The Effect of Certain Groups on the Basic Properties
of Polyqucaternarv Ammonium Hydroxides
ROBERT L GOETTE
DliEFRP.TI L-N FFr1EN E[i T TI. E CI." A.ITF C,,iiN(a. OF
iHL I. i Nr. ]T-:ir' F F L-P ri
IN PA.FT.L t.iL[i Ltl [NI Or ih4 li i.E IR) FIENi T PE iT THfE
DEC.1E [ OF EDCTOC R OF priL-:l.-ifh\
L'UIVUERITn OF ILORMiD.\
| j r j r i -. i
TABLES. OF COR EifS
LIST OF TABLE ............... .............................. ii
LIST OF ILLUSTRATIOHS. ........................... ........... I
I. IrNRODUCTION ........................................ 1
A. Literature view ............................. 1
B. Statmeat of the Proble ......................
C. Souree and Purification of Reaetants...........
II. PPREPAATION CF TERTIARY AMINS ...................... 7
A. General Disaasion.......*.................... 7
B. Experimental .................................. 9
III. PREPARATION OF UNSATURATED QUAT3RNARY AIMONIIM
UALIDES .............................. ... ........ 15
As General isoussion ............................. 15
B. Expertmental.................................. 17
IV. POLYMERIZATION OF UNSATURATED QUATERNART AMMOTYM
HALIES ......................................... ..... 29
A. General D lSsion .................. ........... 29
B. Experimental ........... ......... ....... 30
T. ION EXCHAME CAPACITY OF RESIST ..................... 40
A. General Diseualon. ............................ 40
B. Experiment................................... ....... 42
VI. DISCUSSION OP RE.SU S.............................. 5f,
AOK0ltWDSE,- S. S.............................................. 1b
BIOGRAlHICAL ITMS ................................... ...... 82
C0OWITTEE REr'?T............................................ 65
LIST OF TABLES
I. Unsaturated Tertiary minr and Tertiary Anina
Hydrobromid.e .. ............ ..... ........o ..... .... 14
II. Unsaturated Quaternary Amoniumn Broaides ********.****.** 27
III. Unsaturated Quaternary AInonii m hlorides e*............. 28
IVT Data on Titration of Resins A-H o...................... 44
V. Data on Titration of Resins I-P .............*........... 46
VI. Properties of Ion Exohange Resins ...................... 52
LIST OF ILLUSTRATIONS
I. Ion Exahange Capelty Titrations of Polymers A-D ...... 48
II. Ion BEwhange Capality Titrations of Polymers E-H ,...... 49
III. Ion Exshange Capeity Titrations of Polymers I-L a...... 50
IV. Ion Exeheno capacity Titrations of Polysersl -P ....... 51
As Literature Review
The absence of information in the literature ooneerning the poly-
merization of unsaturated quaternary cnonium compounds to anion exchange
resins of high basicity led Butler and Bunch (1) to investigate the poly-
merization of various unsaturated quaternary iaonium coripourds Aith per-
oxide catalysts. Tertiary butyl hydreperoxide proved to bo the mnot satis-
factory catalyst in preparing polymerm from unsaturated rqunt.ernrur mmoniua
halides. Resins capable of operating in a pH range of 11 to 12, but having
oapaoities no greater than 0.40 milliequivalents of anion prr milliliter
of wet resin, were synthesized in this study.
Butler and Ingley (2) have shown that the presence of a halo:e.nated
allyl group in a quaternary ammonifa derivative tends to decrease the poly-
n.erization rate. This was substantiated by the fact that tne coeffioient
of swelling of a triallyl-2-ehloroallyl a0sonium bromide vol'F-er was eon-
siderably greater than that of a tetraallylamnonium bromide rjumnnr prepared
under similar conditions# indicating a lower degree of oros~linkings The
halogenated polymer had a higher ion-mmchange capacity per unit weight and
a lower ion-exchange capacity per unit volume than the non-haloc.natod
Investigation of unsaturated iuoternar. t' onium brrlide. containing
the vinyloxyethyl group by Butler and this author (3) showed thtt the vnA -
oxyothyl group did net enter into the polymerisation under the conditions
The work of Butler and Johnson (4) showed that the triple bond did n*
enter into the polymerization ihen quaternary a.aonium ompounds containing
the propargyl group were tested.
Butler, Bnach, and Ingley (5) have shown by titration that the poly-
mars obtained by polymerilation of unsaturated quaternary moniua salts
fuation as stroanly basio itn exohage resins Titration eurres resebled
a typical strong base-strong maid titration urve. Under the conditions
polymerization used in the work, the polymers showed a sall aine sapwait
aa the result of thermal dooapositiln of the quaternary oeanium salt. The
hydroxide form of the pol ers doaoposed by a Boe1nn degradltiojn ean
hated. Polymers prepared by polymerizati.n at low temperatures showed de-
ereased swelling eoefficoints and correspondingly daeeread capacities,
probably as the result of screening. Polymers prepared by suspension poly-
merization showed an increase in eapaeity with dereasing swelling oeet-
fioient. The polymors prepared by bulk pelymerisz.ioa showed a definite
relationship between the ooeffloient of swelling mad the ion exchange
ompaity. The higher the woeffisient of swelling, the more nearly the
theoretical capacity of the resin is approauhod* These workers ali found
that the hydroxyl ions ware roplased more rapidly than chloride iona under
the oonditions rhioh they used. Although the initial anion oonoentration
did not affect the ultimate epaceity of the retin, the initial ph was hig*w.
B. Statement of the Problm
In the work done by Butler and oo-workers (1,2,354,5) no specific
study of the basli properties of the polymers had been made by varying
the substituent groups on the nitrogen atota It was therefore decided
to investigate the effect of certain groups on the basic properties of
poly quat ernary ammonium hydroxides.
In order to conduct this investigation it was necessary to obtain'
various aliphatic or aromatio derivatives of inmoniu~ bromide or chloride
having a minimum functionality of six. The proposed procedure ras to
heve three allyl groups in each compound and to vary the fourth group*
Since there were only two suoh compounds whioh had been previously pre-
pared, it was necessary to prepare several new oocipounds for this investi-
In order to determine heather the butene-2 double bond enters into
the polymerization of l,4-bia(trialkylammoniua)butene-2 dibromide compounds,
quaternary amonium salts containing two and four double bonds, in addition
to the butene-2 double bond, and l,4-bis(trialkyla-onium)butone dibroride
compounds containing two and four double bonds were prepared. Therefore,
v.ork was directed toward the synthesis of these new compounds.
It was also decided to attempt to produce resins of higher capacity
than those prepared by unch (6) and Ingley (7). It can readily be seen
that the lower the equivalent weight of a quaternary ammonium salt, the
higher will be the theoretical exchange oapaoity (nmlliequivahlnta per
gren) of the polymer produced from the salt. There are several weys of
accomplishing this task of producing a lower equivalent weight. The poly-
mer may be produced in the form of the chloride, or the molsoilar weight
of the quaternary mIonium salt mlay be lowered by use of low molecular
wight substitutes groups, such groups giving a minimum fueotinallty of
six, or a low molsoular weight quaternary omoniu salt, without the
minimum finetingality needed to form a eress-linked polymer, may be oo-
pol. yeriaed with a quaternary isonim salt which has the necessary
tPnctionality to produce a cross-linked polymer. With these ideas in
mind, investigation of several types of ion exchange resins produced
frR various ls4-bis(trialkylumonium)butene-2 dihalides was undertaken.
After a review of the literature, it was found that it would be necessary
to synthesize several new eaopounds in order to carry this line of in-
vestigratIon to a suesessful oonclusione
C. Source and Purification of Reactants
Diethyl aine, and l,4-diohlorobutene-2 were obtained from Carbide
and Carbon Chemicals Company. The tetrahydrofuran, ethylene bromohydrint
methyl bromide, methyl mine, and dimethyl aine were obtained from the
MUtheson Company. The allyl chloride was obtained from Shell Cha ial
Corporation. The beta-clloropropionitrile and the diallyl cyaniaide,
vhie was hydrolysed to make the diallyl rine used in this research pro-
ject. were obtained from 1Aeriean Cyananid Company. Benzyl bromide was
obtained from Golumbia Organic Chemicals Company. The tertiary-butyl
hydroperoxide was obtained as a 60% solution from the Luoidol Division,
ovadel-Agene Corporation. All of the'oompounds mentioned above were
utilized without further purification.
Allyl bromide was obtained from Dow Chamical Company and the fraction,
boiling between 70.0-70.20, was recovered for use.
The 1,4-dibronobutane used in this project was synthesised from
tetrahydrofuran and 48: hydrobromio acid according to the procedure given
by Cason and Rapoport (8) for making 1,5-dibromopentane. The dibremo-
butane recovered for use boiled at 820 under 14.5 a*
1,4-Dibromobutene-2 was made according to the procedure of Prevost (9).
The material boiled at 61-6 at 4.8 ami
Bis(diallylamino)methane was synthesized by the procedure of Lewis
(10). Material boiling at 830.0-80.20 at 4.2 ma. was recovered for use in
Die(Jimethylmino)methene was produced in the s~ manner as bis(diellyl-
aino)methane (10) with one change in procedure. The mine was not ex-
tracted with benzene since its boiling point was so close to that of benzene.
Inatea& the product was merely separated from the water layer and dried
over solid aiMN.
1,4-Bis(diethylmilno)butene-2 and 1.4-bia(dimethylaino)butme-B
were both made by the procedure of Willstatter and Wirth (11). Better
yields of these caopounds were obtained by the use of 1,4-diohlorobuteae-2
instead of l,4-dibraoobutene The substitution of the diohloro oempoune
was made after reading an ertiele by saundsen and oo-workers (12), in sieh
they had obtained larger yields than hbe been obtained by this author with
the use of 1,4-dibromobutane-2.
It is of interest to note thet 1.4-bi(diethylsmine)butne-Z was also
obtained by reacting 1,2-diehlorobutense- with diethyl mine in the sme
maner as mentioned by Willstatter and Wirth. The yield of the product we
smeseat lower than that obtained using the l,4-dichlorobutene-2, but
Allyldimethyl mine wa obtained by merely reeating allyl chloride
with dimethyl mwine. The product boiled at 62.3-63.0C.
Diallylaethyl smine was syntheeized by the procedure of Partheil ad
von Broieh (13). The maine boiled at 1110.
Triallylbe.sylarnonii. bromide and tetreallylupfonila bromide were
made by the sae procedure which Bunch used (14,15).
