr r3crystallizatlon

yiolod 0.2 g. of white solid, Thiis product decoiiposod

over a long ran- and ras not coi.pl't4ly decomposed at

360,. Fulrt'ler attempts to ide.itify theoe picducts were


2. Degrada.tion of poly-dial lyldiethyl amnionium bromide

Twenty drops of 60% t-butylhydLiopero:-ide (ap.roxi-

rntely 0,012 g./drop) was added to a solution of 8.0 g.

of diallyldiethyl airmionium bromide and 4.0 ml. of iwter.

The mixture was allowed to remain open to the atmosphere

in an oven at 60 for 48 hours, Tho resulting i:hite

hygroscopic product was ground to a fine powder and dried

for several da:.- in a vacuum desiccator. Eight grams of

product, meltinC with consider.jle decomposition at

346-514, was obtained. The product was quite soluble in
water' and ethanol and gave an i-Lediate halogen test i en

treated with lAgI;g solution.

The product was converted to the hydroxide form in

an attcipt to degrade it. It was bclievod that tlhe loss

of ethylene and water from the hydroxide form would result

in a poly-tertiary ,mine or simple.- products that could be

studied. Sevcn and one-tenth grc-is cf poly-diallyldiethyl

ammonium bromide, dissolved in 200 ml. of water, was allowed

to pass through an ion-exch-nge column of Nalcite SAR (con-

verted to the hydroxide fonu). The solution was recycled

three ties and tested for bromide ion; after the third

cycle, the test was less than ten parts per million.

The poly-diallyldiethyl ammonium hydroxide solution

showed a faint pink color when tested with phonolphthalei;.i

tho pl value obtained from a Boclca- pHl meter flluctuated

considerably .d was ti:okin as 11.75 to 12.05.

lhe solution was ovaporatoe to on:e-fourth of the

orlriial volurie on a hot plata and to di-yness on a stewa

bath. The tarry residue vioighed appro::i.atel, five crens.

The p-ro.uct v:a vato insoluble and for:..d a gel when

heatrd with water. The p.-oduct was very slightly soluble

in ethyl c1co.icl, carbon disulfid,, dinlethyIl ormamide,

carbon tetrac'_loride and chlorcJor..; insoluble in benzone

and diethyl ether, lhero ta, co.-,slderable doubt as to

wfet.heor the product was soluble to any extent in these

solvents, or Ut .:t :..r a small q.c.itlty o- p.-o.~-ct formed

a I,.l.

The tr:i,- residue was diCested in carbon tetra-

chloride ;nd yielded a product which could be ground into

a finc poooi dor atez vacuum dryinz. The product decomposed

over a \:id. id:-n.-e znid i:as not co:.pletoly decomposed at 360*.
Analysis found. C, l:9.1, li9.5i; .., 8.39, 8.23X; P, 7.6.

InfraroJ sp.ctre of the pi:oduct we:-e obtai-ed; the tociinique

of depociti:A' a fili frori et:anol, carbon totrLchiloride

or carbon disulfide solutions was employed; t:ih tec:'iique

of incorporation a small qnrltity sample in KBr powder

and pressing a salt plate was also seod. .. 31cs(39)

kindly carried out this pr'ccedu_-e.

When bromine (35 in CC14) was added to a rLixture

of product in hot CC14, an orr--'o precipitate iwas foi-.cd.

This addition product was filtered, dried a.-d ground into

a fine powder. The product dCco.iposed over a ijidc rr.ce

and was not conplstely docompos3d at 360. Analysis found:

d, 5:' .s-

The addition of bromirno a:-d the absorption bsnd

at 6.10,p indicate so e degroo of unsaturation of the

poly-tertiary ctriLle resid-Lo. Colthup((0) lists the

stratchi-n fir. -L-ncy rinee of an ulnconjugated carbon-carbon

double bond fro.,i 6.06 to 6.25~,u

It was hoped that a molecular weight of the original

pol7-"uater?'nry ax-ioni:m bromide cold be ap--ro..irated

from a molecula-r ireiCht determi.ntion of the poly-ari.e.

