Synthesis and characterization of poly(amide-sulfonamides

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5-1-1985

Synthesis and characterization of poly(amide-sulfonamides): new candidates for reverse osmosismembranes.Thevarak Rochanapruk

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TABLE OF CONTENTS

ABSTRACT * i as

ABBREVIATIONS II

ACKNOWLEDGEMENTS Ill

1.0 INTRODUCTION 1

1.1 Polyamides .. .. .. .. .. .. 7

1.2 Polysulfonamides .. .. .. .. .. 19

1.3 Poly (amide-sulfonamides) .. .. .. 28

2.0 OBJECTIVE .. .. 34

3.0 RESULTS AND DISCUSSION 3E

4.0 EXPERIMENTAL .. 54

4.1 General information .. .. .. ..54

4.2 Synthesis of monoacetanilides 17-18 .. 57

4.3 Synthesis of the diamine monomers 21-23 60

4.4 General low temperature solution

polymerization procedure . . . . . . 63

4.5 General Yamazaki polymerization

procedure . . . . . .. . 64

REFERENCES . .75

APPENDICES

NMR Spectra

Monoacetanilide derivatives 17-19 . . 78

Diamine monomers 21-23 . . . . . . 80

Infrared spectra

Monoacetanilide derivatives 17-19 . . 83

Diamine monomers 21-23 . . . . . . 86

Polymers 24-33 89

Thermal Gravimetric Analysis

Polymers 24-33 99

LIST OF TABLES

1. Semipermeability of Cellulose Acetate Membrane

to Aqueous Solution of Various

Electrolytes . . . . . . . . . . . . 6

2. The Effect of Inorganic Salts on Membrane

Flux and * Salt Rejection . . . . . . 13

3. Polycondensation Reaction of p-Aminobenzoic

Acid using Triphenyl Phosphite in Various

Solvent System containing 4* Lithium Chloride 18

4. Thermal Properties of Polyamides and

Polysulfonamides under Nitrogen Atmosphere . . 27

5. Results of the Selective Sulfonylation

Reaction of 4,4'-0xy Dianiline, 4 , 4 '-Methylene

Dianiline and Anhydrous Piperazine . . . . 40

6. Results of the Hydrolysis Reaction of the

Monoacetanilide Derivatives 17-19 with

6 Molar Hydrochloric Acid 43

7. Results of the Polymerization of 21-23

with Terephthaloyl , Isophthaloyl and

Sebacoyl Chloride using Low Temperature

Solution Technique . . . . . . . . 46

8. Results of the Polymerization of 21-23

with Terephthalic and Isophthalic Acid

using the Yamazaki Reaction . . . . . . . . 49

9. Solubility of Poly (amide-sulfonamides)

in Various Organic Solvents . . . . . . . . 53

List of Figures

1. NMR spectrum of monoacetanilide 17



4. NMR spectrum of diamine monomer 21



7. IR spectrum of monoacetanilide 17



10. IR spectrum of diamine monomer 21



13. IR spectrum of polymer 24










78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

9B

99

23. TGA

24. TGA

25 . TGA

26. TGA

27 . TGA

28. TGA

29. TGA

30. TGA

31 . TGA

32 . TGA

curve of

curve of

curve of

curve of

curve of

curve of

curve of

curve of

curve of

curve of

polymer 24

polymer 25

polymer 26

polymer 27

polymer 28

polymer 29

polymer 30

polymer 31

polymer 32

polymer 33

100

101

102

103

104

105

106

107

108

109

ABSTRACT

Commercially available aromatic diamines such as

4,4'-diamino diphenyl ether and 4,4'-diamino diphenyl

methylene were treated with N-acetylsulfanilyl chloride

to give the amino-sulfonamido-acetanilide derivatives.

These derivatives were treated with 6 M hydrochloric

acid to give the diamine monomers containing a preformed

sulfonamide linkage. These monomers were polymerized

with various diacid chlorides using a low temperature

solution technique. Polymerizations using the Yamazaki

reaction have also been investigated.

The polymers obtained were characterized using

infrared spectroscopy, thermal gravimetric analysis and

differential scanning calorimetry.

ABBREVIATIONS

ABSC = N-acetamidobenzene sulfonyl chloride

(N-acetylsulfanilyl chloride)

Ac = Acetyl

DMAc = N ,N-dimethylacetamide

DMF = N ,N-dimethylformamide

DSC = Differential Scanning Calorimetry

IR = Infrared

m.p. =melting point

Me Methyl

NMR - Nuclear Magnetic Resonance

\inh. = Inherent viscosity

NMP = N-methyl-2-pyrrolidone

PDT = Polymer decomposition temperature

Ph = Phenyl

Py = Pyridine

Tg = Glass transition temperature

TGA = Thermal Gravimetric Analysis

TLC = Thin Layer Chromatography

II

ACKNOWLEDGEMENTS

I wish to express my sincere thanks and gratitude to

my research adviser Dr. Jerry Adduci for his continuous

guidance and support throughout the project. My thanks

is also extended to my graduate committee, the Rochester

Institute of Technology for the partial funding of this

project and Dr. J. Sutherland for the evaluation of the

mechanical properties of the polymers.

Ill

1.0 INTRODUCTION.

Since the early 1970's, reverse osmosis has

undergone rapid development as a process for the

desalination of brackish water (1). In reverse osmosis,

saline water is placed in contact with a suitable

membrane at a pressure exceeding the osmotic pressure of

the solution. Fresh water, or water with lower salt

content, permeates the membrane and is collected for

use. A concentrated brine is discharged from the high

pressure side of the membrane as a waste stream.

Reverse osmosis development has been directed primarily

toward the production of fresh water from natural

brackish water. However, reverse osmosis units have

also been tested in a variety of other water and waste

treatment applications, including water recovery and

concentration of wastes from sewage plants. For a

membrane with a given specific permeability, the fresh

water output or flux of a reverse osmosis device is

directly proportional to the membrane thickness.

Membrane area can be maximized and thickness minimized

in the hollow fiber form. Fine hollow fibers provide a

thin, self supporting membrane with a very high

surface to volume ratio desirable for reverse osmosis.

The important properties for a reverse osmosis

membrane are flux rate, salt rejection and durability.

The water permeation rate or flux rate of the reverse

osmosis membranes can be expressed as gallons per day

per square foot (g.f.d.) or cubic meter per square meter

per day (ms/m^/day) based on the outside diameter of the

membrane. The selectivity of a reverse osmosis membrane

is often expressed as the X salt rejection (SR), which

is defined by the equation:

X SR <Cf-Cp)/Cf x 100

where Cf = salt concentration in feed water,

Cp = salt concentration in the permeate.

The salt rejection required in a revese osmosis

application depends upon the proposed water use.

Generally, for the production of potable water, a

permeate concentration of <500 ppm is desired. Thus, a

salt rejection on the order of B5X - 95X is required for

brackish water desalination <1000-5000ppm) and >98.5X

for sea water desalination (35,000 ppm).

The rejection of a reverse osmosis membrane varies

with the solute composition in the feed water.

Multivalent ions are generally rejected better than the

monovalent ions. Another factor which influences the

salt rejection is pH. The durability of a reverse

osmosis membrane is usually influenced by both the

membrane properties and the nature of the system in

which it is operating. The decline in performances of

the membrane can be attributable to membrane compaction,

fiber collaspe, fouling (slime or scale), chemical and

biological degradation.

One of the most widely used reverse osmosis

membranes to date is cellulose di-triacetate 1 .

As demonstrated by Reid and Breton (2), cellulose

acetate membranes showed salt rejection ranges of 86 -

99X of electrolytes. The electrolytes used were the

chlorides of sodium, magnesium and calcium. In

addition, ammonia, sodium bromide and sodium fluoride

were tested.