II. PREPARATION OF TERTIARY JINES
A. General Discussion
It was necesa y to synthesize both' saturated and unsaturated tertiary
muin" as intermediates for the preparation of the uns turated quaternary
amnonlum compounds. Two method were used to synthesize the tertiary sainess
a modification of the aamonium hydroxide synthesis reported by Butler and
Benjamin (16)) and the method described by Willstatter and V.irth (11). The
latter method was modified as a result of work published by Amundsen and
In preparing triallyl aine (previously reported)# allyl chloride and
a 28,s aqueous am-onia solution were placed in an iron bomb uhioh was imed-
iltely sealed and heated for a time at an elevated temperature. The bomb
and contents were then cooled in ice and the nine layer separated. More
nine was salted out of the water layer with NaOH* The combined nine
layers were fraotionated after drying over solid NaQI for at cast 18 hours
The 1,4-bis(dialkylamino)butne-2 and 1,4-bis(dialkylamine)butane *sa
pounds were prepared by adding the secondary amine dropwise to a baerAzne
(dry) solution of either 1l4-dibromobutene-2, l,4-dichlorobutcne-2, or 1,4-
dibrraobutane contained in a three neck, round-bottom flask fitted with a
water-cooleJ reflux condenser, meehanieal stirrer and an addition funnel.
The mixture was stirred at rooi temperature for at least 24 hours. The ratio
of sine to halogen campound was two moles to one mole respectively. At the
end of the period of stirring, an excess of coneentrated sooilm hydroxide
solution was added, Phen the reaction mixture had separated into ti.o aIcrs,
the nine layer was removed and the nine purified by fractiLnal distillation.
In the second method, the procedure was slightly modified when the
secondary amine was vTry volatile. In this case, the line was dissolved
in dry beezene and the halogen oompound added dropwise. The rest of the
procedure was identical.
A heated column 2 a 40 a., packed with insh Berl saddles was used
for fraetlaantion of the aopounds. The pot wan heated with a Glau-Sol
heating mantle. The distilling pot, head, and the part of the column
which extended beyond the heating jacket were well insulated with glus
wool. Ground glass joint equipment was used for both the preparation mad
purification of the sMines. Tiperatures recorded for the boiling points
are uncorrected. All pressures were measured by means of a Zimmerli gaup.
The refractive indices were determined by means of an Abbb refractam-
etar at 250 Ce. white light ws used as the source of illumination. Con-
stant temperature was maintained by circulating water thro'lgh the refrao-
tamster from a constant temperature bath. Before taking a reading, sufficient
time was allowed for the mine to acquire the smse temperature as the lens
of the anstruna4b.
The speoifio gravities were determined at 250 . with a calibrated 10
ml. Kimble specific gravity battle, equipped with a standard taper thermaaeter.
Freshly distilled portions of the ompounds were used in both the epealfle
gravity and refractive index determinations.
The nitrogen content of the mine was found by the Kjeldahl mu-thed.
INreurio oxide Wms used as a catalyst. The sodium hydroxide solutieft Au-
tained two parts sadilu thioislfete for eaeh part of aereurie oxide.
The properties, analyses and yields of these new tertiary maines re
isuarised in Table I. Individual details not covered in this general dis-
cussion oan be found in the experimental part of this section.
Individual details not included in the general procedure are given
in this section. All temperatures are in degrees centigrade, and its
symbol is omitted in conformity with the present usage in soient-fi re-
Synthesis of Triallyl raine.
Allyl chloride (490.2 ml., 6 moles) and 28'; aqueous acmonia solution (540
ml., 8 moles 'Nl3) vwre plhcod in an iron bomb equipped with a pressure
gauge and stirrer. The bomb was placed in an oil hath at 1350 and the o-
tents stirred. The pressure rose to 220 lbs./in2 within 15 minutes. After
a short time, the pressure decreased considerably and the bomb was hosted
at 140-1550 for 3- hours. hen the bomb had cooled to room temperature,
it was placed in an ie bath before opening. The oily layer was removed.
The water layer was saturated with NaOI and the oily layer dwioh formed
was removed and combined with the original s1 ine layer. Lath were dried
over solid 01O for 18 hours before distillation. Some allyl aine and
diallyl amine were obtained. The triallyl aine boling between 148-90
was collected and TOirched 131.3 g. The yield was 48%* Sinee triallyl maine
has been reported previously, it was characterized by means of its physloal
Synthesis of 1,4-bl3(diallylanino)butone-2.
(CH2:CH-CU2 )2-N-HCH2-CH=CH-H2-N-(CH2-CHnCU2 )2
This compound was prepared by two methodat (1) reaction of diallyl amine
with 1,4-dibromobutone-2 and (8) resetion of diallyl aine with 1,4-lickoro-
I. One-fourth mole (55.5 g.) of 1,4-dibromobutene-2 was dissolved
in a minimum amount of dry benzene in a three meek flask equipped with
mechaneial stirrer, reflux oondenaor and addition funnel. Diallyl amins
(60.6 g., 0.5 mole + 25s excess) was added dropwise uith external cooling
of the reaction flask. Stirring at room temperature was continued for 24
hours* A saturated solution of RaQH (100 g.) was added to the flask and
the mixture was stirred overnight. The benzene layer was then removed
and dried over solid sodium hydroxide for 144 hours. The benzene was re-
moved and the smine distilling at 92*3 at 0.4 am. was eollooted. The
product weighed LS g. The yield was 37.4%*.
Analyssle Caled. for C16262'a N, 11.57. Foundsi H 11.45.
Physical Constantes DR 0.8822; nD 1.4820; b.p. 92-35 at 0.4 m.
IrD oelod. 81.95; ErD found 81.47.
e. One mole (125 g.) of 1,4-dichlorobuteme-2 was diseolved in 300 ml.
of dry benzene in a thre neck fLask equipped with meahanial stirrer,
reflux condenser, and addition funnel. Diallyl s1ine (194 g.. 2 solee)
was added dropwise. Stirring at room temperature was continued for 48
hours. A saturated solution of NlOH (200 g.) was added to the flask and
the benzene layer then removed and dried over solid WaCB. The beneane was
removed and the amiLn distilled at 102 under a pressure of 0.8 -m The
product weighed 167.7 g. The yield was 6W8.
3. An attempt was made to make l,4-bia(diallylmineo)butenma by re-
actLag 1.4-libromobutene-2 with diallyl sine in the preeence of a paste of
stadium bicarbonate in water. A yield of 5.46 was obtained. This procedure
was unsatisfactory under the conditions used.
Attapted Synthesis of 1,4-bir(diall-,1lsino)butrne.
( a21aH-CH2 )g-N-( CH2 )4"- -(CH2-CB=CH2 )2
1. l,4-Dibromebutsne (54 g., 0.25 mole) was dissolved in 100 ml. of
dry b'enzene and diallyl amine (48.6 g., 0.50 mole) was added dropwise with
stirring. The reaction was stirred at room temperature for S6 hours A
saturated solution of sodium hydroxide (80 go) was added to the flask.
Three layers were obtained. The lower one was discarded, the top one dried
over Na~I, and the middle one was distilled from solid NaOH. The top layer
of the distillate thus obtained, was added to the top layer previously ob-
tained. Both amine layers were dried over the solid NaOH for about 16
hours before distilling. After the benzene had been removed, two fractions
were obtained, having the following physical properties b.p. 77-90 at 11
Ma., n-9 1.46901 and b.p. 79-900 at 11 ia., a9 1.4712. Each fraction was
only a few ml. in size. A sodium fusion was run on the second fraction
Nitrogen was present and halogen was absent. The refractive index of 1,4-
dibromobutane was 1.5153 at 29*
2. Four grams (0.0186 mole) of 1,4-dibrnoobutane and 7.23 g. (J0.744
mole) of diallyl amine were mixed in 20 al. of dry benzerm This mixture
was allowed to stand at room temperature for two days. The ahite crystals
were filtered off and dried. The product weighed 5.7 g., givingg a yield of
74.5': of the mine dihydrobramide.
Analyisi Caled. for ClbHo0N2Br2g Br, 58.95. Foundi Br, 38.70.
Physical Constantss m.p. 58B.
No material was isolated which could be considered as the 1,4-bis(di-
allylnmino)butone; only the dihydrobromide of the mine was obtained.
Attempted Synthesis of l,4-bis(dJethylanion)butEne.
1. 1,4-Dibromobutane (54 og. 0.26 mole) was dissolved in 100 al. of
dry benzene and diethyl mine (73.1 go, 1.00 mole) was added dropwiue with
stirring. The reaction mixture ws stirred at roan temperature for 12
hours ad then was refluzed gently for 1- hours. After the eontoets of
the flaek had cooled to room temperature, a ooAuentrated solution of Ka0H
(80 .g) was added to the reaction mixture. Three layers were formed aad
the upper layer was separated ad dried over solid atH1 for a short time
rA then it was distilled. The lower two lyeors were disoerded. Only
benzene and diethyl miLne were obtained from the distillation of the dry
upper layer. A very small mount of oryntallLne residue remained iLae
2a Four gras (0.0186 mole) of 1,4-dibromobutane and 5.44 g. 0.0744
mole) of diethyl mine were mixed '-i 20 ml. of dry benzene. This mixture
was allowed to stead at room temperature for 24 hours. whitee crystals
began to precipitate within half an h-ur after the two oompounds were
mined. The white crystals were removed by filtration, dried, and weighed.
A yield of 4.5 g. or 63.8 of 1,4-bis(diethylemlno)butnae dihydrobromide
Analysis Caled. for C12530nf2Br2 Br, 44.15. Found Br, 45.92.
physical Consetats m.p. 800
No material wan isolated Which oo-Id be considered to be l.ri s(di-
ethylmnino)butane; only the dihydrobromide of the sine was obtained.
Attempted Synthesis of 1.4-bis(dimBethvylaino)butaie.
Dimethyl mine (22.54 g.o 0.5 mole) mes poured from a cold trap into
the resetion flask which contained 100 ml. of cool dry beazome. la4-DL
bromobutane (54 ge, 0,25 mole) was added dropwise with stirring* Grystala
formed very shortly after the 1,4-dibromobutie had been added. After the
ice bath was removed, the relation proceeded smoothly with a very slight
evolution of heat. The reaction waY stirred at room temperature for urabo
18 hours. The re otion mixture was treated with a concentrated solution
of NaCi (80 g.) and the upper layer which formed separated from the two
lower lqers. After the upper layer had dried over solid NaGH for a short
period of tie, it was distilled. Nothing was obtained from the distilla-
tion, except benzene.
