Group Title: effect of certain groups on the basic properties of polyquaternary ammonium hydroxides ..
Title: The effect of certain groups on the basic properties of polyquaternary ammonium hydroxides ..
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Title: The effect of certain groups on the basic properties of polyquaternary ammonium hydroxides ..
Physical Description: 61 leaves : ; 28 cm.
Language: English
Creator: Goette, Robert Louis, 1929-
Publication Date: 1953
Copyright Date: 1953
 Subjects
Subject: Ammonium salts   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Dissertation (Ph.D.) - University of Florida, 1953.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
General Note: Bibliography: leaf 60.
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Bibliographic ID: UF00098038
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
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Resource Identifier: alephbibnum - 000551409
oclc - 13336673
notis - ACX5884

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The Effect of Certain Groups on the Basic Properties

of Polyqucaternarv Ammonium Hydroxides












By
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


Page

LIST OF TABLE ............... .............................. ii

LIST OF ILLUSTRATIOHS. ........................... ........... I

Seot ion
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,

VII. SUlMaY............................................

DIBLIOGRAI'HY........................................... 60

AOK0ltWDSE,- S. S.............................................. 1b

BIOGRAlHICAL ITMS ................................... ...... 82

C0OWITTEE REr'?T............................................ 65










LIST OF TABLES


Table Page

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


Graph Page

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










Is IIrODUTICTION


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

polymer.

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

used.
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.






2

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-

gation.

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










4

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









6

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

experimental ,ork.

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

nirertheless atisfaetory.

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

co-workers (12).

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.









9

B. Experimental

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-

ports.

Synthesis of Triallyl raine.

(cT2;clH-cnH2)s-

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

constant e

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-

butane-2.










10

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.









11

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.

(C2Hi)2-N-(CH2)4-N-( 2H5)2











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

distilling pot.

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

was obtained.

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.

(GA3)2-W-(CH2)4-(7LCHs)2

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










18

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.













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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

15










16

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.










17

Bo Experimental

Synthesis of 1,4-bis(triallyleBmonium)butine-2 dibriaide.
+ +
(Che=G-CH 2)3-N-2"ICHC-GH-C2-N- (CH2"'Cn2 )3
Br- Br-

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

one*











tempted Syntheeei of l,4-bia(diallylathylmmoniam)butene.2 dibro-

mide.


(C-CZ-0G92)2-tH.,-< B-ea2-0 02-aw )2
Br- Br-

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

with l,4-dibraoobuteae-2.

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

(023=c-wz2 )3-1j-3
Br-

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
wN-CHI-CR=CBH-CHH -N*
G-- =g .(H-C ~ ,-CB^.=CC.3
HB2=2B-CH 2
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.










20

Syrnthesi of 1j4-bis(allyldimothylodmnia)buteme-2 dibraeide.

(%3)2" *((E)2
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)
C1l C1"

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.










21

Attempted SyntheaIs of 1,4-h.Is(diall-.1ncth.lnlm nlum)buteno-2 di-
chloride.

(CH,=CH-CH2 )2--C -CHCH-C2 CH-CH-CHi)
Cl- Cl-

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










22

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

the compound.

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)
Br- Br-

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

obtained.

Attempted Synthesis of bi diallyloethylImonium)mithase dibromide.

(Gc12,H-CB 2)2, 9 H( 2-c00c2)2
N-CE2-N.
Ca3 Br- aBr-CH









23

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
"N-OH2
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

drying pistol.

Analysis Caled. for C11E4N42Br.. Br, 46.42. Found Br, 46.85.

No melting point was obtained since the compound was never obtained in

crystalline form.

Synthesis of triallylanilinium bromide.


Br-
The compound was synthesized by two methods, differing only in the solvent

used and the reaction time.










24

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

was unrclcassful.

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--

diohloride.

(CH2 dnH-M2)2 ,(C2-CHi2CH2)z
N-C12-CHaCH-C02-N\
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.










25

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)-

butene-2.

Synthesis of Trioll l-2.-hydrox:ethylr Jr.ionliL- bromide.

(CBH2CH-CH )3-N-GH2-CH2-C
Br-

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

crystalline form.

Attempted Synthesis of Triallvlcvanomethylanmonlum chloride.

(CH02 "-H2)3-N-0CH2-CN
C1"

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-










26

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
Br-

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

the compound.


