The behavior of cellulose acetate as a reverse

osmosis membrane can be best explained by examining its

internal structure. In addition to the amorphous

region, cellulose acetate's internal structure posesses

a moderate degree of crystallinity . As suggested by

Fuller and Pape (3), the crystalline regions in

cellulose acetate have strong intermolecular forces,

large enough to restrict the Brownian motion and hold a

large percentage of polymer chains in a highly ordered

region. Reid and Breton (2) proposed that, when water

molecules are introduced into cellulose acetate, they

are concentrated in the amorphous regions. It is

postulated that they are hydrogen bonded to the carbonyl

oxygens of the acetyl group, thereby filling the voids

with bound water. In a structure such as this, it is

proposed that two different diffusion mechanisms

occur. Firstly, the ions and molecules that cannot

enter into hydrogen bonding are transported across the

membrane by hole type diffusion. That is, their

diffusion depends upon the probability of hole formation

in the membrane. Filling the pores of cellulose acetate

with tightly bound water reduces the probability of hole

formation, thereby reducing the diffusion of this type.

Secondly, those ions and molecules that can combine

with the membrane through hydrogen bonding and can fit

into the bound water structure, are presumed to be

transported across the membrane by alignment of the

hydrogen bonds with the membrane.

After these molecules combine with one side of the

membrane, they migrate across by transferring from one

hydrogen bonding site to another and are finally

discharged from the other side of the membrane. The

hydrogen bonding concept for the semi-permeability of

cellulose acetate was supported by the fact that using

electrolytes such as sodium chloride and sodium bromide,

which can enter into hydrogen bonding with cellulose

acetate, were effectively rejected by the membrane. On

the other hand, sodium fluoride used as the electrolyte,

was found to be less rejected by the membrane. This can

be explained by the fact that the smaller fluoride ion

can enter into hydrogen bonding and diffuse at a greater

rate.

A low rejection would be expected for those

solutes that can enter into water-cellulose acetate

structure through hydrogen bonding. Ammonia is an

example of this type of solute. It was found that the

permeability for ammonia was 30X or about one third of

that for sodium chloride (2).

Table I: Semipermeability of Cellulose Acetate

Membrane to Aqueous Solution of Various

Electrolytes (2).

Pressure on Electrolyte Concentration (X) Salt

Membrane (psi) Rejection

850 NaCl 0.11 M 96

850 Na.SO. 0.018 M 971 T

800 NH3 0.04 M 30

800 ocean water 4X 96

800 NaF 0.0012 M 86

850 NaBr 0.0012 M 93

715 MgCl1 0.031 M 99

After long term usage, cellulose acetate membranes

show poor chemical and mechanical stability (4).

Because of this, many new polymers have been developed

and evaluated as candidates for reverse osmosis

membranes. Polymers having significant desalination

properties are polyacrylonitrile, poly (vinylene

carbonate), Nylon 6-6, poly ( isobutyl vinyl ether),

polytetrahydrofuran and a copolymer of ethylene

dimethacrylate and hydroxyethyl methacrylate. In

addition, a polymer blend of ethyl cellulose and

poly (acrylic acid) also has good desalination properties

(5).

1.1 Polyamides.

Polyamides with the general structure of

(HN-R-NH-CO-R'-CO) have been developed and evaluated

as candidates for reverse osmosis membranes. These

polymers can be prepared using a low temperature

solution polymerization technique or an interfacial

polycondensation method (6,7,8).

Among the new polyamides synthesized,

poly (m-phenylene isophthalamide) 2 gave a promising

performance as a reverse osmosis membrane.

As was demonstrated by R. McKinney and J.H.

Rhodes (9), this polymer gave a 98. 4X sodium chloride

rejection, with an electrolyte concentration of

5000 ppm and a pressure of 1000 psi . The flux rate

for water was 2.5 gal/fta/day.

Poly(m-phenylene isophthalamide) can be prepared by

reacting m-phenylene diamine with isophthaloyl chloride

using a low temperature solution or interfacial

condensation method.

The structure of this polymer is kinked due to the

meta linkages of the amide groups in the polymer

backbone. These kinked regions form the amorphous

region in the polymer. One would expect

poly (m-phenylene isophthalamide) therefore to be highly

amorphous, and have many empty volumes or voids in the

polymer membrane. Since there are fewer regions of

crystallinity (ordered region) in this polymer as

compared to cellulose acetate, 2 should therefore have a

lower water diffusion rate than cellulose acetate.

Experimentally this was found to be the case (9).

On the other hand, linear polymers, for example

polyterephthalamide of p-amino benzhydrazide 3 ,

gave a salt rejection of 98. OX and flux rate of 8.7

gal/ft*/day using a pressure of 1000 p.s.i.. Sodium

chloride with a concentration of 5,000 ppm was used as

the electrolyte (9).

"[-^^H-^-^^^

Another polyamide that has an unusual structure and

properties is copolyoxamide 4 . This polymer posesses

both a highly hydrophilic oxamide linkage and a

hydrophobic aromatic diacid unit. This combination

provides both high water permeability and high

mechanical strength in aqueous solvents (4).

r V HOOHH0 ,

f-C"a-CHri-S-S-i-CHrCHa-i-S-^^.?_N

The membrane from this polymer (4) was prepared

by casting a 10X (w/v) polymer solution in

N,N-dimethylacetamide containing 6.6X (w/v) lithium

chloride on a glass plate, heated in an oven to remove

the solvent, and gelled in water. Scanning electron

microscopy of this membrane showed the structure to

consist of voids ranging in size from less than lum to

lOOum. In addition, regular voids of 200-300 A in

diameter were also observed. This membrane showed

sodium chloride rejection values of 85 - 99X and high

rate of water diffusion.

10

Tirrel and Vogl (4) also found structural

differences in membrane cast from trifluroacetic acid

and N ,N-dimethylacetamide - lithium chloride mixtures.

Electron micrograph cross sections of membrane cast from

N ,N-dimethylacetamide - lithium chloride mixtures,

showed two dense surface layers connected by a regular

array of capillaries, 4 - 5 um in diameter. This

structure is a unique feature of this system and is

comparable to the structure of a cellulose acetate

membrane (4 ) .

Membranes cast from a trif luroacetic acid-

polymer

solution, consist of voids ranging in size from less

than lum to lOOum (approximately the entire film

thickness). In addition , regular voids of 200-300 A

in diameter were also observed in the solid portions of

the membrane. Membranes cast from N

acetamide- lithium chloride mixtures showed a better

flux rate than those cast from trifluroacetic acid (4).

The effect on the membrane flux rate in the

presence of inorganic salts has also been investigated

in detail. As demonstrated by M.A Kraus and co-workers

(10), a typical aromatic polyamide membrane cast under

certain conditions from a binary solution, i.e. a

solution containing only the polymer and the solvent,

1 1

gave a different flux rate than a membrane cast from a

solution containing inorganic salts. The membrane cast

from a binary solution exhibited a water flux rate of

0.85 m8/m2/day. Membranes prepared under the same

conditions using the same polymer mixed with inorganic

salts such as lithium chloride or lithium perchlorate

exhibited fluxes as high as 250 - 600 m/ m*/day. The

effect of various inorganic salts on the flux rate of

the aromatic polyamide membranes are summarized in

Table II.

12

a

Table II: The Effect of Inorganic Salts on Membrane

Flux and X Salt Rejection.

Salt Salt Concentration X Rejection Membrane Flux

X (w/v) Molari ty Urea NaCl (m*/m*/day)

LiCl 5 1.2 77 . 34

LiCIO.4-

10 0.47 78 - 51

LiClO- 5 0.94 85 - 42

ZnCl^ 10 0.73 83 99 46

Mg(ClO^)^ 5 0.22 80 96 38

Mg(ClO^)^ 10 0.45 72 96 63

ZnCl^ A 10 0.73 88 99 92.4

Py.HCl ) 20 1.73

Mg(ClO^)^10 0.45 80 99.9 189

Py . HC1 ) 20 1.73

a

Membrane consisted of a 1:1 mixture of

poly m-and p-phenylene isophthalamide.