* ca *ra
III* -RZPARATrTOgJ OF UNSAITURATD QUATERNARY AMMONIUM HALIDES
A. General Diselssicl
The quaternary monium halides were synthesized by two mothodsi
(1) by adding the alkyl, aryl, or substituted alkyl broaide dropwise
with stirring to the tertiary amine, dissolved in a dry solvemt; and (2)
by adding the tertiary maine dropwise with stirring to the diholobutene-2,
dissolved in a dry solvent. The apparatus used was a round-bottom flaak
equipped with a mechanical stirrer, water cooled reflux condonsor with
CaCI2 tube attached, and an addition funnel. Acetophenonne, aotons,
methyl ethyl ketone, benzene, end hexanol-1 were the solvents used. Most
of the reactions were stirred at room temperature for 24 hours. Some of
the compounds precipitated out of th* solvents very easily, but others had
to be salted out with dry diisopropyl other* All of the quaternary Wnom.-
ina halides were washed with the ether and then played in a vaouun ioaiooa-
tor to dry. Since the coapounds obtained were quite hygrosoopia, they vere
not recrystalli;ed for analysis. The ether used for salting out -urposes
was first dried over calcium bhloride and then the last traces of moisture
were removed by playing the ether over sodium ribbon. The ether was fil-
tered before use.
The bromide contea of the quaternary uammnium salts (unpurified) was
found by direct titration with a 0.1 nonnrl solution of silver nitrate
Dichlorofluoresoein was used as an indicator. The end-point was a sudden
ch nce from vhite to pink in the color of the silver braoide particle*.
Dextrin was used to prevent coagulati:n of the silver halide. A 50 ml.
buret with 0.1 ml. graduations wa used.
Three, 0.3 to 0.6 gS ssnples, of the quaternary aanonium halide were
weighed by difference. in-m a 125 ml. Erlerma yer flask. The halide was then
dissrrad in about 20 ml. of distilled water and about 0.05 g. of dextria
ad 3 drops of indiestor were added. The solution was titrated in diffuse
light. -'th several of the quaternary ammonium alta it was seassary to
dry tha in an Abderhalden drying plital before analysis.
The qusternary moniu malts were very soluble in water. law moleun-
lur weight aloohols, and ketnae. The produeta were stored under anhydrous
ounditions to prevent absorption of moisture.
Individual details about the preparation of these salt are discussed
in the experimental part of this section.
Synthesis of 1,4-bis(triallyleBmonium)butine-2 dibriaide.
(Che=G-CH 2)3-N-2"ICHC-GH-C2-N- (CH2"'Cn2 )3
This compound was prepared by two methodat (1) the reaction of allyl
bromide with 1,4-bir(diallylsaine)butene-2 and (2) the reaction of triallyl
mine with 1,4-dibromobutene-2.
1. Oae-half mole (123*2 g.) of 1,4-bie(diallylwnino)butene-2 was dis-
solved in 100 ml. of dry aestophenone and allyl bromide (11g.. 1 mole) was
added dropwise with stirring. The reaction flask was cooled, as neoeIsary,
in ice water. There was such a large amount of solid formed that it was
necessary to add 50 ml. more of acetophanone during the reaction. After
addition of the allyl bromide was complete, the reaction was stirred for
another hour. Diisopropyl ether was added and the Awite, hygrosoopio solid
filtered off and washed twice with dry dilsopropyl other. The product,
after drying in a vacuum desieeator for several hours, weighed 244.2 g.
The yield was 100%.
Analysis Calod. C223H6N2Br2i Br, 32.72. Found 32.47.
Physical Constantes m.p. 155-70.
2. Eight grian (0.0373 mole) of 1,4-dibromobutene-2 was dissolved in
10 ml. of dry eaetone and the triallyl mine (10.2 g., 0.0746 mole) was
added dropwise with stirring. After a short time a viscous liquid separated.
thinhn an hour, the viscous liquid had turned to a fine, white, hyc.rosooplo
solid. This solid was washed well with dry dillsopropyl ether and dried in
a vacuum desiccator. The dry product weighed 15.5 g. The yield was 85.31.
The physical constants corresponded with the previously listed data in method
tempted Syntheeei of l,4-bia(diallylathylmmoniam)butene.2 dibro-
(C-CZ-0G92)2-tH.,-< B-ea2-0 02-aw )2
This eapound we- prepared ly two aethodei (1) rseation of methyl bromide
with 1,4-bia(diallylmino)butane-2 ad (2) reaction of diallylmUthyl asim
1. Methyl bromide (0.014 mole) uhih had been liquifled was added to
l.4-bis(dilllylraino)butuM-2 (0.007 mole) and then the tube containing the
two omapoudi me sealed ad allowed to stant at roam temperature for three
days. At the end of this tie t.he tube wan opened. The product was in the
form of a dare vieeovs liquid, oontt.;L ig very few crystals. Reerystalliza-
tion was unsuecessful.
2. l,4-Dibremebutene-2 (8 go, 0.0873 mole) was diesolved in 15 ml. of
dry aaetone and diallylmethyl inea (8.3 g., 0.0746 mole) added dropwise
with stirring. A viscous liquid, aeeapanied by the evolution of heats
separated. The liquid soon beeae so visTous that another 15 ml. of arsetb
was added. After the mixture had stirred at room temperature for an hour,
heat was applied so that the meatone refluxed gently. 3Sine no solid was
obtained, the viseone liquid was re ved, washed with dry diisopropyl ethers
ad dried in a vauum desiccator. Recrystellisation was unsueeesful. lb
analysis eould be obtained which serrespaoded to the ealoulated value.
Synthesis of triallylaethylnamonium braoid.e
Triallyl mine (68.5 g., 0.5 mole) we dissolved in 190 ml. of dry acetone
and methyl bromide wos bubbled in slowly with eooliag and stirring. ThAe
some methyl braoidte ollected in the old trap, which was sonneoted, by
means of rubber tubing, to the top of the reflux condenser, the passage of
the bromide was discontinued and the reaction flask and contents allowed to
warm up to room temperature. The reaction stood overnight at room tempera-
ture. The fine, white, hygroscopio solid was filtered, washed well with
dry diisopropyl ether, and dried in a vacuum desicoator. One hundred six
grams of product were obtained giving a yield of 91.5%.
Analysis Calod. for Cl o18NBrs Br, 54.42. Found Br, 34.44.
Physical Constantil m.p. 89-910.
Synthesis of 1,4-bis(allvldiethylaemooium)butene-2 dibromide.
(C2H5)U Br- Br(C, H)2
G-- =g .(H-C ~ ,-CB^.=CC.3
l*4-Bil(diethylmnino)butene-2 (16 al., 0.0686 mole) was dissolved in 30
al. of dry aetone and allyl bromide (12 al., 0157 mole) was added drep-
wise with stirring* After about half an hour, the mixture warned up to
about 500 and crystals began to precipitates Stirring was continued for
an hour after the flask had cooled to room temperabare. The white, slirght-
ly hygrsceople solid was removed, filtered, wrshed well with dry diise-
propyl other, and dried in a tvacuu desioeator. The dry product weighed 27.0
.o The yield was 39.3%.
Analysis Calcd. for CG8H36N2Br2s Br, 36.29. FP~und Br. 36.81.
Physical Constantsi mp. 172-83o
It was necessary to dry this pound in the Abdcrhalden drying pistol
before an analysis v A'ich corresponded to the calculated value was obtained.
Syrnthesi of 1j4-bis(allyldimothylodmnia)buteme-2 dibraeide.
NI X-CHG-a =M-CB2-B
2GHUB&gSE Br- Br-C'a-VFfl62
lo4-Bis(dlmvthylwuino)butenure (46.4 g., 0.507 mole) was dissolved in 75
ml. of dry aoetona and allyl bromide (75 g.o 0.63 mole) was added drepwige
using a polymer kettle equipped with mechanical stirrer, reflux sondensTr,
thermometer, and addition funnel. Toward the eid of the reaction, there
was such a large aount of solid formed that more dry saetone had to be
added. The reaction continued at room temperature far an additional hour.
The light yellow solid was removed and washed well with dry diisoprepyl
ether before drying in a vaUem desiccator. The dry solid weighed 10.3
g. The yield was 92.7%. The oompound was recrystallised frame both hemanol
and myl alcohol.
Analysits galed. for C14INugazr&Z Br, 41.60. Fo- I Br,. 41.57.
Physical Constant, am.p. 183-40.
Attempted Syathehsi of 1,4-bis(triallylm ontam)butsm-8 diohloride.
( CBrs-ur )3-^ -saaacH-- 2- ur.( e2)
1,4-Dishlorobutea-t (1.17 g.. 0.0094 mole) and triallyl mine (2.57 g.o
0.019 mole) were mixed in a teat tube vhioh we stoopered aid allowed to
sta d st resa temperature. At the sad of two months there wa approximately
a 60% yield of dark-red, viseous liquid. Upmn longer standing more liquid
separated. Sine the dibraaide had been prepared no further work was done
on this emipound.
Attempted SyntheaIs of 1,4-h.Is(diall-.1ncth.lnlm nlum)buteno-2 di-
(CH,=CH-CH2 )2--C -CHCH-C2 CH-CH-CHi)
This compound was made by two methods (1) the reaction of methyl chloride
with l,4-bis(diallylmino)butenm-2 and (2) the reaction of 1,4-dichloro-
butene-2 with diallylmethyl sine.
1. l,4-Bis(diallylsmino)butene-2 (1.72 go. 0.007 mole) ad methyl
chloride (0.71 go, 06014 mole), both chilled, were mixed in a tube .lhich
was immediately sealed end allowed to stand at room temperature. Only a
very small sount of viscous liquid separated even upon prolonked standing.
2. The diallylmethyl mine (1 g.. 0.01 mole) and l,4-dichlorobutene-2
(0.63 g., 0.005 mole) were mixed in a test tube vhioh was aimediately
stoppered and allowed to stand at room temperature. A rather lorgo quant-
ity of viscous liquid separated. No purification or analysis ase attempted.
Since the dibromide had been obtained in good yield, itivcrtiFation of this
compound was not pursued further.
Attorpted Synthesis of 1,4-bis(all ylimethylarmnoniUi)butone-- dichlnoride.