Since oxtromo difficulties arc encountered in molecular

wei-ht detoirm-inatio-:s of polyelectrolytes, a molecular

weight of the poly-amine could be used to deduce a molecu-

lar .:?i 'ht of the: original poly-quaternary derivative by

assu.i:n- an overall loss of Cj2s r from the poly- 'uatornary

amonirmn bro:i-de. A determination of this type would prove

very useful, since a value of the constant in the Staudiaer

equatio-, relating viscosity end r olccul.r weil-At, could

be c.clculatd and furth-.1 molecular weight determinetions

of poly- uatern ry .;ro,'.uctc could be ap .roximated. liowevcr,

all attempts to detcrmi:ln the molecular weight of th:r poly-

rin. ~roved unsuccessful. ZThe boiling point el-:vnaion

and 2r-..ozin. poi:t depression methodIs wee retrIicted by

the insolubility of the product iand the t mpersature

differe-nti cl, 'eb folloin-: solvc-nt : ver. tri, ond

proved 'unsat is:fectory: water, eth;nol, t-bultcnol, eyclo-

heoanol, triothanol amine, diei!anol eITnin.., nonem th-lene

clyCcol, cr.:tpho:', npthal<-. b, benzene, ce-clohexene, -lacial
acetic acidc, nittrbonzene, 2,4,6-t.irib:olqo'oO.lili.O, bromo-

bcnzene, ci-d oth:l:l..-c dibroraide.

3. Polyme.-ization of diallyl amine hydrochloride
By polymorizin- diallyl amine hydrochloride and

treatl ~r the polymor i;ith LaOH solution, it was thought

tLat a poly-mmin:, similar to the poly-amine in the

previous section, could be obtained and studied.

Ten craas of diallyl amino hydrochloriJo (ro-

cr~7tallized from- acel-one-ethanol three tirns; o..p. 164-

50) :c.s dissolved in 5 nl, of water and treated -with

25 drops of 6C," t-I'vtyl hy-dropcro--ide solution (0.012 g,/

drop). (ir mi::tur rc.ral..cd in an open b,'l:oe- at 600 fcr

three days. Ten grams of product was obtained. The

product was insoluble in water and formed a gel. The

product was treated with ethanol but was insoluble. The

wash ethanol was treated with acetone and only a faint

cloudiness was obtained which indicated there was very

little unroacted diallyl amina hydrochloride present.

After soaking in an acetono-ethanol mixture or picking up

moisture from the atmosphere, the product exhibited elastic

properties. The product did not react with iNaOH solution

to give a poly-amine, as was hopod. However, the properties
of this polymer definitely indicate some degree of cross-

linking. This was the only monomer in this study with

two allyl groups to show characteristics of cross-linking

upon polymerization.

4. Polymerization of 1,4-bis(diethylallylammonium)
butone-2 dibromide

Since Butler and Goette41) have indicated the

butene-2 double bond in 1,4-bis(diethylallylamnionium)

butcno-2 dibromide did not enter into the polymerization,

oxidation of those butene-2 double bond was considered

as a point of attack for degradation studies. Although

the polymer was made and some of its characteristics

studied, further degradation studies were not carried out.

The polymer was prepared from lS.0 g. of 1,4-bis(diethyl-

allylarmaonium)butcno-2 dibromide and 45 drops of 60O

t-butyl hydropero.lde dissolved in 9 ml. of water. After

5 days at 600 in an open beaker, 18 g. of polymer was ob-

tainted. It was soluble in water and othanol. It was re-

crystallized from 100 ml, of ethanol by addi:; 200 ml. of

50,' acetone-dioxane solution. The rosidue was very vis-

cous; after washing, decanting and drying in a vacuum

desiccator, a hygroscopic product melting at 348-$54

(with considorable decomposition) was obtained.

5. Attempted polymeoizations of monomers with the double
bond farther removed than the allyl position

As was shown in the proposed mechanism involving

intramolecular-intermolecular polymorization, the allyl

groups offer an ideal situation for the formation of

strain-free six-membered rigrs. It was hoped that prepara-

tion of monomers containing the double bond farther re-

moved from the nitrogen center would eliminate the possi-

bility of forming a six-mo:libered ring structu-e. If the

intramolecular-intexmolecular type of growth was necessEry,

monomers of this type would require formation of r..ngs

larCor than six-ncmbered and, consequently, the probability

of their formation would bo greatly decreased. In most

cases, the attempts to prepare monomers of this type were

unsuccessful anid polym rization studies could not be per-

for-.d. In the following attempted reactions, it was diffi-

cult to determine whether polymerization had occurred.