13

The combination of magnesium perchlorate/

pyridinium hydrochloride with 2 gave the best results in

X salt rejection and water flux rate. Many experimental

facts indicate that the "salteffect"

is primarily due

to the changes in the solvent activity. Evidence was

obtained from the Nuclear Magnetic Resonance spectra of

the polymer solutions. It was observed that a lithium

chloride-

aromatic polyamide interaction caused a down

field shift in the NMR signal of the amide protons of

the polymer (11). It was also found that under certain

conditions, such as temperature, pressure and time, the

amount of the solvent lost from a cast membrane before

coagulation decreased with increased additive

concentration. This is due to a decrease in the

solvent's vapour pressure. By increasing the additive

concentration, the membrane will contain a higher

solvent to polymer ratio at the instant of coagulation,

resulting in a more open structure.

In addition, solvent evaporation will lead to an

asymmetrical structure already in the membrane, as was

shown by scanning electron microscopy (12). The

asymmetrical structure should be more pronounced with a

higher additive concentration. As the solvent

evaporates, the salt-polymer concentration near the

solution-air interface increases thus impeding further

14

evaporation of the solvent. The diffusion is slow in the

highly viscous solution, and the salt-polymer

concentration equalization is slow relative to

evaporation rate. An asymmetrical structure results upon

coagulation, since the polymer concentration is higher

at the upper surface and lower within the membrane.

Both the evaporation and coagulation phenomena are

important in determining the final structure of the

aromatic polyamide membranes.

The effects of inorganic salts in solution of aromatic

polyamides need further study.

Polyamides can be prepared by an interfacial or

low temperature solution polymerization techniques. An

example is the synthesis of poly (m-phenylene

isophthalamide) 2 .

HN

0NH. cl-c

D.C-Cl

DttAc /Py.- H H O O -i

t-ionigjH

^

Polyamides can also be prepared by the reaction

between a diamine and a dicarboxylic acid using the melt

polymerization technique, for example the preparation of

Nylon 6-6, 5 .

^*

2HN-f-CH24-NH2+ H00C-[CH2-J-C00H

fO 0 -.

nh{ch2}nh-c{ch2]-c-

4 -I

2Y\H20

A new method for polyamide synthesis was

reported by Yamazaki and co-workers (13). A high

molecular weight polyamide was obtained Cinh. = 1.5

dL/g in cone, sulfuric acid) when p-phenylene diamine

was reacted with isophthalic acid in the presence of

triphenyl phosphite, pyridine and lithium chloride.

.MM^^MMi

(PKO)//Pj/Licl

NMP / ioo'c) WtiH

16

It is postulated that the reaction proceeded via

the N-phosphonium salts of pyridine followed by

aminolysis:

'H.

-I-

/J 6 5

N

1 I H-P-OCOR

+r'cooh

, \

C H O OC6H56 D

1

r iRhJHj-

>R1CONHR2

? C6HgOH + P OH

Cj.Hj.oJ

Imai and co-workers (14) have also prepared

various aromatic and aliphatic polyamides using the

Yamazaki reaction. The polymers obtained gave high

inherent viscosity values. For example the polymer

obtained from the reaction between 4 , 4 '-oxydianilie and

terephthalic acid gave an inherent viscosity value of

2.39 dL/g in concentrated sulfuric acid. Using

isophthalic acid, the polymer obtained gave an inherent

viscosity value of 1.98 dL/g, suggesting high molecular

weight materials.

Important factors in the Yamazaki reaction are

temperature, solvent, monomer concentration, metal salt

type and reaction time. The best solvent for this

rection was found to be N-methyl-2-pyrrolidone with the

monomers concentration being 0.6 mole.

The results for the polymerization of p-aminobenzoic

acid using the Yamazaki reaction are summarized in Table

III.

17

a

Table III: Polycondensation Reaction of p-Amino Benzoic

Acid Using Triphenyl Phosphite in Various Solvent

Systems containing 4X (w/v) Lithium Chloride.

b

Solvent System X Yield Inherent Viscosity

(ml/ml) (dL/g) c= 0.5 g/dL

Dioxane/Pyridine (40/10) 21 0.07

DMF/Pyridine (40/10) 11 0.06

DMAc/Pyridine (40/10) 99 0.71

Pyridine (50) 100 0.21

NMP/Pyridine (10/40) 100 0.29

NMP/Pyridine (20/30) 100 1.21

NMP/Pyridine (30/20) 100 1.57

NMP/Pyridine (40/10) 100 1.27

NMP/Pyridine (45/5) 100 1.26

a) Monomer concentration = 0.4 mole, triphenyl

phosphite concentration = 1 mole/mole of monomer,

temperature = 100C, reaction time = 6 hrs.

b) measured in concentrated sulfuric acid at

30C.

1.2 Polysulfonamides

Polysulfonamides with the general structure

(-SOj^-R-SO^NH-R'-NH-) can be prepared in high

molecular weight by the reaction of a disulfonyl

chloride and a diamine using an interfacial

polycondensation technique. A series of high molecular

weight polysulfonamides were prepared from the reaction

of an aromatic disulfonyl chloride with various

aliphatic diamines by 5.A. Sundet and co-workers (14).

An example of this is the rection between 1,6

hexamethylene diamine with benzene disulfonyl chloride

to form a polysulfonamide 7 .

imcl rfCH2-]-NH:

r V H / V o

19

Using an interfacial polymerization technique,

polymers with the inherent viscosity ranging from

0.1-2.62 dL/g were obtained. Higher molecular weight

polymers were obtained when sodium carbonate rather than

sodium hydroxide was used as the acid acceptor. This

was attributed to a reduction of the sulfonyl chloride

hydrolysis at the lower pH. In addition, the carbonate

may be acting to "saltout"

the diamine more rapidly

into the organic phase.

In the synthesis of polysulfonamides, pH control is

important. Sulfonamides dissolve in 10X sodium

hydroxide solution because of the acidity of the

sulfonamide group.

^ e? f-A-J-

_V>

-N-S-

-N=S- -N-S-

o o o oe

Thus interfacial polymerizations carried out at

higher pH levels cause the formation of the anion

o

(-SO^-N-) which can be sulfonated in sufficient

amounts to form a branched and/or insoluble polymers.

This phenomena was observed in the reaction of

1,2-ethylene diamine and 1 ,3-benzenedisulfonyl chloride,

using sodium hydroxide as the acid acceptor.

Sundet and co-workers (14) were unable to prepare

wholly aromatic high molecular weight polysulfonamides

due to the low basicity of the aromatic diamines and the

lower reactivity of sulfonyl chlorides as compared to

20

carboxylic acid chlorides. Low molecular weight

polysulfonamides were also obtained by C.S. Marvel and

his co-workers ( 15 ) by reacting aromatic diamines with

aromatic disulfonyl chlorides. The polymers obtained

using solution polymerization technique with

N,N-dimethylacetamide or tetramethylene sulfone as the

solvents, gave a range of inherent viscosity between

0.02-0.19 dL/g.

Op ,, 0 0 H H

cIs-Ar-scI + nHj-Ar-nh, v J_s-Ar-sn-Ar1-n-

m n i- r\ ft

, @"

"

^ ^^1,3:14

Imai and co workers (16), were able to

synthesize wholly aromatic polysulfonamides

using a low temperature polymerization technique.

Unlike Marvel and co-workers (15), 2-methyl pyridine was

used as the solvent and pyridine as the acid acceptor in

their reactions. This combination of solvent and acid

acceptor gave a polysulfonamide with an inherent

viscosity of 0.43dL/g with 99X yield. The formation of

high molecular weight polymer was attributed to the

21

solvent's ability to sufficiently dissolve or swell the

polymer thus permitting complete polymerization.

Polymerizations using amide type solvents such as

N,N-dimethylacetamide (a good solvent for aromatic

polysulfonamides) , produced inferior results. Aromatic

sulfonyl chlorides are known to react with

N,N-dialkylamides to give the ammonium salt (17). The

reaction of which, produced a mixture of sulfonamides

(through path A) and the amidines (through path B) in

the following equation.

Arso2cI rco<h!