Sa c



0 0 0. ? d 0

S t -C- co






N 4





H r4 r H -








oa Bss s


* *
9 a





i i
H *-.


H -

a a


.4.4
2 7'



'i;
27


0
3-4 0

0' '-


41 d
a
^1^ *


F.

o l. _


3 m u


E*





4 1
h d




o 0
o o




U
o U

g 0
0 0



















r











5 q
O .
i- .!F
* I




-C S
V0 0






o o
-'4 0a
. c r '


I .~a
co 1





















, *



u .


3 N


.5
r
-


I-




U
a


X

S
wa .




b.






5-4
ri


h1










*


-4
p


*o
s-


I-
S9
w s


S.

j 0


NC..





*



Xe





BS


a
.3



2-I


8 i0
* r
a C



n !
aI

O>
w
I-







Eg
fI S
* 0'

3 I



ia
..I0

i:s


a u







i~sti|


22i
r r4 *-4
NN N



r r
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0 U U
8 5









> r-I -
Is
a


-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










30

B. Experimental

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-

allylemonium bromide,

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










31

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

2.3 g.

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









35

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-

annoninu bromide.

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-

methylann'onium)methene dibromide.

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

liquid.

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,

viscous liquid.

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









35

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-

eTmoniun bromide.

Four copolymers of those two salts were synthesized. The molar ratio of the










36

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

bromide*

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

br-mide.

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









38

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

bromide.

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

smi-s)lid.

eapolymer of triallyl-2-hydroxyethylamonium bromide and tetraullyl-

anmonium bromide.

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









39

650 for about three weeks. The copolymer was a dark, elastic, water-

insoluble solid.

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-

samonium bromide.

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
40










41

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

volumetric flask.

A compilation of the properties of all ion exchange resins studied

herein may be found in Table VI.










42

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.
Ead Point
of Titra-
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
of Titra-
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.










TABLE IV


DATA ON TITRATION OF RESINB A-


Time Tol. pa of
in HBr A B C D E P G H
Min.

O 0

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










TAB LE1V
(eeant'd)

Time Vol. pH of
in HBr A B 0 D E F G H
Minl


69

72

75

78-

81

84

87

90

93

96

99

102

105

108

111

114

117

120

125

126

129

132


11.50

11.38

11.20

10.95

10.60

10.21

9.97

9.28

7.84

6.74

6.24

5.73

4.00

5.08

2.73


7.70

7.90

7.00

6.60

6.20

5.99

5.63

6.20

4.30

3.65

3.30

3.08

2.98


6.72

6.54

6.46


6.15

5.87

5.70

5.40

4.80

4.32

4.00

3.80

3.54

3.45

3.28

3.18

3.03

3.00

2.93

2.80


4.05

3.24



2.79

2.64

2.54


11.81

11.75

11.67

11.59

11.46

11.51

11.11

10.82

10.40

10.08

9.71

9.18

7.50

6.73

6532

5.91

5.12

3.28

2.91

2.68

2.53

2.41


11.58

11.23

11.06

10.76

10.43

10.12

9.80

9.64

8.82

7.20

6.68

6.28

5.98

6.51

3.89

3.10

2.80

2.62

2.50


11.22

10.90

10.53

10.14

9.70

8.70

7.05

6.68

6.11

5.07

3.37

3.03

2.88

2.70


10.12

9.70

9.10

7.43

6.68





4.76
6.26
4075



2.86

2.63










TABLE V

DATA ON TITR/PION OF RHSIN I-P


Tfil Tol. pa of
in HBr I J K L M I 0 P
Min.