a) Attempted polymnrization of diethyllallyl-

butene--yl ammonium bromide.--A nmiture of 1.15 G. of

diethylallylbutene-3-yl semmonium bromide, 3 drops of 60

t-butylhydroperoxide solution and 1.0 ml, of watsr w:as

reacted at 600 for three days. A brown solid was obtained

which was soluble in water,

b) Attempted polymerization of diethylbute:ie-3-yl

Dpnten-h-vl ammonium bromide.--A mixture of 0.5 g. of the

very hygroscopic sorn-solid diethylbut oi-3-yl penten-l.-yl

ammonium bromide, 5 drops of 60/ t-butylhydrop oroxide

solution, and 3.0 ml. of water was reacted at 600 for five

days. A dark viscous liquid was obtained; it was soluble

in water and ethanol.

c) Attn~mpted polvymerization of diallyltetraethyl-

decamethvlene diemmoniurm dibro.Tide.--A mixture of 3.0 g.

of diallyltotratethy1decamethylene diawimonium dibromide,

6 drops of 60% t-butyllTydroperoxide, and 1.5 ml, of water

was reacted at 60S for three days. A light yellow solid

was obtained which was soluble in water.

If polymerization occurred in the above cases, it

is assumed that the products were not cross-linked since

the products were water-soluble,

6. Attempted infrared studies

Since it was postulated that an alternating intro-

molecular-intermolocular chain reaction could causo a

piperidino ring structure throughout the poly.mr, an infra-

red study of related struct'-es was carried out, In this

work hctrocylic ring structures, aminos, amine salts,

quaternairy derivatives and many of the polymoeic deriva-

tives discussed in this section wore studied. IRany of

the con.pounds were obtained conmlcrrcially and the others

were propa2ed. Spoctia o2 the following compounds were

obtaLied; pipeiil.ie, 2-~1.;thylpiperidino, 2,3-dixrethyl-

pipe:iidic, 1,2-dpiiperidinoethlan, 1,2-dimorpholino-

et'haiio, diallylpiporazino, pyrrolidino, Ni-allylpyrrolidine,

diallyla.ni:e, tr-iallylaE1i.e, dimethylallylamine diethyl-

allylamL-. and aminc sclts and quaternary derivatives of

some of thIoze compounds.

ilow.-ver, all the attempts proved unsuccessful,

since a ri--r structure could neither be identified from

the s.ectra of the above compounds nor correlated to t'-e

spectra of the polrie.ric derivatives,

7. Solvo:t effect on polymerization

The possibility of solvent interaction during the

polymerization must be considered as a factor affecting

the nature of the polymer--. If a growing chain-fre. radical

could react with a solvent radical in preference to a mono-

mer molecule, the degree of polymerization would be reduced.

Thus, it mirht be possible to have a monomer molecule con-

taininr several unsaturated groups and yet obtain a polymer

of a low degree of polymer-i"ation and sli-ht cross-linki:.c.

The following espe.1 ients were carried out vw-:ioii tho sol-

vent Pnd solvent conce traction.

a) A mixture of 3.0 ". of trinllylbutyl c1-monium
bromide, 3.0 ml. of water, and 6 drops of 6C-, t-bc.tjylydro-

pero::ide solution was reacted at 600 for 76 hours. A hard,

water-soluble solid uas obtain ed. The product was dissolved

in 10 ml. of water; 10 drops of initiator was added a~d the

mixture was reacted fcr an additional ieQk at 60. The

product w-s water-soluble*

b) Two grc.ms of triallylbutyl azr-.onium broilide,

4 drops of initiator, and 2.0 ml. of vater were reacted
at 1000 for 38 hours. The product was wator-solublo,
c) Two grcas of triallrlbutylammoniumi blo-nido,

2 drops of initiator, nnd 0.08 ml, of wate-:; wei.' reacted

at 1000 for 38 hours. The resulting Z]le, glossy p-oJ-uct
was socked in hot water, filtoeed, aLd dried. One and

seven-tenths gre:-s (085 yield) of water-insoluble product

was obtained. Tie procedure was that of Bunch, (42) who

reported a 52.5% yield.

d) Three grams of diallyldiethyl anmnonium bromide,

10 drops of initiator, and 0.3 ml. of water were reacted at

1000 for 38 ho; rs. The product was water-soluble.