B

Arso,-o-c=n;^t R

Cl

Armhz

Ar-so,-nh-Ar

R.C0.N.CH3

CM,

HCl

N

AR'

AR-S03H HCl

22

It was assumed that N ,N-dimethylacetamide reacted with

the aromatic disulfonyl chlorides to form the sulfonic

acids which resulted in the termination of the

polycondensation and yielded only low molecular weight

polysulfonamides.

Polysulfonamides can also be prepared using

active di-1-benzotriazoyl disulfonate and aromatic

diamines under mild condition. It was shown by L.A.

Paquette (19) that l-hydroxy-2(lH) pyridone

benzenesulfonate reacts with an amine to form the

exclusively sulfur-oxygen cleavage products. Reacting a

di-benzotriazoyl disulfonate with an aromatic diamine

yielded a polysulfonamide 8 (20).

VJ--- S-O-N N

H'N<5>^3}--

{-0#v^^.+ .A

23

Various solvents such as N-methyl-2-pyrrolidone

and hexamethyl phosphoramide were used in the

preparation of 8 . The acid acceptors varied ranging

from sodium carbonate, pyridine to N-ethylmorpholine.

For the polycondensation of di-1-benzotriazoyl

disulfonate with bis(4-aminophenyl ether), the solvent

and acid acceptor combination which gave the highest

inherent viscosity (0.55 dL/g) was hexamethyl

phosphoramide and 2,6-dimethyl pyridine.

High molecular weight polysulfonamide esters 10

have also been prepared (21). Reacting di-1-benzotriazoyl

disulfonate with an aminophenol, a diphenol monomer 9

was obtained by the cleavage of the sulfur-oxygen bond.

N*

*O-S-AR-S02-0.NN"

. 2H,N-Ar10H

1 1 /%

-^HO-AR-NH-SOj-AR- SOj-NH-AR-OH 2 HO-N N

2k

The diphenol 9 was reacted with an aromaticdi-

acid

chloride such as terephthaloyl chloride, using

tetraethyl ammonium chloride as a catalyst, to give 10

in good yield.

HO-AR-NH-S02-AR-NH-AR-OH + ClCO-AR-CO-Cl

0 i

AR-NH-S02-AR-S02-NH-AR-OC - AR-CO

N

10

The polymerization was carried out using an

interfacial technique. The best results were obtained

when a chloroform/water solvent mixture was used. The

polymer obtained in this case had an inherent viscosity

of 0.86 dL/g in N ,N-dimethylacetamide.

In general, aromatic polysulfonamides exhibit

lower thermal stability than that of aromatic

polyamides. R.C.Evers and G.F.L. Ehlers (22) found that

piperazine aromatic polysulfonamides 11 decomposed

around 300-350C.

N-SO,-AR-SO

11

N

AR

<>^)>.

-CK-

Polyamides showed a higher decomposition

temperature around 410-450C (6). The lack of thermal

stability shown by polysulfonamides can be attributed to

the nitrogen-sulfur (N-S) bonds in the polymer backbone.

The thermal stability of polyamides and polysulfonamides

are summarized in Table IV.

2b

Table IV: Thermal Properties of Polyamides (6) and

Polysulfonamides (22) under Nitrogen Atmosphere.

Polymer

/ \(-N N-SO,

-N N

S0'

v--SO,

CH,

-e-N i

CH, SO,

Inherent TGA

Viscosity curve (C)

0.07 350

0.12 355

0.07 310

SA

"<Q><g>"-^<Q>^-<>S0A

N 4 CH,+NH-CO *\(_)/"CO-^j-

N/A

400

1.27 380

0.40 395

470

a) Polymer decomposition temperature.

27

1.3 Poly (amide-sulfonamides) .

Poly (amide-sulfonamides) ,12, with the general

structure (NH-CO-R-SO^NH-R'-) can be prepared by

reacting eithermeta-

or para-chlorosulfonylbenzoyl

chloride with various diamines using an interfacial

polymerization technique (23).

0 0

Cl-c- AR-S-ClII

0

H,N-R-NH2

0 Oh

NHC-AR-S-N-R-

12

R. -tCH,}--CH2CH2-

^)o^> ,

"<H-

AR

. <^

The polymers obtained had inherent viscosities

ranging from 0.14-0.18 dL/g. Nearly all of the polymers

were soluble in a wide range of organic solvents such

acetone, m-cresol and N ,N-dimethylacetamide.

2c

Poly (amide-sulfonamides) were also soluble in basic and

acidic solvents such as formic acid, glacial acetic

acid, pyridine and 10X aqueous sodium hydroxide

solution.

The thermal gravimetric analysis curve of the

aliphatic poly (amide-sulfonamides) showed a

decomposition at 320-360C in a nitrogen atmosphere.

Some aliphatic poly (amide-sulfonamides) showed a melting

temperature range of 150-300C, as determined by DTA,

differential thermal analysis. Low melt temperatures,

amorphism and high solubility behaviour of

poly (amide-sulfonamides) can be attributed to the

presence of non-ordered structures having a head-to-tail

and head-to-head linkages.

(CO-R-SO-NH-R'-NH-SO-R-CO-NH-R

'-NH ) (CO-R-SO-NH-R

' NH-)

Head-to-Head Head-to-Tail

Poly (amide-sulfonamides) were also determined

to be less thermally stable than the aromatic polyamides

due to the presence of the sulfonamide group, despite

the rigidity imposed by the aromatic rings in the

main polymer chain (23).

29

Another type of polymer worth describing is the

polyacylsulfonamide-amides 13 . This class of polymer

can be prepared by a ring opening reaction of

N,N'-arylene disulfonyl bis(succinimides) with various

diamines (24 ) .

+ H2N-R-NH2

to oho oho ohh-i

! i u M i n 11 1 i

C-CHi-CHj-C-N-S-AR-S-NCCHjCHj-CN-R-N-

1 'ii ii

o o

13

AR <>->,

R -._(

CH2A- "CH,CH,-

---, <Q>-<>

30

Solution polymerizations were carried out using

polar solvents such as N-methyl-2-pyrrolidone and

N,N-dimethylacetamide. The polymers obtained showed

inherent viscosities ranging from 0.18-0.40 dL/g. These

polymers were soluble in polar aprotic solvents such as

N,N-dimethylacetamide, as well as in basic media such as

sodium hydroxide and pyridine. It is interesting to

note that these polymers were also soluble in acidic

media such as formic acid and m-cresol, despite having

the acidic sulfonamide linkages (24).

Differential thermal analysis of 13 showed a

melting temperature in the range of 150-200C. Thermal

gravimetric analysis showed these polymers to have an

initial X weight loss at around 200C. It is believed

that polyacylsulfonamide-amide 13 decomposes by the

formation of bis-succinimides and the aromatic

disulfonamides i.e.

r o o ho o

-J-NHC-CH!CHrC-N-S-AR-S-NH-C-CH2CH.-C-NH-R-L

L0 o o o

_L

AN-R-N

0

]?o o

H,N-S-AR-S-NH' ii

o o

31

This type of decomposition was supported by the

appearance of the characteristic absorptions atv= 1770

cm andV= 1700 assignable to the imide carbonyl in the

infrared spectra of the decomposition residue of all of

the polymers at 300C under nitogen (24).

Poly (amide-sulfonamides) membranes are known to

exhibit reverse osmosis properties. Due to the

commercial value of these polymers, they usually are

patented and synthetic details are never fully

disclosed. A poly (amide-sulfonamides) reverse osmosis

material was prepared by the polymerization of an

aromatic diamine 14 with isophthaloyl chloride or

adipoyl chloride (25).

-<>-<>'

CH2 0, S02 ,

S

NH2

*" "

S02NH2 ,H

'NH2 14

The polymer was determined to have a tensile

strength of15kg/mmB and a 10X elongation at break. The

polymer was cast from N ,N-dimethylacetamide to give a

50u film. The film was stable in air at .$ 400C. As a

desalinating membrane, it showed a water permeation rate

of 1.7 m8/mB/day and a salt rejection of 65X for water

containing 5000 ppm sodium chloride.