0

3



9

12

15

18

21

24

27

30

33

?6

39

42

.45

48

51

E4


12.AO



12.52

12.40

12.29

12.P8

12,P6

12..2

12.20

12.19

12.19

12.17

12.15

12.12

12.06

12.08

12.03

12.00


12.10 12.22

12.20 12.23

12.20 12.25

12.20 12.27

12.19 12.15

12.18 12.15

12.11 12.12

12.11 12.11

12.09 12.08

12.07 12.04

12.02 12.05

12.00 12.02

11.99 12.00

11.97 11.99

11.92 11.96

11.91 11.89

11.89 11.87

11.85 11.82

11.80 11.78

11.76 11.72

11.71 11.68

11.69 11.61


12.28

12.29

12.0SO


12.28
11. 28

12.27

12.20

12.12

12.11

12.08

12.06

12.04

12.00

11.95

11.90

11.87

11.82

11.78

11.75

11.69

11.62

11.55

46


12.o5

12.32

12.29

12.26

12.21

12.19

12.16

12.13


12.37

12.57

12. 6

12.34

12.853

12.Z2

12.31

12.26


12.31

12. 0

12.28

12.25

12.23

12.22

12.20

12.19

12.17

12.13

12.12

12.1C

12.06

12.08

12.03

12,00

11.99

11.93

11.99

11.87

11.82

11.79


12.31

12.30

12.27

12.23

12.22

12*21

12.20

12.18

12.15

12.12

12.10

12.06

12.06

12.05

12.0

12.01

11.97

11.95

11.92

11.90

11.88

11.83


12.12 12.21

12.09 12.20

12.07 12.18

12.05 12.18

12.02 12.12

12.00 12.09

11.98 12.07

11.93 12.03

11.88 12.00

11.87 11.97

11.85 11.92

11.80- 11.88

11.75 11.82

11.72 11.78


18 11.98

19 11.96

20 11.92

21 11.90










TABLE V.
(cont''d


I


pH of
J K L M N 0 P


Time Vol.
in HBr I
Min.

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


87

.2

30

75

70

57

52



1i

L8

35
6
fi

,0

5O

0

2

58





0

0

0

B

5

3


11.62

11.53

11.47

11,38

11.25

11.11

10.85

10.59

10.29

10.00

9.73

9.43

9.08

8.40

7.80

6.78

6.48

6.20

5.98

5.60

4.80

3.30

2.88

2.68.


11.53

11.43

11.32

11.18

10.99

10.72

10.42

10.15

9,88

0.58

9.26

8.78

7.60

6.91

6.68

6.33

6.11

5.82

5.36

3.02

3.08

2.78


11.48

11.35

11,21

11,02

10.78

10,43

10.10

9.70

9.30

8.58

7.20

6.61

6.38

5.97

5.40

4.00

5.29

2.99

2.78


11.75

11.68

11.62

11.57

11,49

11.89

11.28

11.13

10.90

10. O

10.28

9.97

9.64i

9.30

8.61

7.15

6.56

6.23

5.90

5.43

3.76

3.02

2.72


11.78

11.73

11.69

11.62

11.57

11.49

11.41

11.30

11.12

10.90

10.62

10.25

9.89

9.52
9,02

7.53

6.72

6.26

5.88

5.23

3.42

2.9,

2.70


11.67

11.59

11.63

11.44

11.82

11.18

10.99

10.68

10.32

9.93

9.55

9.08

7.72

6.72

6.26

5.83

5.07

3.18

2.79


11.72

11*66

11.68

11.48

11.37

11. -O

10.98

10.BR

10.10

9.67

8.09

6.79

6.23

5.57

3.44

2.92

2.68







GRAPH I


D \C NB A











B) R C Ad














I 1 1'5 jo j5 0
'1 ~?. 2024 N Ui r

Le-e'd:

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 ).

49




















































1, 1. 2? 25 y) 35 40 5
z2. ci -D.2Cr2L4 1 -TYr

I.e~c r.d:

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
5-:







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-
.. E

"as
e*S
N 3


I -
:3
S.h
"fR P&


'a *~ 0 U U N0


V% N a W
I t E i
idi~a


4 0 m N a M M f M m w O ^


U






N
I




i Eq


* 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


u4
Is
nt




ri.
-a:



At
0;
3*

e-
&
M-










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

from 60-100l.

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-

ent groups.

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










57

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

ara present.










V11. SUMMAR


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

aromatic halide.

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-










59

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.









BIBLIOG.AHT


(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.
42.

(7) Ingley, F. L., Ph. D. Dissertation, Univ;rsity of Florida, 1950. p.
40.

(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.
22.

(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.
26.

(15) BanEh, R. L., Ph. D. Dissertatlon, University of Florida, 1949, p.
25.

(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










ACKNOWILDGMENTS


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

Disserteaion.

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.










BTOGRArHICAL ITEMS


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

Eta SipFna








C'j:.TITIES REPORT


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
Philosophy.

January 31, 1953



Dean, College of Arts and Seiences



Dean, Graduate School


SUPERVISORY CO mITTEES



maskUt
n Qbf4i~innap


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