e) Three grams of diallyldiethyl amnioniuiu bromide,

10 drops of initiator, and 50 drops of dimethyl formamide

were reacted at 1000 for 38 hours. The product was water-


8. Initiator ef-fct on polymerization

The effect of other initiators, with rosnact to

t-butylh7droporo-dide, was determi.id in the following ex-

porinents. Va:iousa initiators were tried with monomers

containir:l one, two, and three double bonds to se? if

t-b-;.,tylh-dropero-:ide is unique in its property of yiIldii

non-cLoslinurd poly:-rs with monorn-rs containing, two allyl


One gram each of triethylallyl ammonium bronide,

diallyldiet'.hyl arz-oniun bromide and 1,4-bis (diethylall'rl-

aruonium)butono-2 dibromide were dissolved in 1.0 ml. of

water and reacted for one waek at 600 with 0.05 g. each

of t-butylh-;dro'pl:-oxide, di-t-b;:tylpero-:'de, and benzoyl-

Tle lack of cross-linki :i was indicated in every

case by the wator-solubility of the products. Poly:-.o~i'a-

tion took place only in the rs -octive reactions of diallyl-

diethyl arnonlni bromnde and 1,4.-bis(diethyltallyl7anronium)

butene-2 dibro:-ido with t-b:;tylh:rdropero Aido. In the othir

cases, the strrtin nonomors were rocovere'd and identified.

In an attempt to ovrluate the initiating property

of 2,2'-azoisobutryonitrile, the azo initiator was reacted

with hoxaallylethylene diamr'onium dibroride, since it was

thou'-it that an easily isolated, insoluble product would

be obtaiiod if polyeri-zatioi occur-i. T.i mono.', dcis-

solvod in 10 ml. o2 dLC:thyl foi-._-;idJ was allo-.;oJ to react

for two W32.-:3 at 60 in an opjn vusjoi.


ITT: AAL,'U' YL'TJ-iYLW::1; JIAnt"0iiI~4

Wei-b.t of Vei-t of Perccnt :it. of H1O
ionomer Initiator Initiator Insoluble nemaliks
Prod ct

5.00 g. 0,013 g.

5.00 g. o.025 -.

5,0o g. 0,050 c.

5*00 -. 0.10 g.

5.00 g.

5.o0 g.





0.25 g.

0.50 g.

0. 0

Soluble LigL-t viscous liq.
after twio weeks

Soluble Ligrht viscous liq.
after two wo ks

Soluble Viscous liq. after
two we -a s

0.75 r'. sav7 viscoua liq.
after 2 weeks

3.26 g. Gelatinous after
12-15 hr. Flex-
ible solid 2 wks.

4.37 g. Gelatinous after
6 hr. Grittle
solid at 2 wks.

The initiating effect of 2,2'-azoisobutr7onitrile

upon the polymerization of diallyldiothyl ammonium bronide

was doternmiied in a similar manner* Two rrars of diallyl-

diethyl tcmmoonium bromide (mI.p. 155*) dissolved in 10 ml. of

dimethylformamide was allowed to react with varyinr amounts


of azo iaitiator at 750 frr firtooCn dc;s. hle JirduLct was

water soluble lin voir cas.;; tohe Letcn.aiL' ~io: of the aUount

of pol-,i.. ization was rather difficult Unjreaacted monomer

U;0s Jo3.ratjad 2o." tile roLction prod.u.ct by extraction dth

hot aceto..o. Attumpta r1ccrystallizatioln iom acetooe and

Othanol rOi sultUdL in l ll lu-~iation.



Wt. of Ut. of .-
rionoi:er Initiator ,ciursB

2.iX .*:. 0.02 -. 1.0 'atcr soluble; portion
insoluble in hot acetone
m2neted at 295-300*

2, .10 5.0 ..:rter soluble; nclted
at 305-7*

2.00 g. 0.20 g. 10.0 Water soluble; melted
ct 306-7o

9. "',Vect of o-::e'- in the pclT,' riza.tion

It was considred that c::cen could exiit so:-o

inhfi.Itirn factor in the polTicrizatio'. and coittri' -te to

the f.ct that sol'.ble ,:--d non-crozsli:nro pol -r.o s were

obtani. d i:ith rinolo.-;:-s cc:.tair.n-i tiro -llyl Crcups. The

follcwing c::.,crimernt were perfori:'cod to determine the

ef-ect of o:-:-'cn.