32

Improvements in the membrane flux rate and X salt

rejection were obtained when the sulfonamide substituents

in diamine 14 were N-methylated (26).

f-<5>^> NHCO

R

NH-CH3

* =

S02NHCH3

15

A solution of 2, 2'-bis(methyl-aminosulfonyl )

4 , 4 '-diamino-diphenyl-ether-isophthaloyl-chloride

co-polymer 15 , having a reduced viscosity of 2.0 dL/g

in N,N-dimethylacetamide at 30C, was cast and gelled

in ice water to give a membrane having a water flux rate

of 1.3 m8/m2/day and B8X salt rejection for water

containing 5000 ppm sodium chloride. In comparision a

cellulose acetate membrane showed 0.3 m8/m*/day water

flux rate and a 97X salt rejection for water containing

5000 ppm sodium chloride.

35

2.0 Objective.

The aim of this research project was to

synthesize and characterize several novel

poly (amide-sulfonamides) having the general structure

16A and 16B shown below. These polymers are unique in

structure from those previously synthesized and are

potential candidates for reverse osmosis membranes.

rH HO . HO O _

n-Ar-n-s-^T jVn-c-Ar-c

n^'

N

16A

HO 0 _

fO-i--"-^^

16B

A,,-^CH,^

(

---

M-,, fe^

3^

Once synthesized, these polymers would be characterized

by dilute solution viscosity, infrared spectroscopy,

thermal gravimetric analysis and differential scanning

calorimetry. In addition, films of these materials

would be evaluated for mechanical and reverse osmosis

properties.

^

3.0 Results and Discussion.

The synthesis of the title polymers involved;

(1) synthesis of an amino acetanilide containing a

a preformed sulfonamide linkage,

(2) deblocking of the amino acetanilide to form the

diamine monomers,

(3) solution polymerization of the diamine monomers

with the appropriate dicarboxylic acid or

derivative to form the poly (amide-sulfonamides) .

The amino acetanilides 17-19 were prepared by

reacting N-acetamidobenzene sulfonyl chloride with

excess 4,4'-oxy dianiline, 4 ,4 '-methylene dianiline and

anhydrous piperazine in refluxing tetrahydrofuran .

H2N-AR-NH2 + CH,CONH-/Q\s02Cl

THEh*-aJ|@,

HO

?NHCOCH3 4 HCl

*--"- CHq^17

' 18

N-S -/(""^YnhCOCH,

v_v

IS

36

A 1 to 2 molar ratio of the N-acetamidobenzene

sulfonyl chloride to the diamine was used to reduce the

formation of an unwanted diacetanilide product 20 , a

2:1 adduct. The diacetanilide is formed because

products 11-13 have a free amino group capable of

reacting with a second molecule of N-acetamidobenzene

sulfonyl chloride. These diacetanilides and their

corresponding dianilines have been synthesized and used

in the preparation of novel poly (amide-sulfonamides)

(27).

The sulfonyl chloride was added dropwise to a

vigorously stirred refluxing solution of the diamine in

tetrahydrofuran for a period of two hours. Thin layer

chromatography (ethyl acetate / hexane/ acetone 2:1:1)

of the reaction mixture for the 4,4'-oxy and methylene

dianiline always showed the presence of the

diacetanilide product (slowest moving component)

and the unreacted diamine. Since no acid acceptor was

used in this reaction, the hydrogen chloride liberated

was picked up by the excess starting diamine and the

mono-acetanilide product. Evidence for this was

the fact that the precipitate formed after the

completion of the reaction was found to be soluble in

water.

37

Thin layer chromatography analysis of the ethyl acetate

extract of this solution showed it to consist of mainly

starting diamine and a trace of the mono-acetanilide

product. The individual components in the reaction

mixture were separated using dry column chromatography.

The yields of the pure mono-acetanilide 17-19 were low.

These low yields can be attribute to the formation of

the diacetanide product 20 , despite the care that was

taken to avoid its formation.

h,n/0/X\0/NH S0/O/NHC0CH3

CHjCONH-n^jYsOjCl

^P-HL-

20

X *-CH2-

,-O

38

The NMR spectrum of 17 showed the methylene protons

atfc= 3.7 ppm and the acetyl protons at= 2.1 ppm. The

spectrum for 19 showed a singlet (BH) at= 2.5 ppm

corresponding to the protons in the piperazine ring.

The acetyl protons were also observed at = 1.8 ppm. The

microanalysis of 17 gave a result which favourably

corresponded to its structural composition.

The infrared spectra of 17,18,19 showed the

characteristic N-H absorptions at V= 3350, 3220, 3290

cm-* for 17, 18 and 19 ,

respectively. Table V

summarizes the results of this selective sulfonylation

reaction .

39

Table V: Results of the Selective Sulfonylation

Reaction of 4,4'-Oxy Dianiline, 4,4 _

Methylene Dianiline and Anhydrous Piperazine

Compound Melting X Rf Microanalysis

Point(C) Yield X C H N

17 175-176 48 0.59 cal 63.79 5.31 10.63 8.10

fd. 63.51 5.35 10.32 7.98

18 146-147 46 0.60

b

19 144-145 63 0.58

a) ethyl acetate/hexane/acetone (2:1:1) as

the mobile phase.

b) diethyl ether/methanol (3:1) as the

mobile phase.

40

The acetyl group in 17, 18 and 19 was removed

by treatment with 6 M hydrochloric acid under reflux

condition for thirty minutes. This hydrolysis reaction

gave the desired diamine monomers 21, 22 and 23 in a

fairly good yield.

v*@*'"'@S COCH,

i) Hcl Kg *@"@"T@"H'

21 X * -CH,-

22 X" -0-

23 H N N SOs

\ /NH,

41

The NMR spectra of 21, 22 and 23 showed the

disappearance of the acetyl protons at= 2.1 ,= 2.2 ppm

andfl=1.8 ppm, respectively. The diamine monomers

21 , 22 and 23 , all gave favourable microanalytical

results and a single spot on thin layer chromatography.

The infrared spectra of the diamines 21 ,22 and

23 showed the absence of a carbonyl absorption band at^

1690 cm*i,"0= 1680 cm*i andv= 1680 cm**respectively,

indicating a successful deblocking reaction. The

diamine monomers 21 and 22 showed a yellow colouration,

even after treatment with decolourizing charcoal and

column chromatography. Diamine monomer 23 was a white

crystalline solid.

The results of the hydrolysis reaction are

summarized in Table VI.

42

Table VI: Results of the Hydrolysis Reaction of the

Mono Acetanilide 17 , 18 and 19 with

6 M Hydrochloric Acid.

Compound Melting X Rf Microanalysis

Point(C) Yield X C H N S

21 164-165 74 0.86 cal 64.58 5.38 11.89 9.06

fd. 64.53 5.43 12.07 8.95

22 104-105 76 0.80 cal 60.84 4.78 11.83 9.01

fd. 60.57 4.63 11.54 9.29

b

23 202-203 71 0.59 cal 49.79 6.22 17.42 13.27

fd. 49.48 6.50 17.72 13.51

a) ethyl acetate/ hexane/ acetone (2:1:1) as

the mobile phase.

b) diethyl ether/ methanol (3:1) as the

mobile phase.

43

The diamine monomers 21 , 22 and 23 ,purified by

column chromatography, were reacted with terephthaloyl

chloride, isophthaloyl chloride and sebacoyl chloride,

using a low temperature solution polymerization

technique to give the poly (amide-sulfonamides) 24-32.

h,n-Ar.Nh-s/Q\nh, ? dc-AV-c-cl4-n-ar-nh-so,/Q^nhc-*r1-c-J-

32

24 AR

25 AR

aj -cO)cH.(nv*r1-

-ic+e

27 AR:

28 AR

29 AR*" = CH,).

30 _f_ N ?*-*

3j -<-\_r

-f-

"(3^ -@"Nco<cH,)reo-fc

44

The reactions of 21 with terephthaloyl ,

isophthaloyl and sebacoyl chloride were conducted at

room temperature, to give polymers 24, 25 and 26 .