(CH3)2, ++ h 3)P
oCr 2-CH=CH- CCMr -N
H2 .KCI- -CIC 'C.-C1.CH2
This eaomound was made by two methodAo (1) the reortion of l,4-bis(di-
methylmino)butene&2 with allyl chloride and (2) the reaction of diallyl-
methyl mine with 1l4-difhlorobutene-2t
1. l,4-"is(d4imthylamino)butene-2 (0,7 g., 0005 mole) and allyl
chloride (0.75 g., 0.01 mole) were mixed in a teat tube wvhioh r.s iamediate-
ly stoppered and allowed to stand at room temperature. Within a short period
of time, both solid and liquid separated. No purification or analysis was
att arpt ed
2. Allyldtaethyl mine (1 g., 0.0118 mole) end l,4-diohlorobutene-2
(0.74 g., 0.006 mole) were m!xed in a t~et tube hioh nas immediately
stoppered. After standing& at room temperature for six hours, there was
a 50% yield of a visoous liquid. No attempt was made tn rify or analyze
Investigation of this oompolind was not pursued further.
Synthoais of bis(triallrly aaonium)aothane dibromide.
(co2,mn-c2)9-.a-s2-M-( CR-CGRm 2)
Bis(diallylmlno)methanu (8 ml., 0.0326 mole) was dissolved in 17 ml. of
dry hexanol and the allyl bromide (5.7 ml., 0.065 mole) was added dropwise
with stirring. Stirring at room t.aperature was oontLnued overnight. The
mixture was then heated gently for 3-4 hours, then oooled and removed from
the flask. The product was salted out of the hexanol ua a vsoous liquid
by use of dry diisopropyl ether. The vieoous liquid was washed well with
more ether and dried in a vaeuum deilcontor.
Analysise Baled. for C19B32N2Br2l Br. 35.65. Found Br, 35.40.
No melting point was obtained since the compo nd was never obtained in
crystalline form. It was necessary to dry this product in the Abderhalden
drying pistol before an analysis corresponding to the eeloulated value was
Attempted Synthesis of bi diallyloethylImonium)mithase dibromide.
(Gc12,H-CB 2)2, 9 H( 2-c00c2)2
Ca3 Br- aBr-CH
Bis(diallylamino)methane (4 ml., 0.016 mole) and methyl bromide (1.8 ml.,
0.032 mole), both cooled in dry ioe and aoetone, were mixed in a test tube,
whioh was i~nediately stoppered and placed in an iron tube for a day at
room temperature. The viscous liquid which formed was washed well with
dry diisopropyl ether and then dried in an Abderhalden drying pistol.
The compound was not obtained in pure enough form for an analysis
whiih would correspond to the calculated value. No melting point deter-
mination was made since the compound was not a solid.
Synthesis of bis(ellyldimothylaemonluma)methane dibromide.
(C~3)2 Br" BRg CH)2
ICHsH-CAH'* GCB-CH2 CH2
Bis(dimethyleaino)methane (5.1 g., 0.05 mole) was dissolved in 20 ml. of
dry benzene. Allyl bromide (12.1 g., 0.1 mole) was added slowly to the
above solution with stirring. After a short period of stirring, s8me
solid began to precipitate. Stirring was continued for several hours more.
The solid was washed well with dry diieopropyl ether and placed in a vaouum
desiccator to dry. Very shortly the solid became viscous and finally
turned to liquid. This viscous liquid was well dried in an Abderhalden
Analysis Caled. for C11E4N42Br.. Br, 46.42. Found Br, 46.85.
No melting point was obtained since the compound was never obtained in
Synthesis of triallylanilinium bromide.
The compound was synthesized by two methods, differing only in the solvent
used and the reaction time.
1. Diallyl anilino (17.4' .. 0.1 mole) was dissolved In 30 mi. of
dry roctone rnd allyl bromide (12.2 ,., 0.1 mole) was added drop.ise with
stirring. After the addition vrao complete1, he stirring at room temperature
was continued overnight. T.r electionn was then heated gently for about
three hours. After cooli kg, the reaction was treated with dry diieopropyl
ether end the small amount of viscous liquid which separated was dried in
a vacuum deslocator. The compound was very dark red. Recrystallization
2. Ulallyl aniline (17.4 g., 0.1 mole) waM dissolved in 30 ml. of
pcetonitrile and the allyl bromide (12.2 g., 0.1 mole) was added dropwise
with stirring. After stirring overnight at room temperature, the reaction
mixture was heated gently for three hours and then stirred at room tempera-
ture for three dvas. At the Pnd or this time, dry dileopro7yl ether was
added 'o salt oit the comnound. A very small yield of dnrk,viscous liquid
was obtained. After beinir washed several times with more ether, the liquid
was dried in a vnouum desiccator. Recrystallization was unsueoesiful.
Attempted Synthesis of 1,4-bis(diallyl-2-oyanoeth'lammonium)butente--
(CH2 dnH-M2)2 ,(C2-CHi2CH2)z
nC-ca2-oa CC GT~ C2-0 2-CI
1,4-Bis(diellylnaino)butene-2 (12.3 g., 0. O mole) and ^chloropropioni-
trile (9 g., 0.1 mole) were mixed in an Erlr-nrve' r flask which was then
allowed to stand at room temperature, with oooasional agitation. No heat
was evolved. After several hours erystels began to procipitate. These
crystals were filtered off, washed well with dry dlisopropyl ether, and dried
in a varuum desicantor.
Alnalysist Calod. for C2,IIN4Cl2s, Cl1 16.67. Calod, for
ClH 8iJ.ClZ I 01l, 22.21. Fouads Cl, 22.25.
From the analysis obtained, it is evident that HC1 split out of the
/-chloropropionitrile to form the dihydrochloride of 1,4-bis(di Allyl mino)-
Synthesis of Trioll l-2.-hydrox:ethylr Jr.ionliL- bromide.
Triallyl smine (16 g., 0*12 mole) was dissolved in 25 ml. of dry acetone
and the ethylene bromohydrin (14.6 g., 0.12 mole) was added dropwise with
stirring. The stirring was continued at room temperature for several days.
The reaction mixture was cooled in a beaker and dry diisopropyl ether added.
A viscous liquid separated whieh would not solidify. The liquid was dried
in a vaeutna desicoator.
Analysiss Calod. for C11H20NOBra Br, 30.50. Founds Br, 30.10.
No melting point was obtained sinee the compound was not obtained in
Attempted Synthesis of Triallvlcvanomethylanmonlum chloride.
Triallyl amine (16 g., 0.12 mole) was dissolved in 20 ml. of aeetonitrile
and the chloroaeotonitrile (8.9 go, 0.12 mole) was added dropwise with sti
ring. The reaction was stirred at room toperature for three days. The
mixture was then poured into a beaker and the compound precipitated by the
addition of dry diisopropyl ether. afrtr several vBashings with more dry
other, the product was played in the vacuum desiccator. After several dea
in the vacuum desheoator, the compound solidified. Attempts to recrystal-
lize tho product from the following solvents WPre made Rbsolute ethnnol,
mgl alcohol, hazanol-l, methylethyl ketene, methylisobutyl ketone,
ethylene dichloride, butyl cellosolve, and dioxane. Alyl alcohol _as the
only substance which avTe any indication of possibly being a suitable
rrcryetallirinr solvent. Since no rure trlillylcoynomethylaM~onnium chloride
oould be obtained, no analysis or melting point datn was secured.
Svnthecie of diallyldimethylammonium bromide.
(0Ha2-eHcag 2)--( 3R)2
Diallylmethyl Mine (11.1 g., 0.1 mole) was dissolved in 30 ml. of dry
acetone and the methyl bromide ws bubbled in slowly with oofling nd stir-
ring. Ihen ame methyl bromide collected in the cold trap, whish ws oo-c
noted by means of rubber tubing to the ton of the reflux condenser, the
passage or the bromide was diseontired nd the reaction 1aek mad contents
allowed to wanr un to room temperature. The mirture was stirred overnight
During the course of the reaction, a viscous liquid formed which turned to
a solid and then beek to a visaous liquid. The reaction mixture was cooled
in a beaker and dry diisopropyl ether added with vigorous stirring. A very
hygrosconic slid precipitated. The solid was washed several times with
more ether and wee then dried in a vaouu dresiccator. The product weighed
20.6 c. ,iving a l0 yield.
Analvsise Caled. for C3HljGBrn Br, 38.88. Found, Br, 39.08.
No melting point was obtained because of the extra hygroscopieity of
0 0 0. ? d 0
S t -C- co
H r4 r H -
oa Bss s
o l. _
3 m u
. c r '
r r4 *-4
N CO -4
0 U U
> r-I -
-i -i 1-
IV. POLYMERIZATION OF UNSATURATED QUATERNARY AMMONIUM HALIDES
A. General Diseussion
The general procedure followed in polymerising the unsoturrtcd quater-
nnry amroniumr oom-ounds with t-butyl hydroperoxide was as follows one
gr.a of the halide, enough vater to make a concentrated solution, and 0.012
g. of t-butyl hydroperoxide were mixed well and placed in an oven at 66
for an average time of 24 hours. This ratio of quaternary annonilm halide
to catalyst was maintained in making larger quantities of the polymers.
The polymer -as removed and hot distilled water added. If the poi ne"r
failed to dissolve in the water, it was broken down to small insoluble
particles. The resin was then washed with hot distilled water until the
filtrate did not give a test for the halide ion. The polymer was dried in
the oven at 65. Then the resin was dry, it was ground to 20-60 mesh
material. Only polymers of this mesh size were used in the experimental
work. The dry volume and settled wet volume were measured before the resin
was placed in an ion exchange column (a glass tube 20 or 42 mm. in diameter
closed at one end by a 50 mesh stainless steel disk upon which the resin
rested). A 4% solution of sodium hydroxide was passed through the resin
bed until the acidified effluent was halogen free. The hydroxide form of
the polymer was then washed free of excess sodium hydroxide and a 43 solu-
tion of potassium bromide was passed through the resin bed until the efflu-
ent was free of hydroxide ions. The bromide form of the polymer was then
washed free of excess potassium bromide and dried at 650. The dry polymer
was screened and the 20-60 mesh material stored for future use. All of the
water- nsoluble resins were cycled once before storage.
Individual details are discussed in the experimental part of this
sec ion. 29
Polymer of l*4-bis(triallylmvionim)butene-2 dibromide.
Fourteen greas of 1.4-bis(triallylaionium)butene-2 dibromide, 0.163 g.
of t-butyl hydroperoxide, rnd 1.03 g. of vater were well mixed in a beaker
and pFlaed in an oven at 656 for 24 hours. The polymer was light tan and
waterr insoluble. Twelve gram of the material was obtained. The yield was
BRA. The 20-60 mesh resin weighe3 6.1 g. Lid had a dry volume of 13.2 ml.
and a settled wet volume of 18.2 ml. The swelling ao-efficiet (wet volue
divide by the dry volume) was 1.38. After one oyeol, the 20-60 mesh
motorial weighed 4.3 go
Polymer of 1.4-bis(diallylmethylamnonium)butene-2 dibrcaide.