a) A mixture of 8.0 g. of diallyldiethyl anunonium

bromide (moip 155*) 4,0 ml. of water, and 33 drops of

60cv t-butylhydroperoxide solution (appro.dimately 0.012

g,/drop) was allowed to react for 76 hours at 60-659, The
reaction was carried out in a nitrogen atmosphere, nitrogen

was passed through a combustion tube filled with copper

turning, two wash solutions of alkaline pyrocallol, a

CaSOc dryiie tower, and into the reaction vocsel. The

system was flusled. with nitrogen before the reaction was

started. Eight grams of hydroscopic product was obtained

after dryiln for several days in a vacuum desiccator at

less than 1 mm. pressure, The product decomposed over a

wide rnnrm and nelt d with decomposition at 355-600 The

product was soluble in water but was relatively insoluble

in ethanol, forming some gel. The degree of solubility

of this product in ethanol differed from the solubility

of polydiallyldiethyl samonium bromide, Which was prepared

open to the atmosphere.

A determination to show any possible difference

in the analysis calculated to include complete catalyst

incorporation in the polymer, and the actual analysis of

the polymer, was made. Since the conditions prevented the

reaction of atmospheric oxygen, the only oxygen present

in the polymer would be contributed by the catalyst or

from solvent interaction by the OH radical.


iMoles of catalyst = 33 drops x 0,6 x 0.012 g./drop x
Smole = 0.00264 mole
90 g.
1 mole = 034 mole
Molos of monomer = 8.0 g. x 23 0034 mole
234#2 g.

0.034 mole nonomer
C.00261: :-lole cat.'ilvst

= 12 mole moimomor
mole catalyst

(assuming com-
plete catalyst
in polymer)

TA :L: I::

I..AL'-'.:. OF .POL.-DIJ LL'L.7JJ -_iriL A:I,...,T:JII 3- I1" 1

Monomer Polymer Actual Analysis
(theory) (Assumiii: com-
plete catalyst
incorporl. ationl) I II Avlg

c 51.31 51.30 51.2 51.5 51.35
H 8.56 8.63 8.38 8.26 8,32
i 5.98 5.82 5.46 5.53 5.50
;'Br 34.15 33.21 33.8 34.0 33.90
%0 o 000 1.04 Total 99.07

Total 100.00 100.00 Oxygen by difference 0.931

An infrared absorbtion band at 6.10M4 indicated
some degrco of unsaturation of the polymer; a measurement
of the doCroo of unsatbration was attempted. This method
consisted of catalytic hydrogenation at atmospheric pres-

sure and was carried out according to the modification of
Parkin. (3)

A weighed quantity (approximately 0*06 c.) of

platinum oxide and 20 ml, of distilled water was placed
into a hydrogenation flask equipped with a magnetic stirrer

and a rubber-tipped side arm. After the system was evacuated

and flushed with hydrogen three times, the magnetic stirrer

was started. After complete absorption of hydro-en by the

platinum oxide, the stirring was stopped and a weighed

sample, dissolved in 3.00 ml. of water, was introduced

through the rubber tip from a calibrated hypodermic syringe.

At this point, the pressure was equalized to compensate

for the addition of the 3.00 ml. sample. The stirring was

started and the reaction continued until further absorp-

tion of hydrogen had ceased. Since the stirring mechanism

caused some heat to be generated, the system was allowed to

core to equilibrium before measurements wo:-e made. The

following table gives a summary of the data,

Since all the attempts to recrystallize the pol-mer

sample proved unsuccessful, the crude sample was hydro:ena-

ted after careful drying. However, a later method proved

successful in extracting any monomer left in the crude

polymer sample and a value of pure polymer fraction was
determined, With this correction, an average value of 0.193

moles of hydrogen absorbed per mole of monomer unit charged

00 0 7 Io A 0
* r 0 0 0 0

00 0 00o0 0 0
0 0 0 0 0 0 0 0
000 000

* A 0 0 0 o o
0 Q O0 C\l C'- H XfE '>Q
N(O -^' O N NO H 00
S'001 AO l 00 00 8
C * *00 0 0 0 0
0 0 0 * * *
000 0 0
o o o' c o' o










0 c
oN 0
o o o

0 0 0
0 0 0

S0 0

0 0

G A 4

a ,a ,o
o 0 0


0 0 0
o 0 0

o a 0

0 i A r co
M O O oN
0- 0 O; 0 0 0
0 00 * *
0 0 0




0 2
a I


t P
P -j

H - Tr H
to H 0
43 40, 3 g

030 0 4
eC a

0r 0
04O H E1
o ) *rc

E as rj o











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