The polymers obtained had a very low inherent

viscosities , indicative that they were low in molecular

weight. A higher inherent viscosity of 0.49 dL/g was

obtained for 24 when the reaction temperature was kept

at 0-3 C. Polymers 27, 28 and 29 had the inherent

viscosities of 0.31 , 0.31 and 0.49 dL/g respectively.

The low inherent viscosity values obtained were

atteibuted to incomplete dryning of the diamine

monomers and solvent. Repeating the experiment using

monomer 21, dried over phosphorus pentoxide and

refluxing toluene in a drying pistol under vacuum, gave

polymers 24 , 25 and 26 which still had low inherent

viscosity values.

The results of the polymerization of 21 , 22 and

23 with terephthaloyl, isophthaloyl and sebacoyl

chloride using a low temperature solution polymerization

technique are summarized in Table VII.

Table VII: Results of the Polymerization of 21 ,22 and

23 with Terephthaloyl, Isophthaloyl and Sebacoyl

Chloride Using Low Temperature Solution Technique.

Polymei Reaction Inherent X

Yield

Tg_(C)

X Weight

Temp. <C) Viscosity Loss at

(dL/g) 300C

(MBST) 24 21-23 0.25 91 243 5

(MBST)24*

0-3 0.49 83 260 20

(MBSI) 25 21-23 0.19 70 220 7

(MBSS) 26 21-23 0.30 88 B7 6

(OBST) 27 0-3 0.31 83 253 12

(OBSI) 28 0-3 0.31 70 256 12

(OBSS)29*

0-3 0.49 82 142 14

(PBSS) 32 0-3 0.20 75 94 6.5

a) measured in N ,N-dimethylacetamide at 25C

with the concentration= 0.50g/100ml.

* Film forming polymers.

4-.

The polymers 24-29 f synthesized using the low

temperature solution technique showed a decomposition in

structure at 300- 360C in a nitrogen atmosphere.

In one polymerization, 2,6-dimethyl pyridine was

used instead of pyridine as the acid acceptor. An

example of this was the polymerization of 23 with

sebacoyl chloride to give polymer 32 . Using a 1-ml

syringe, sebacoyl chloride was injected into a

stirred diamine solution to give a precipitate of

polymer 32 almost instantaneously. Polymer 32 , having

a highly flexible aliphatic chain in the polymer

structure showed a 6.5 X weight loss at 300 C . The

glass transition temperature was also found to be at

94C. Polymer 32 had an inherent viscosity of 0.20

dL/g, suggesting a low in molecular weight material.

Since the inherent viscosity values for the polymers

prepared by a low temperature solution technique were

low, a new polymerization technique was employed in

order to achieve higher inherent viscosities.

Higher molecular weight polymers were obtained when

the Yamazaki reaction was used (13). When 22 was treated

with isophthalic acid, a polymer 28 , having an inherent

47

viscosity of 1.21 dL/g was obtained. The reaction of 21

with terephthalic and isophthalic acid gave polymers 24

and 25 with moderate inherent viscosities values of

0.38- 0.50 dL/g. The low inherent viscosity values for

polymers 24 and 25 were attributed to incomplete dryness

of the monomers.

Polymer 27 showed an inherent viscosity of 0.45 dL/g.

However, polymers 24 , 25 and 27 , despite their low

inherent viscosities values, formed tough transparent

films when cast from N ,N-dimethylacetamide solution.

Polymers 30 and 31 prepared from the

piperazine-benzene-sulfonamido monomer 23 and

terephthalic, isophthalic acid, showed low inherent

viscosities values of0.20- 0.22 dL/g. These polymers

formed brittle films when cast from

N,N-dimethylacetamide solution.

The results of these Yamazaki polymerizations

are summarized in Table VIII.

4b

Table VIII: Results of the Polymerization of 21 , 22

and 23 with Terephthalic, Isophthalic Acid

using the Yamazaki Reaction.

Polymer XYield Inherent Tg(C)

Viscosity

(dL/g)

X Weight

Loss at

300C

(MBST) 24 99 0.50 260 20

(MBSI)25*

100 0.38 198 19

(OBST)27*

100 0.45 273 20

(OBSI)28*

96 1.21 268 18

(PBST) 30 81 0.22 200 9

(PBSI) 11 74 0.21 273 8

(OBSP) 33 93 0.22 238 16.5

a) measured in N ,N-dimethylacetamide at 25C

with the concentration = 0.500g/100 mL.

* Film forming polymers.

^9

One advantage the Yamazaki reaction has over the low

temperature solution polymerization is the utilization

of a dicarboxylic acid instead of the diacid chloride.

The step growth polymerization process requires high

monomers purity in order to form a high molecular weight

material. Since the diacid chloride are very reactive,

they can react with water in the atmosphere to form a

dicarboxylic acid which terminates the step growth

polymerization process leading to lower molecular weight

polymers.

The dryness and purity of the diamine monomers,

the dicarboxylic acid and the solvent used are important

factors in the Yamazaki reaction. All of the diamines

monomers used in this project contained a preformed

sulfonamide group, which can strongly associate with

water or solvents used by hydrogen bonding. Despite the

fact that all of the diamine monomers gave favourable

microanalyses and showed a single spot on the thin layer

chromatography, it was necessary to purify the monomers

using dry column chromatography and recrystallization.

50

Recrystallization of monomer 22 twice, gave a white

crystalline product. This monomer when reacted with

isophthalic acid gave a high molecular weight polymer

having an inherent viscosity of 1.21 dL/g.

Another interesting polymer was synthesized by

reacting 22 with 2,5-pyridine dicarboxylic acid to

form poly ( imino-1 , 4-phenylenesulfonylimino-1 ,

4-phenyl-

ene-oxy-1 ,4-phenyleneiminocarbonyl-2

carbonyl) 33.

-*<Q>Hso4^H?tQlco

N

33

Polymer 33 had an inherent viscosity value

of 0.22 dL/g and a glass transition temperature of

23BC. A film cast from N ,N-dimethylacetamide polymer

solution was brittle. Since the Yamazaki reaction

technique was used, it is believed that some of the

2,5-pyridine dicarboxylic acid may have reacted to form

anitrogen-phosphorus linkage in the triphenyl phosphite

complex 34 .

51

The formation of this complex would reduce the amount

of the dicarboxylic acid available for the

polymerization process.

COOH

hooc' ^ C6HSN

H-P-OCOR1

%/ \

C H 0 OCHc6 5

6 5

Having obtained a low inherent viscosity for 33 , the

reaction of 2,5-pyridine dicarboxylic acid with other

diamine monomers was not further investigated.

All of the polymers 24-33 were found to be soluble

in N ,N-dimethylacetamide, N-methyl-2-pyrrolidone and

concentrated sulfuric acid. Some of the polymers were

also found to be partially soluble in a 10X sodium

hydroxide solution. The solubility test results are

summarized in Table IX.

From the results presented in this report, it can be

concluded that it is possible to prepare high

molecular weight polymers containing a sulfonamide

groups in the polymer backbone. Lack of time and

monomers, prevented a large scale preparation of

polymers 26, JZ9 and 32 .

The mechanical and reverse osmosis properties of

polymer 24 ,25 ,

27 and 28 are currently under

investigation.

52

a

Table IX: Solubility of Poly (amide-sulfonamides) in

Various Organic Solvents.

Solvent Polymer

24 25 26 27 28 29 30 31 32 33

N ,N-dimethylacetamide

N-methyl-2-pyrrolidone

N ,N-dimethylformamide

cone, sulfuric acid

Pyridine

10X sodium hydroxide

2-methoxy ethyl ether

tetrahydrofuran

acetone

chloroform-------

+ + + + + + + + + +

+ + + + + + + + + +

+ + + + + + + + + +

+ + + + + + + + + +

+ + + + + +

----

--

+--

----

95X ethanol

ethyl acetate

+ = soluble

= partially soluble or swelling

- = insoluble

a) determined at 25C

53

4.0 Experimental

General information

1) Pyridine and N-methyl-2-pyrrolidone were distilled

under reduced pressure and stored under nitrogen.

2) All melting points were determined in capillaries

using a Mel-temp apparatus and are uncorrected.