One grand of l,4-bia(dialylMtyllemtby onita)butenm-2 dibromides 0.012 g. of
t-butyl hydroperoxida. and 0.1 g. of water were well mixed in a beaker and
plated in an oven at C50 for 12 hours. At the end of this time., 0.024 s
of eatalyst ras added and the mixture allowed to remain in the oven for as
additional 24 hours. The polymer was light tan and water insoluble. The
dry resin weighed 0.6 g. The yieli was 60%.
Polymer of 1..4-bis(allyldiethylummonium)buteae-2 dibremide.
One grMi of 1,4-bis(allyldiethylaonuta)butenai dibramide, 0*018 g. of t-
butyl hydroperoxide, and 0.06 g. of water were well mixed in a beaker an
plaedJ in an oven at 650 for 18 hours. The pol.lyr was a rather hart.
tan-oclored, water-soluble solid.
Cooolyuer of 1,4-bis(allyldiethylammonium)butene-2 dibr aj4-a cd t era-
Nine grams of l,4-bis(allyldiethylamoniima)butone-2 dibrwaide, 3 g. of tetra-
allylemonita bromide, 0.0144 g. of t-butyl hydrbPeroxidae and 0.4t g. of
water were well mixed in a beaker and placed in an oven at 65 for 22 hours,
The copolymer was a tan, water-insoluble solid. Ten gras of the resin was
obtained giving a yield of 835.%. After grinding and sizing, 6.4 g. of 20-
60 mesh polymer was obtained. This material had a dry volume of 10 ml. and
a settled wet volume of 26 ml. The swelling coefficient was 2.6. After
one cycle, the 20-60 mesh part of the resin weighed 5.8 g.
Copolymers of 1,4-bis(tri-ll:'lnnooium)butenc-2 dibrornido and 1,4-bis-
(allyldimethyl~a onium)butene-2 dibromideo
Four copolymers of these two salts were made. The molar ratio of the two
components was varied (1 to 9j 2 to 8; 3 to 7; and 4 to 6)*
1. l,4-Bis(triallylamoninu)butene-2 dibrnoide (0.49 g., 0.001 mole)$
1.4-bis(allyldimethylanionium)butene-2 dibremide (3.469 g., 0.009 molo),
and enough water to make a clear solution, were mixed well and then 0.048
g. of t-butyl hydroperoxide was stirred in. The mixture, in a beaker, was
placed in an oven at 500 for 24 hours, then at 650 for 24 hours, and fi-
rally at 750 for 24 hours. The copolymer was a light-tan, water-insoluble
solid. The dry resin weighed 3.4 g. giving a yield of 85,. The copoly-
mer was ground to 20-60 mesh. This material weighed 3.2 g., and had a dry
volume of 5*0 ml and a settled wet volume of 13.0 ml. The swlling coef-
ficient was 2.6. After one cycle, the weight of the 20-60 mesh material was
2. 1,4-Bia(triallylononium)butene-2 dibromide (7.53 g., 0.015 mole),
and 1,4-bis(allyldiaethylwaonium)butene-2 dibromide (23 g., 0.06 mole),
were mixed with enough water to give a clear solution. The t-butyl hydro-
peroxide (0*18 g.) was stirred in and the mixture placed in an oven at 500
for 24 hours, then at 65 for 24 hours, and finally at 750 for 24 hours.
The oopolymer was a licht-tan, water-insoluble solid. The dry reain
weighed 15.4 g. The yield was 50. The 20-60 mesh material weighed 15.9
g. and had a dry volume of 21 al. and a settled wet volume of 72.8 al. The
swelling coefficient was 3.46. After one oyoles the amount of 20-60 mesh
material obtained was 13.1 g. It should be noted here that the atbalyst
to quaternary muuonium salt ratio is one-half the usual value.
5. 1,4-Bia(triallylamunium)butene-2 dibronide (10.98 g., 0.0228
mole), and l,4-bis(allyldimethylmanoniat)butern-2 dibromide (20.E go,
0.0525 mole) wre mixed with enough water to give a clear solution. The
t-butyl hydroperoxide (0.18 g.) was stirred in and the mixture, in a beaker,
placed in an oven at 500 for 24 hours, then at 650 for 24 hours, and final-
ly at 750 for 24 hour. The polymer was a tan, water-insoluble solid. The
dry resin weighed 15.8 g. The yield wes 50.1 The 20-60 mesh material
weighed 15.4 g. and had a dry volu of 24 ale and a settled wet volume of
75 l. The swelling ooefficient wa 3.12. After one oyale, the amount of
20-60 mesh material obtained was 13.7 g. It should be noted here that the
ontalyst to quaternary mamonian salt ratio is one-half the usual value.
4. 1.4-Bls(triallyla-ioniu)butene-2 dibromide (14.65 g., 0.030 mole)
and 1,4-bia(allyldinathylamontm)butene-2 dibrodmde (17.3 g.. 0.045 mole)
were mixed with enough water to give a olear solution. The t-butyl hydre-
peroxide (0.18 ge) was stirred in and the mixture, in a beaker, played in
an oven at 500 for 24 hours, then at o6 for 24 hours, and finally at 750
for 24 hours. The sopolymer wra a ton, wmgber-inseluble solid. The dry resin
weighed 17.9 g. The yield wa 5si. The 20-60 mesh material weighed 16.1
5. and had a dry volume of 21.5 ml. and a settled wet volae of 63.2 ml.
The swelling coefficient was 2.48. After one syele, the mount f 20-00
mesh material obtained was 13.8 g. It should be noted here that the
ontalyst to quaternary mamonium salt ratio is one-half the usual value*
l'ol'rer of bi ( t r i nll an lurn)ncth anij dibromide.
One gra of bis(triallylaemonium)methane dibromide, in the form of a vie-
cous liquid, was placed in a small beaker. The t-butyl hydroperoxide
(0.012 g.) was stirred in and the mixture placed in the oven at 650 for 13
hours. The polymer was a dark-red, water-insoluble solid. The dry resin
weighed 0.8 g. for a yield of 80W. More of the monomer was polv or:eod so
that a total of 8.8 g. of 20-60 mesh material was obtained. This enount
of the resin had a dry volume of 14.2 ml. and a settled wet volume of 49.2
ml. The swelling coefficient was 3.46. After one cycle, the amount of
20-60 mesh material obtained was 6.4 g.
Copolymer of bis(triallyl~anonium)methene dibromide and tetraallyl-
Bis(triallylmaonium)methane dibromide (4.5 g.), tetraallylamzonium bromide
(1.5 g.), and water (0.5 g.) vere well mixed and then 0.072 g. of t-butyl
hydroperoxide was stirred into the mixture. The material was placed in an
oven at 1000 for 48 hours and then at 650 for 48 hours. The copolymer wa
a dark-red, viscous, water-soluble liquid.
Conal-rner of bls(r il]t:'l.Eiori'ima)Ycthane dibro'ide rnd bis(allyldi-
Bis(triallyl~nionium)methane dibromide (1.8 g.), bis(allyldimethylrionloum)-
methane dibromide (4.3 g.), and water (0.168 g.) were mixed -well and then
0.084 g. of t-butyl hydroperoxide was stirred into the mixture. The solution
was placed in an oven at 560 for 20 hours. Both quaternary aMonium bromides
were viscous liquids whioh had been previously dried in an Abderhalden dry-
ing pistol. A the end of L0 hours of heating, the mixture was placed in
a vacuum desiccator to rrnove ca nuch of the water as possible. Another
0.004 g. of catalyst was added and the mixture replaced in the oven at
560 for several days. The copolymer was a dark, viscous. wnter-eoluble
Polymer of bis(diallylmethylaononium)methLan dibromide.
One gre of bls(dilllyliethylemoniux) ethane dibronide and foir drops of
water were well mixed. One drop (0.012 g.) of t-bftyl hydroperoxlde was
stirred in an.! the mixture placed in the oven for 24 hours at 560. The
polyner was a dark, partially water-inuoluble, elastio solid. The weiigt
of the dry resin was 0.09 g. The yield wa 9%.
PolyMer of triallylaniliniua bromide
One gra of triallylanilinium bromide, in the form of a visoous liquid,
was placed in a beaker and 0.012 t. of t-butyl hydroperoxide was stirred
in. The mixture was placed in an oven at 650 for 24 ho-rs. At the end
of this time. another 0.024 g. of catalyst was added. After ab.ju. a week
the polymer was found to be a dark, tar-like, partially water-soluble,
Polyer ofi trial lley canmethylamonita chloride.
One grnm of triallyleyanemethylmamoniia chloride and 0.03 g. of water wa
mixed well in a beaker and 0.012 g. of t-butyl hydroperoxide was stirred
in. The mixture was placed in an oven at 650 for two days, then the tmper-
ature was raised to 1000 for two days. At the eat of this tine the polymer
was a dark, hard, water-inaoluble solid,
Polymer or triallrlmethylwumoniau bromide.
Triallyluethylimonium bromide (19.8 g.) and 0.6 g. of water were well mixed
and 0.24 g. of t-butyl hydroperoxide was stirred in. The beaker contain-
ing the mixture was placed in an oven at 650 for 66 hours. The polymer
was a liglt-tan, water-insoluble solid. The dry resin weighed 16.5 g.
for a yield of 83.V. The 20-60 mesh material weighed 14.7 g. and had a
dry volume of 34 ml. and a settled wet volume of 52 ml. The swelling co-
effieient was 1.52. After one cycle, the mount of 20-00 mesh material
obtained was 12.9 g.
Polymer of triallvlbenzyl~mtonium bromide.
TriallylbenzylEamonium bromide (23.3 g.) and 1.27 g. of water were well
mixed in a beaker and 0.29 g. of t-butyl hydroperoxide was stirred in.
Tho mixture was placed in an oven at 650 for 48 hours. At the end of this
time, a crust of crystals had formed over the top of the mixture. Another
0.29 g. of catalyst was stirred in and the mixture replaced in the oven
for a week. The polymer was a tan, viscous, water-insoluble liquid.
Other conditions of polymerization were attempted. The catalyst to
quaternary anmonium bromide ratio was doubled (0.024 g. to 1 c.), and the
temperature of the polymerization was raised to 1000. The same tan, vis-
cous water-insoluble liquid was obtained.
Polymer of dlallyll L hrla.nojnim b'romnde.
One grea of diallyldimethylanmonium bromide ra~d 0.024 g. of water were well
mixed in a beaker and 0.012 g. of t-butyl hydroperoxide was stirred in.
The mixture was placed in a 650 oven for four days. The polymer was a hard,
light-tan, water-soluble solid.
Coc.ly, ;er of triall:ylmethvl rmmorium bromide and diallyldimethyl-
Four copolymers of those two salts were synthesized. The molar ratio of the
two c)mpononts was varied (1 to 9; 2 to 8; 1 to 1; and 4 to 1).
1. Trirjlylmwthylasaonlum bromide (1.2 g., 0.005 mole), und di-
allyldimethylsamonium bromide (9.3 g., 0.045 mole) were mixed with 0.29
g. of tater in a beaker. The t-butyl hydropcroxide (0.13 g.) was stirred
in end the mixturao r.s placed in an oven at 65 for approximately 64 hours.
The copolymer was a areei-colored, water-insoluble solid. The dry resin
weighed 7.8 g. rhe yirl,' :"as 74.31. The 20-60 mesh material weigehd 6.1
g. and had a ary volume of 10.0 ml. and a settled wt volume of 104 ml.
The swelling coefficient Tra 10.4.
2. Triallylmethylmmoniam bromide (3.5 g., 0.015 mole), and diellyl-
dimethyleumonium bromide (12.4 g., 0.062 mole) were mixed with 0.29 g. of
water in a beaker. The t-butyl hydropwroxide (0.15 ge) was stirred in si
the mixture was placed in an oven at 650 for a-praxiaately 64 hours. The
copolymer was a crescolored, water-insoluble solid. The dry resin
weighed 11.4 g. 'he yield was 71.7. The 20-60 mesh material weighed 9.9
g. and had a dry volume of 13.9 ml. and a settled wet volume of 97 il.
The E ellL-g coefficinmt was 6.97.
3. Triallylmethylsmonium bromide (9n.3 ., 0.04 mole), and diallyl-
dinethylanionlum bromide (8.3 g., 0.04 mole) were mixed with 0.43 g. of
rater in a beaker. The t-butyl hydroperoxide (0.21 r.) was stirred in and
the mixture was placed in an oven at 05 for approximately 64 hours. The
copolymer was a light-tan, water-Lna3luble solid. The dry resin weighed
13.7 g. The yield was 78..0. The 20-60 mesh material weighed 12.0 g. and
had a dry volume of 17.1 ml. and a settled wat volume of 65.3 ml. The
swelling coefficient was 3.22.
4. Triallymsethylemmonlim bromide (13.9 g., 0.06 mole), end diallyl-
dimethylammoniun bromide (3.1 g., 0.015 mole) were mixed with 0.41 g. of
water in a beaker. The t-butyl hydroperoxide (0.20 g.) was stirred in
and the mixture was placed in an oven at 650 for approximately 64 hours.
The copolymer was a light-tan, water-insoluble solid. The dry resin
weighed 13.0 g. The yield was 76.5.. The 20-60 mesh material weighed
11.4 g. end had a dry volume of 17.0 ml. and a settled wet volume of 44.7
ml. The swelling coefficient mas 2.62.
Copolymer of ^rillylbenrz;lnronrie bromide and tet rall-.'l l .onium
Triallylbenzylemmonium bromide (13.9 g.) and tetraell:'ylar oniinb0i bromide
(1.3 g.) were mixed well with 0.96 g. of water in a bAaker. The t-butyl
hydroperoxide (0.26 g.) was stirred in and the mixture was placed in an
oven at 650 for 24 hours. At the end of this time, a a-all portion of the
mixture was found to be water soluble, so an additional 2.6 g. of tetra-
allylamonium bromide, 0.58 g. of water, and 0.30 go of t-butyl hydro-
peroxide viere added and the mixture replaced in the oven for 80 hours.
The copolymer was a brown, v;ater-insoluble solid. The dry resin .-ifghed
9.3 g. The yield was 61.Q%. The 23-60 mesh material weighed 8.4 g. and
had a dry volue of 11.0 ml. and a settled wet volume of 135 ml. The
swelling coefficient was 12.5.
CopolYmer of triRllylmethyluaT.oni'r bromide and t-traallylr.-.mo;irm
Triallylmethylennonium bromide (10.5 g,) and tetraallylumoniun bromide
(3.9 g.) were well mixed with 0.26 g. of water in a beaker. The t-butyl
hydroperoxide (C.14 g.) was stirred in and the mixture was placed in an
oven at 650 for 36 hours. The monomers had sopolymerized within the first
30 minutes. The eopolyrer was a lght-ta., water-insoluble solid. The
dry resin weighed 12.0 g. The yield was 839.. The 20-60 mesh material
weighed 11.6 g. and had a dry volume of 18.5 ml. and a settle wet volume
of 37.0 ml. The swelling coeffiaient was 2.04.
Copolymer of diallyldimethylimonium bmraide and tetreallylaumonium
Diallyldimethylamnonium bromide (7.7 g.) and tetrnallylamoniut bromide
(3.2 r.) were well ruired with 0.70 .. of wvter in a beaker. The t-butyl
hydroperoxide (0.13 g.) was stirred in and the mixture was played in an
oven at 650 for 48 hours. The oo-olymer was a oresa-oolored, water-in-
soluble solid. The dry rosin weighed 9.2 S. The yield was 84.%3. The
20-60 mesi material weighed 8.6 g. and had a dry volume of 15.0 ml. and
a settled wet volume of 53.5 ml. The swelling ooeffloient was 2.58.
Polymer of triallyl-2-hydroxrethylammoniu bromide.
One gram of triallyl-2-hydrox;,ethylammonium bromide, in tho form of a
viscous liquid, vas planed in a beaker and 0.012 g. of t-butyl hydro-
poroxide vas stirred in. Tho .ixturo vas placed in an oven at 65 for
two dars. then the temperature va: raised to 1000 for two dCays. within
tho first hror, the mixture became Hark red ani quite viscous. After
foar days of heating the polymer was a dark, water-injoluble, elastic
eapolymer of triallyl-2-hydroxyethylamonium bromide and tetraullyl-
Trialyl-2-hydroryethylamionium bromide (3.95 g.) and tetrallylsmnoniu
bromide (1.3 g.) were mixed with 0.14 g. of water in a beaker. t-Butyl
hydroporoxide (0.06 o .) was stirred in and the Mixt'ire placed in an oven at
650 for about three weeks. The copolymer was a dark, elastic, water-
Copolymer of triallylanilinium bromide and tetraallylanmonium bromide.
Triallylanilinium bromide (3.0 go) and tetraallylamonium bromide (0.9 g.)
were mixed with 0.1 g. of water in a bedker. t-BFtyl hydroperoxide (0.048
ge) was stirred in and the mixture placed in an oven at 650 for about three
weeks. The copolymer was a dark, visco's, partially water-soluble liquid.
Copolymer of triallylcyanomethylawtoniun chloride and ttrolll-
Triallyloyanomethylmmoniu chloride (3.2 g.) and tetraallylammonium bromide
(1.3 g.) were mixed with 0.36 g. of water in a beaker. The t-butyl hydro-
peroxide (0.06 g.) was stirred in and the mixture placed in an oven at 650
for about three weeks. The copolymer was a dark, viscous, almost cam-
pletely water-soluble liquid.
Polymer of tetreallylrnmonhim bromide.
Tetraallylanmonium bromide (11.1 g ) and 0.34 g. of water were well mixed
in a beaker. t-Butyl hydroperoxide (0.13 go) was stirred in and the mix-
ture placed in an oven at 660 for 60 hours. The polymer was a tan, water-
insoluble solid. The dry resin weighed 11.1 g. The yield was 100.0%.
The 20-60 mesh material weighed 10.5 g. and had a dry volume of 19.2 ml.
and a settled wet volume of 28.5 ml. The swelling coefficient was 1.48.
V. ION EXCHANGE CAPACITY OF RESIM
A. General Disouesion
The method of obtaining the ion exehange epaoities of resins has
been previously described by Butler, Buneh, and Ingley (5). This method
was used in this investigati-n with several modifications.
The goaeral procedure used was as follow. All of the resins studied
had been through one ooaplate exchange cy-le. The bromide form of the
resin was thoroughly dried at 850 and then oaoled in a desiocator before
neir)hing out a 2.0000g. sapla into a 400 ml. beaker. One hundred ml. of
4% Ka&R solution was added to the resn. After about 24 hours the lolu-
tijn was filtered off and the resin washed at least four times with dis-
tilled water. Another 100 ml. of 4% NORH solution was added to the resin.
This process va3 contimed until there were no more than 10 parts of Br"
per million in the solution above the resin after the sodiui hydroxide
solution had stood over the resin for 24 hours. The concentration of
bronide ion was estimated by ca~parison with a standard solution treated
similarly with halogen free nitric acid and silver nitrate solution. Oht
the bramide ion euncentration reached the desired level of less than 10
parts par million, the hydroxide form of the resin was washed free of em-
cesB hydroxyl tons. Simes the solution had to be filtered fra the resins
it was necessary to use same distilled water to wash the resin from the
funnel into the original beaker. The initial volume of water and resin was
about 50 ml. T;io beer containing the resin was played in position for
measuraent of the pH. A mechanical stirrer mad Beean Medel -2 p ma4ter,
equipped rith Beokman f4990-75 rless eleetrode and Beekman #4970 salsael
electrode, were placed in position for obtaining the pH during the titration
of the resin. In general, 100 ml. of a 0.1 N hlr solution was added to
the beaker, and the time of addition observed. After 3 minutes, the pH
was recorded and the first milliliter of acid added at once from the burkt
A second 3 minute interval was allowed to pass, and the pH was determined
again. This process of addition and measurement of pH was continued until
the titration was completed. The results of the ion exchange capacity
titrationa carried out in this investigation are given in the experimental
part of this section.
The hydrobrotie acid used in these titrations was standardized against
standard sodium hydroxide solution* Approximately 0.2 N acid was used.
The 0.1 N potassium bromide solution was made by dilution of a 0.2 N
solution prepared by weighing the salt and making up the solution in a
A compilation of the properties of all ion exchange resins studied
herein may be found in Table VI.
B. Ep erBT antal
The resins, whose ion exchange oapaoities Rere determined, end the
letter used to represent esoh resin in the graphs and tables, are given be-
lcw. Also included is tle end point of each titration.
Monomer or Monomers Letter tion (ml.)