3) lH NMR spectra were determined using a Hitachi

Perkin Elmer R-20 operating at 60 MHz with

teramethylsilane as the internal standard.

4) Unless otherwise stated, infrared spectra of all

samples were done as potassium bromide pellets or

films using a Perkin-Elmer PE-681 infrared

spectrophotometer .

5) Dry column chromatography were done using Kieselgel

60 F254 as the stationary phase.

6) Microanalyses were determined by the Analytical

Division of the Baron Consulting Company, Orange,

Connecticut 06477.

5k

7) All concentration processes were done by using a

Biichi rotary evaporator with the temperature not

exceeding 60C.

8) Terephthaloyl and isophthaloyl chloride were

recrystallized from n-hexane.

9) Terephthalic acid , isophthalic acid, 4,4'-oxy

dianiline and 4 ,4 'methylene dianiline were obtained

from Aldrich Chemical Co.; anhydrous piperazine and

triphenylphosphite were obtained from Eastman-Kodak

Co. and were used as such.

10) N,N-dimethylacetamide spectrograde 99+X was obtained

from Aldrich Chemical Co. and was used as such.

11) Thermal gravimetric analyses of all polymers were

determined by using a Perkin-Elmer TGS-2 thermal

analysis under a nitrogen atmosphere with the heating

rate being 20C per minute.

12) Differential Scanning Calorimetry analyses were

determined using a Perkin-Elmer DSC-4.

A heating rate of 10-20C per minute and a

range of 0.5-2.0 meal per second was used.

55

13) Thin Layer Chromatography analyses were carried out

on Eastman Chromagram sheets (13181 silica gel).

14) Inherent viscosities were determined using a Canon

viscometer no.l C426 at a constant temperature of

25C, the polymers concentration was 0.50g in

100 ml N ,N-dimethylacetamide.

15) Solubility tests were performed qualitatively at

25C.

56

Synthesis of N-acetylimino-1 , 4-phenylenesulfonylimino-

1, 4-phenylenemethylene-l , 4-phenyleneamine 17 .

In a 5000 ml three necked round bottom flask fitted

with a Friedrich condenser and a mechanical stirrer,

90 g (0.45 mole) of 4 , 4 '-methylene dianiline was

dissolved in 2500 ml tetrahydrofuran. The solution was

stirred under reflux for thirty minutes. To this

solution was added dropwise from a pressure equalizing

funnel, 53.06 g (0.22 mole) of N-acetamidobenzene

sulfonyl chloride in 500 ml tetrahydrofuran. The

mixture was stirred under reflux for five hours. The

solution mixture was cooled and the precipitate

filtered. Evaporation of the filtrate gave a brown

viscous syrup which was chromatographed using hexane/

ethyl acetate/ acetone (3:2:1) as the eluting solvent.

This gave brown crystals of 17 with Rf = 0.59 (ethyl

acetate/hexane/ acetone 2:1:1). The product was dried

overnight in a vacuum oven at 70C and was used as such

for further transformation.

yield = 43 g (48X)

m.p. = 175-176C

Analytical for CZIHZ0N3S 03

calculated:C= 63.79X H= 5.31X N= 10.63X S= B.10X

found:C= 63.51X H= 5.35X N= 10.32X S= 7.98X

IR data(KBr):V= 3350 cm-* (N-H),V= 1685 cm - (C=0) ,

v= 1150 cm'* (S=0)

57

Synthesis of N-acetylimino-1 , 4-phenylenesulfonylimino-

1 , 4-phenylene-oxy-l , 4-phenyleneamine IB .

Using the procedure previously described in the

synthesis of 17, 150 g (0.750 mole) of 4,4'-oxy

dianiline in 2500 ml tetrahydrofuran was reacted with

87.56 (0.37 mole) of N-acetamidobenzene sulfonyl

chloride in 500 ml tetrahydrofuran .

yield = 69.60 g (46X)

m.p. 146-147C

Rf = 0.60 (ethyl acetate/ hexane/acetone

2:1:1)

IR data (KBr):v= 3220 cm-* (N-H)

<J= 16B0 cm-* (C=0)

V*

= 1160 cm-i (S=0)

This product was dried overnight in a vacuum oven at

70C and was used as such for further transformation.

Synthesis of N-acetylimino-1 , 4-phenylenesulfonylpiperi-

zinyl. 19

Using the same procedure for the synthesis of 17

and 18 , lOOg (1.16 mole) of anhydrous piperazine in

1500 ml tetrahydrofuran was reacted with 135. 63g (0.58

mole) of N-acetamidobenzene sulfonyl chloride in 500ml

tetrahydrofuran for five hours. Filtration of the

precipitate and evaporation of the excess solvent gave

white crystalline solid. The solid was redissolved in

methanol and was chromatographed using diethyl ether/

methanol (4:1) as the eluting solvent. This gave pale

yellow crystalline solid of 19 with the Rf = 0.61

(diethyl ether/ methanol 3:1). The product was dried

overnight in a vacuum oven at 70C and was used as such,

yield = 105.2 g (63X)

m.p.= 144-145C

IR data (KBr):>)= 3280 cm-* (N-H)

-0 = 1680 cm-i (C=0)

>)= 1170 cm-* (S=0)

59

Synthesis of Amino-1 ,4-phenylenesulfonylimino-1

phenylenemethylene-1 ,4-phenyleneamine 21 .

Using a 500 ml rmind bottom flask fitted with a

condenser and a magnetic stirrer, 9 g(0.02 mole) of 17

was treated with 100 ml 6M hydrochloric acid. The

mixture was refluxed for thirty minutes. The mixture

was cooled in an ice water bath and was neutralized by

the careful additions of sodium bicarbonate to gave a

yellow precipitate of 21 , which was dried overnight in

a vacuum oven at 70C.

yield = 5.98 g (74X)

This crude product was dissolved in acetone and was

chromatographed using hexane/ ethyl acetate/ acetone

(3:2:1) as the eluting solvent. This gave pale yellow

crystals of 21 . The product was further purified by

recrystallization from methanol. The recrytallized

product was dried overnight in a vacuum oven at 70C.

It was further dried in a pistol over phosphorus

pentoxide and refluxing cyclohexane for twelve hours.

m.p. = 164 - 165C

Analytical for C^ H^ H^ 0Z S

calculated:C= 64.58X H= 5.38X N= 11.B9X S= 9.06X

found: C= 64.53X H= 5.43X N= 12.07X S= 8.95X

IR data (KBr):>>> = 3400 cm'* (N-H),v= 1140 cm-i (S=0)

60

Synthesis of Amino-1 ,4-phenylenesulfonylimino-1

phenyleneoxy-1 , 4-phenyleneamine 22.

Using the same procedure previously described,

30 g (0.07 mole) of IB was treated with 200 ml 6M

hydrochloric acid for thirty minutes. The cooled

solution was neutralized with sodium bicarbonate to give

the crude solid diamine product 22.

yield = 20.38 g (76X)

This crude product was dissolved in acetone and

chromatographed using ethyl acetate/ hexane/ acetone

(3:2:1) as the eluting solvent to give a brown syrup of

22 . The syrup was redissolved in a minimum amount of

ethanol (c.a. 100 ml). Adding 30 ml cold distilled

water to this solution and storing it overnight at minus

25C, gave pale yellow needles of 22 . This product

was dried in the same manner as 21 .

m.p. = 104- 105C

Analytical for C(g HR N3 03 S

cal. :C= 60.84X H= 4.78X N= 11.B3X S= 9.01X

found:C= 60.57X H= 4.63X N= 11.54X S= 9.29X

IR data (KBr):V= 3260 cm-* (N-H)

V= 1155 cm'* (S=0)

61

Synthesis of Amino-1 ,4-phenylenesulfonylpiperizinyl. 23

Using the same procedure as that of 21 and 22 ,

30 g (0.10 mole) of 19 was treated with 200 ml of 6 M

hydrochloric acid for fifteen minutes. The solution was

cooled in an ice water bath and neutralized with sodium

bicarbonate to give a yellow precipitate. The

precipitate was filtered and dried overnight at 70C in

a vacuum oven.

yield = 17.82 g (71X)

This crude product was recrystallized from methanol

to give white crystals of 23 ,which was dried for an

overnight period in a vacuum oven at 70C. It was

further dried in a drying pistol over phosphorous

pentoxide and reflux ing toluene for twelve hours.

m.p. = 202- 203C

Analytical for Cl0 H,s N3 0X S

cal. C= 49.79X H= 6.22X N= 17.42X S= 13.27X

found C= 49.48X H= 6.50X N= 17.72X S= 13.51X

IR data (KBr): \> = 3440 cm - (N-H)

V= 1150 cm-i (S=0)

This product was used as such for the polymerization

process.