Sriallylmethylmmoniau bromide A 30.00
1.4-bis(triallylomoriuJn)butene-2 dibromide B 22.30
Bis(triallylmmonium)erthane dibromide C 19.20
Totraallylemmonium bramide D 18.90
Diallyldimethylmmnonium bromide (3 moles) E 33.30
Tetraallylammonium bromide (1 mole)
l.4-bis(allyldiethylmm-aoniu)butene-2 dibromide (2.04 moles) F 30.60
Tetraallylamoni'ai bromide (1.16 moles)
Triallylnethylemonium bromide (3 moles) G 27.50
Tetraallylamonium bromide (1 mole)
Triallylbenzylummonium bromide (3 moles) 3 24.52
Tetraollylammonlum bromide (1 mole)
1,4-bis(triallylwmmoniau)butene-2 dibromide (1 mole) I 38.40
l,4-bie( llyldimethylsmmoanum)butene-2 dlbr-mide (9 moles)
1,4-bis(triallylmmoni'l)buten~-2 dibromide (2 moles) J 35.40
1,4-bis(allyldimethylamonium)butene-2 dibromide (8 moles)
1.4-bis(triallylumnonia)butene-2 dibromide (3 moles) K 33.57
1,4-bie( allyldimethylammoniui)butene-2 dibromide (7 moles)
1,4-bis(triallyl mnoniua)butonm-2 dibromide (4 moles) L 31.40
l,4-bl(aellyldlmethylmmoonium)butne-2 dibromide (6 moles)
Triallylmethylmmwonitm bromide (1 mole) M 36.47
Diallyldimethylammonium bromide (9 moles)
Triallylmethylamwoniut bromide (2 moles) N 36.63
Diallyldimoth'lammonium bromide (8 moles)
Triallylmethylamonium bromide (1 mole) 0 3W.90
Diallyldimethylmmonium bromide (1 mole)
43 End Point
Monomer or Morono;er Letter tion (ml.)
Triallylmethylwmonium bromide (4 moles) P 32.40
Diallyldimethylanoniau bromide (1 mole)
All of the resins, with the exception of M, were aboum 60 ml. in
initial volume before 100 ml. of 0.1 N IBr solution was added and the
titration with 0.2024 N HBr begun. In the ease of M, the initial volume
was about 76 ml. and 75 ml. of 0.133 N LBr solution was added.
The data obtained from the titration of the resins listed above are
given on the following pages of this section. Graphs of these data follow.
DATA ON TITRATION OF RESINB A-
Time Tol. pa of
in HBr A B C D E P G H
3 0 12.50 12.18 12.19 12.20 12.47 12.22 12.24 12.18
6 1 12.40 12.06 12.14 12.19 12.45 12,28 12.30 12.19
9 2 12.33 12.01 12.09 12.19 12.42 12.24 12.29 12.11
12 3 12.28 11.99 12.04 12.12 12.38 12.22 12,29 12.17
15 4 12.29 11.95 11.99 12.07 12.34 12.20 12.28 12*.1
18 5 12*26 11.90 11.95 12.04 12.32 12*20 12*28 12.12
21 6 12.24 11.86 11.88 12.00 12.51 12.19 12.27 12.07
24 7 12.22 11.78 11.80 11.95 12.30 12.11 12.25 12.04
27 8 12.22 11*70 11.73 11.89 12.28 12.10 12.24 12.01
50 9 12*18 11.63 11;63 11.84 12.27 12.08 12.22 11697
33 10 12.17 11.57 11.50 11.77 12.27 12.06 12.181 1,92
36 11 12.13 11.47 11.38 11.68 12*26 12.03 18,13 11.89
39 12 13.10 11.30 11.15 11.56 12.25 11.99 12.10 11*15
42 13 12.08 11.12 10.87 11.47 12.21 11.95 12.05 11.,0
45 14 12.01 10.90 10.58 11.31 12.13 11.90 12.01 11*73
48 15 11.97 10.62 10.33 11.09 12*09 11.85 11.97 11.67
51 16 11.90 10.35 10.03 10.71 12.02 11.70 11.90 11.59
r4 17 11,85 10.10 9.72 10.27 12,02 11,68 11.83 11.48
57 18 11.79 9.83 9.33 9.72 11.97 11.68 11.77 11.37
60 19 11.76 9.59 8.53 8.04 11.93 11.62 11.68 11.15
63 20 11.89 9.50 7.42 6.55 11.90 11.57 11.57 10.83
66 21 11.61 8.86 7.03 5.85 11.87 11.48 11.43 10.49
Time Vol. pH of
in HBr A B 0 D E F G H
DATA ON TITR/PION OF RHSIN I-P
Tfil Tol. pa of
in HBr I J K L M I 0 P
J K L M N 0 P
in HBr I
69 22 11.l
72 23 11.?
75 24 11.I
78 25 11.I
81 26 11.
84 27 11*.
07 28 ll.
90 29 11.4
93 30 11.3
96 31 11.,
99 32 10.9
102 33 10.6
105 34 10.5
108 35 9.9
111 36 9.6
114 37 9.2
117 58 8.S
120 39 7.0
123 40 6.5
126 41 6.2
129 42. 5.9
132 43 5.6
135 44 4.0
138 45 3.0
141 46 2.7
D \C NB A
B) R C Ad
I 1 1'5 jo j5 0
'1 ~?. 2024 N Ui r
A. P~cl,-wcr c ftr 1 ~le lo=rn ~~ ~iC
1. Fclgc'r oC 1 t 1 a(tz I .'a.-c.r te utre2 r.:i .re
C. tetr&i1 a Bd-c I llzlRlrcrc,,,? ) iethL ne di~r vlp!e
D. :,r ~f t-ro-Al~ j~~ol~;'~r7de
1. I: 20 2 V' -s? :.
,T.1. cf 0.20U 4 1 I' i
Ier,. d r
r. C cl;a.,:r c.f diall I diett; 1 I .. l l. brctlide( i a.c.le ; c P; re trn l l-
a- :i .r.lic, rrc.r ,'ie( I ,..:cle).
F. lC.r.cl rcr f 1.L c le(sa l .l i e t r cr, iit ')t ut .e-2 d It rc lie(2. Cci ,T;.:le )
an I tr traal]i., rla or, I t' .rr. i-e( .l c': olete .
G. ,c.-cl ,er .lf tr ftll:.;.et]-; :arr. r,'uz, br -:, de(" .c..l er srd tEtraall l-
|r .- r de Irde l :.;l q .
H. r, c,-'...-.c.r of triB:]. 1re ,. la.-.r, nlum trc,.Ide(- c-sn ) rnd t etrt all; -
a..-cr, ur. r -. i .e(] r ).
1, 1. 2? 25 y) 35 40 5
z2. ci -D.2Cr2L4 1 -TYr
c-yul.,uv c r of 1.4- 11r rl)Rn~~~s :~rr= dbrcrilde(I mole) as
1 .4 bi i (El-l d i.Tiervy1Irasicr.IuDbut ene-2 aI br-:: 'de(, ic.lcr ).
J Cc rc~;e c I k I e (t r I 1 I]..,' L ) bu tF;, e- d I brc-A e (2 mclB) .9rd
1.L* 'ls(B1@:a. llf ic ra:t a-.mrnuz,)tuter e-2 L',rci.d(8 mVrmsde.
K. 'Zcic.j-nr r cf .lar bl s(o riid I 1)b.A 2 jitrride(3 r r,' a a)ad
I ) gts: l.1. l~t'eLi;y]L= ~c'.n rIm): uct~.r- *?1ir: -bie(7 ic.1ee!..
L. C. .,1~cp e of 1.4 r.isC tr-a1:.1Ironu)btcree2 dlirc'~de( r,oler ) Fkd
b I s (m I I y I d I :.r e t 1,1 rIum ter, o-.1 d I r riI d e m Iea
C iAI IV
II. i a, r) rr r, eN 2
I-. Co>r~.::'.. r c t rlrl I.,l r ch. L. -,lur '.*rcrf1e(l
Z---or. i i,. r -. .1de ( mol )
T- - ; rr of t r !%11. lo-et I ilo r Lr t r..:' Id e(4
- --- I----- I I
3'V; 4' ,, 4*;
mr.l ) a#,,. lall.,'l, I 'netr.;, l-
r, let.) i asc di al l/ ld I T t rh. 1-
n.lI) ari di llyllim thyl-
rol e a) nd dlall., 1.1 et!L: 1-
'a *~ 0 U U N0
V% N a W
I t E i
4 0 m N a M M f M m w O ^
* f 'a4a 'Ma OngMo N
N fl Pi f ii0t-INiM 0i i N
o 0 0 0 0 00 o 1 0
gn N 4 r4 4 ^ r% (m N N mi fl fi Ai Ci fl
R nR$'AAt sa ZIAU
1-1SXstBa 1-1 W8
Vt. DISCUSSION OF RESULTS
The procedure found best suited for preparing the 1,4-bis(dialkyl-
enino)butene-2 compounds was that using 1,4-diohlorobutene-2 and the
secondary eIine in benzene solution. The yields of the one new amine and
the other tertiary mines, previously reported, were considerably larger
when l,4-dichlorobutene-2 Tas used than when 1,4-dibromobutene-2 was used.
The yield of the new tertiary mine was 6P.3%.
The attempt to produce l,4-bis(dialkylamino)butana compounds in order
to ascertain whether the butene-2 double bond entered into the polymeri-
zation was unsuccessful. The dihydrobro idse of the desired tertiary mines
were obtained, but when these mines were liberated with sodium hydroxide,
none of the mines were isolated.
Another method was used to show that the double bond in butene-2
did not take part in the polymerization when t-butyl hydroperoxide was
used as a catalyst. It has been shown previously (1,2) that three allyl
double bonds must be present in the quaternary usonium salt before a
oross-linked, water-insoluble polymer can be obtained. Usin. this infor-
mation, several oompo nds were prepared, varying in number of allyl double
bonds from two to four to six. It was found that a water-soluble polymer
resulted when only two allyl double bonds were present in the molecule,
in addition to the butene-2 double bond, while, on the other hand, when
four or six sllyl double bonds were present, a water.insoluble polymer re-
sulted. The evid-nce obtained in this work shows that the butene-2 double
bond does not take part in the polymerization when t-butyl hydroperoxide
is used as a catalyst.
About half of the quatornary smonil salts were obtained in solid
form. The others were obtained in the forn of viscous liquids, came of
which could be dried enough to secure analyses vhich corresponded to the
calculated values. Perhaps the incomplete polymerization of some of the
iuoternary *aonlum compounds was caused by the Impurities contained in
these compounds. Purification was attempted in almost all cases, but sam
of the products seemed to resist purifloraion. BHnco, these compounds hed
to be used ms obtained. Yields of the quaternary arionriun salts ranged
The bis(trialkylsmlonium)othane dibron.ides did not pol:'morise to
giva very high yields. This fact may be attributed, in part at least,
to the relative instability of the compaonds. This is born out by curve
C on Graph I. A high mine capacity is indioated. Lewis (17) reported
the ease with which the bis(dialkyluino)methane compounds decomose.
It ws found that the quaternary ammonium broaidea which uontalned four
or more allyl double bonds, gave oross-linked, water-insoluble polymers.
hoen only two do'ible bonds were present, a wmtor-solhblo polymer resulted.
In general, the results of this invostigati-,n sunport those previously
obtained (2,3.5) that the higher the coefficient of arelllne, the nearer
the experimental ion exchange capacity of the resin approaches the theo-
retioal exchange capacity.
It was found, in this work, that lowered yields of the resins were
obtained iwen the ratio of catalyst to quaternary gaonium salt ras lower
-ian 0.012 g. of catalyst to 1 g. of quaternarye
The resins obtained in this investigation were of mueh higher capaoity
than those obtained previously by Bunch (6) and Ingley (7). Several of the
resins had extremely large swelling coefficients, thereby lowering their
capacity in milliequivalents per milliliter. With but two exceptions,
the resins produced in this work all had ion exchange capacities above
two milliequivalents per gram. The majority of the resins had capacities
above 0.7 milliequivalents per milliliter. These values compare favorably
with some of the coamercially available strongly basic anion exchange res-
ins. Of the resins investigated in this project, the one showing the
highest capacity and one of the lowest swelling coefficients was a copoly-
mer of 1,4-bis(triallylas onium)butene-2 dibromide (1 mole) aed 1,4-bis-
(allyldimethylmonium)butene-2 dibramide (9 moles). This resin showed a
capacity of 0.96 meq./al. or 3.89 meq./ge
The effect of substitution of certain groups on the nitrogen center
of the ion exchange resins has a definite effect upon the ratio of the
theoretical capacity obtained oxperimentally. This effect can be observed
in Graphs I-III. The substitution of one methyl group for one allyl group
on the tetraallylueaoniam bromide monomer (curve D), produces a polymer
(curve A) in vriioh the experimentally determined capacity more nearly ap-
proaches the theoretitil ion exchange capacity.
In the second graph, curve E shows a copolymer which results in a
higher ratio of the theoretical capacity than the copolymer represented
by curve F.
It oan be easily seen, in Graph III, that the copolymer represented
by curve I shows a higher ratio of the theoretical capacity then the ee-
-ol'-mer corresponding to ourve L.
This increase in ratiq of the experimental capacity to the theoretical
capacity is attributed to the increased basicity of the nitrogen center due
to the presence of gro'ips with greater electron releasing properties.
Since the allyl group can exhibit resonance forms, it will be less elec-
tron roleosin- than such groups as methyl or ethyl. Th'iC, it can easily
be seen that the resins fall in the order -hich one would assume because
of prior knowlcdga of the elcctronio properties of the vartiou :,zbstita-
In makinG. these comparisons, pairs of resins were chosen thich had
approximately the srae swelling coeffiDiEnts. The ratio of the experi-
mental capatoty to the theoretical capacity of eaoh resin was used in the
comparison, rather than the theoretical capooity, since the letter is
fixed Inmediately upon choice of the monomer or monomers.
The other ourres co Id be compared, but it would be rather hazardous
to attempt to draw any ornolusion fro- such exp rimentcl vork containing
two variablesb (sollin; coefficient r.nd nubstituent group), T'he con-
clusions reached abovo, aro thoco rhich the er.pornimnt6l .work in this
project has rugicsted.
In cycling; the resins in ion exchange oolumns, it was apparent that
the enso and rraidity of conversion to hydroxide or bromide was dependent
upon the subetituent gro'aps. resins containing a greater proportion of
the stronger electron releasing groups could be more rapidly exchanged
than those resins containing the weaker electron reloasing groups. The
exchange from the bromide form of the rosin to the hydroxide form was
slower than the exchange froe hy3roxide fern to bromide form, as previously
observed by Dltlor, Bunch, and In.-lcy (5). However, there was eome modifi-
oa' ion in the sepsrare re-os. That is, rith resins which corrtained th?
buton-e-2 group, the cxohange from bromldo to hydroxide was faster than
Ingley observed in the polymer of totraallylnemonium bromide, while the
reverse exchange was slower than in the case of the polymer of totraallyl-
aanonlu bromide. In the case of resins containing the methyl group, the
exchange from bromide to hydroxide was slower than in tetraallylaemonium
bromide polymer, with the reverse reaction being faster than in the poly-
mer of tetraallylamonium bromide. Of course, for these observations to
be completely valid, kinetic studies would have to be made. This varia-
tion in rates is attributed to the decreased basicity of the quatornary
a~moniwn center in the case of the butene-2 derivatives and the increased
basicity when such strongly electron releasing groups as methyl or ethyl
Fifteen new unsaturated q'czternary ammonium halidpe were prepared.
Eipht of theme new compounds were charnoterized. The identity of the re-
maiing seven compounds was assumed on the basis of the means of prepara-
tion, since purification was not effected. The aompounds were prepared by
reaction of the appropriate tertiary Maine and appropriate aliphatio or
One new unsaturated tertiary smine was prepared as an intermediate.
It was characterized and physical constants determined. It was obtained
in largest yield by reacting dialyl amine and 1,4-dichlorobutane-2, neu-
traliing the hydrochloride fonrmd vith sodium hydroxide, separation and
:.urification u" the amine by distillation.
The unsaturated quaternury ammonium halides were polymerized by means
of t-butyl hydroperoxide. Those compounds containing two allyl double
bonds cave thermoplastic, water-soluble polymera, but 'hose containing
four or more allyl double bonds formed thermosetting weater-insoluble
polymers. Canpounis containing two allyl double bonds could be oopoly-
morized rlith a ccrapound containing three or four double bonel to form a
water-insoluble copolymer. It was shown that the double bond of 1,4-di-
aminobutene-2 derivatives did not enter into the polymerization.
The substitution of certain groups on the nitrogen center of the ion
exchange resins was found to have a very definite effect upon the rate of
exchange of the various ions end upon the ratio of the experimental capao-
ity to the theoretical capacity. This effect was found to be consistent
with that which would be predicted on the basis of modern electronic inter-
pretations. The change in the rate of exchange of the various ions anr in-
the ratio of the exprriaental capacity to the theoretical capacity is
attributed to the variation in basicity of the quaternary asmonium center
caused by substitution of groups of differing electrophilic properties
Several anion exchange resins were prepared which compare favorably
in pH range and capacity with those now available.
(1) Butler, G. P. and Bunch, R. L., J. am. Cham. 3oo. 71. 3120 (1949).
(2) Butler, G. B. and Ingley F. L., J. a. Chm. Soo 73, 895 (1961).
(3) Dutler, G. B. and Goette, R. L., J. Am. Chem. Soe. 74, 1939 (1952).
(4) Johnson, R. A, M.. S. Thesis, Universitv of Florida, 1952.
(5) Butler, G. B., Bunah, R. L., and Ingley, F. L., J. AM. Chm. Soo.,
74, 2543 (1952).
(6) Bunch, R. L., Ph. D. Dissertation, University of Florida. 1949, p.
(7) Ingley, F. L., Ph. D. Dissertation, Univ;rsity of Florida, 1950. p.
(8) Cason, J. and Rapoport, n., "Laboratory Text in Organic Chemistry,"
Prentioe-aall, Ino., Now York, N. Y., 1950, p. 270.
(9) Prevost, C., Cmpt. rend., 186. 1209, (1028).
(10) Lewis, N. J., Ph. D. Dssertation, University of Florida, 1951, p.
(11) Villstatter and V.irth, Per., 46, 537 (1913).
(12) Amundsen, L. H., Mayer, R. H., Pitta, L. So. and Malentacehi L. A.,
J. Am. Ohm. Soe.. 75, 2118 (1951).
(13) Partheil, A. and von Broleh, H., Ber., 30, 619 (1897).
(14) unoh. R. L., Ph. D. Discertation. University of Florida, 1949, p.
(15) BanEh, R. L., Ph. D. Dissertatlon, University of Florida, 1949, p.
(16) Butler, G. B. and Benjinin, B. M., J. Ches. Ed.. 28, 191 (1951).
(17) Lewis, N. J., Ph. D. Dissertation, University of Florida, 1951, p. S
The author wishes to express his sincerest appreciation to Dr. G. 8.
Butler, vho conceived this research project and under whose patient guid-
ance this work was carried out. His suggestions and enooura.~ement both
in the carrying out of the research described and in the writing of the
Dissertation, were unstintedly contributed.
The author desires to aexress thanks to his parents, Mr. mnd Mrs. W.
Le Goette, e~n to his laboratory partner, Carl Michaelis, who generously
helped by proof reading the manuscript. It is the wish of the author to
give his sincerest thanks to Miss Emily Smith, who graciously typed the
To the members of the author's Supervisory Coimittee and to the other
staff members, of the Department of Cheiistry and to his student assooBtee
the author wishes to express gratitude for their advice and suggestions.
Robert L. Goetto was born in Gainesvillle Florida, on May 12, 1929.
In September 1945 he entered the University of Florida. He wa grad-
uated in June 1949 with high honors, receiving the degree of Bachelor of
Science in Chemistry.
In July 1949 he entered the Graduate School of the University of
Florida. He was graduated in Septeber 1950. receiving the degree of
Master of Science.
Mr. Goette is currently enrolled in the Graduate Sohool of the Uai-
versity of Florida. He held a Graduate Fellowahip from July 1949 until
June 1952. During the suamer of 1952 he was employed as a Researoh Assia-
tnnt on a Smith, Kline, and French research grant and as a Research Asai-
tent on an Atomic Energy Comaission research grant.
During his undergraduate work, Mr. Goette was employed for two and
a half years as a laboratory assistant in the )Iutritin Laboratory of the
State Experiment Station and for one and a half years as a laboratory
assistant on an Office of Naval Research Project.
He is a member of the American Cheeical Society, Phi Bota Kappa, Phi
Kapoa Phi. GOma SigRB Epsilon, Kappa Delta Pi, Delta Phi Alpha, and Phi
This dissertation was prepared under the direction of the Chairmani
of the candidate's Supervisory Comnittee and has been approved by all
members of the committee. It was submitted to the Dean of the College
of Arts and Sciences and to the Graduate Council and was approved as
partial fulfilment of the requirement for the degree of Doctor of
January 31, 1953
Dean, College of Arts and Seiences
Dean, Graduate School
SUPERVISORY CO mITTEES