62

General low temperature solution polymerization

procedure .

Using a 50-ml one necked round bottom flask, the

diamine was dissolved in 10 ml of spectrophotometric

grade N,N-dimethylacetamide containing 5 ml pyridine.

The solution was stirred and chilled in an ice bath for

thirty minutes. The acid chloride was added rapidly to

the stirring mixture.

The mixture was left stirring at 0-3C for six hours

and overnight at 21-23C.

The polymer was obtained by pouring the mixture

into a beaker containing 200 ml cold distilled water.

The polymer was filtered and dried in a vacuum oven at

90C for an overnight period.

6z

General Yamazaki polymerization procedure.

To a 300 ml three necked round bottom flask fitted

with a thermometer, a condenser and a nitrogen inlet

valve was added the diamine, terephthalic acid, 2 g

lithium chloride, 10.6 ml triphenyl phosphite, 10 ml

pyridine and 40 ml N-methyl-2-pyrrolidone. The mixture

was heated with stirring at B5-90C for 16 hours under

nitrogen. When cooled, the reaction mixture was poured

into a beaker containing 300 ml methanol. The

precipitated polymer was collected by filtration and

dried in a vacuum oven at 90C for an overnight period.

64

Synthesis of poly ( imino-1 , 4-phenylenesulfonylimino-1 ,

4-

phenylenemethylene-1 , 4-phenyleneiminoterephthaloyl )

(MBST) 24.

Using the low temperature solution polymerization

procedure, 0.50 g (1.41x10-3mole) of 21 was reacted

with 0.28 g (1. 41x10 "8mole) of terephthaloyl chloride

to produce polymer 24 .

yield = 0.66 g (83X)

înh. = 0.49 dL/g

Tg = 260C

IR data (film): n) = 3300 cm-* (N-H)

>J = 1660 cm-i (C=0)

\) = 1155 cm-i (S=0)

PDT = 340C

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1 ,4-

phenylenemethylene-1 , 4-phenyleneiminoisophthaloyl )

(MBSI) 25.


procedure, 0.50 g ( 1. 41x10 *8 mole) of 21 was reacted

with 0.28 g (1. 41x10 '8 mole) of isophthaloyl chloride to

give polymer 25 .

5

yield = 0.48 g (70X)

înh = 0.19 dL/g

Tg = 220 C

PDT = 350C

IR data (KBr):-v*

= 3300 cm-i (N-H)

\)= 1655 cm-i (C=0)

*0 = 1155 cm-* (S=0)

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1

phenylenemethylene-1 , 4-phenyleneiminosebacoyl ) (MBSS)

26.


procedure, 0.50 g ( 1. 41x10 "8 mole) of 21 was reacted

with 0.3 ml (1.41xl0"8 mole) of sebacoyl chloride to

give polymer 26 .

yield = 0.65 g (B8X)

înh. =0.30 dL/g

Tg - 87C

IR data (KBr): V = 3340 cm-i (N-H)

>J= 1660 cm** (C=0)

^ 1150 cm-i (S=0)

PDT = 310C

66

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1 ,4-

phenylene-oxy-1 ,4-phenyleneiminoterephthaloyl ) (OBST)

27.


procedure, 0.50 g (1.41x10 '8 mole) of 22 was reacted

with 0.28 g (1. 41x10 '8 mole) of terephthaloyl chloride

to give polymer 27.

yield = 0.56 g (83X)

înh. - 0.31 dL/g

Tg = 253C

IR data (KBr): N> = 3320cm- 1 (N-H)

N) 1660 cm-* (C=0)

"0 = 1155 cm-i (S=0)

PDT = 370C

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1 ,

4-

phenylene-oxy-1 ,

4-phenyleneiminoisophthaloyl ) (OBSI) 28.


procedure,0.50 g

(1.41X10"8 mole) of 22 was reacted

with 0.28 g ofisophthaloyl chloride to give polymer 28.

yield = 0.48 g (70X)

'T.inh. = 0.31 dL/g

67

Tg = 256C

IR data (KBr): -\) = 3320 cm'i (N-H)

v1

= 1660 cm- (C=0)

>J= 1155 cm-i (S=0)

PDT = 370C

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1 ,

4-

phenylene-oxy-1 ,4-phenyleneiminosebacoyl ) (OBSS) 29.


procedure, 0.50 g (1. 41x10 *8 mole) of 22 was reacted

with 0.3 ml sebacoyl chloride to give polymer 29.

yield = 0.61 g (82X)

Tg = 142C

înh.^ 0.49 dL/g

IR data (film): >> = 3250 cm** (N-H)

V*

= 1660 cm-* (C=0)

v*

= 1155 cm-i (S=0)

PDT = 340C

65

Synthesis of poly ( imino-1 , 4-phenylenesulfonyl-

piperazinylenesebacoyl) (PBSS) 32.

Using a 25-ml one necked round bottom flask,

1.01 g (0.0042 mole) of 23 was dissolved in 20 ml

N ,N-dimethylacetamide and 5 ml 2,6-dimethyl pyridine.

The solution mixture was stirred and chilled in an ice

bath for thirty minutes. Using a 1-ml syringe, 0.9 ml

(0.0042 mole) of sebacoyl chloride was injected to the

stirred solution. The mixture was stirred at 0-3C

for six hours and then overnight at 21-24C. The

polymer was precipitated by pouring the solution mixture

into 100 ml cold distilled water. The polymer was

filtered, washed with 50 ml cold distilled water and

dried in a vacuum oven at 50C for overnight.

yield = 1.53 g (75X)

*\inh. = 0.20 dL/g

Tg = 94C

IR data (KBr): \) = 3380 cm-* (N-H)

>)= 1700 cm-i (C=0)

>)= 1160 cm-* (S=0)

PDT = 340C

69

Synthesis of poly ( imino-1 , 4-phenylenesulfonylimino-1 ,

4-

phenylenemethylene-1 , 4-phenyleneiminoterephthaloyl )

(MBST). 24

Using the general Yamazaki polymerization

procedure, 3.53 g (0.01 mole) of 21 was reacted with

1 . 66 g terephthalic acid in 20 ml

N-methyl-2-pyrrolidone, 5 ml pyridine, 5 . 3 ml triphenyl

phosphite containing 1 g of lithium chloride to give

polymer 24.

yield = 4.65 g (99X)

înh. =0.50 dL/g

Tg = 260C

IR data (film): >J= 3300 cm-i (N-H)

>)= 1660 cm-* (C=0)

\)= 1155 cm-i (S=0)

PDT = 340C

70

Synthesis of poly ( imino-1 , 4-phenylenesulfonylimino-1 ,4-

phenylenemethylene-1 , 4-phenyleneiminoisophthaloyl )

(MBSI). 25



3.24 g (0.019 mole) of isophthalic acid to give polymer

25.

yield = 12.14 g (100X)

'T.inh. = 0.38 dL/g

Tg = 19BC

IR data(film): >) = 3330 cm-* (N-H)

\> = 1655 cm-* (C=0)

>)= 1155 cm-i (S=0)

PDT = 350C

Synthesis of poly ( imino-1 , 4-phenylenesulfonylimino-1

phenylene-oxy-1 ,4-phenyleneiminoterephthaloyl )

(OBST). 27



3.32 g of terephthalic acid to give polymer 27.

yield = 12.62 g (100X)

linh. = 0.45 dL/g

71

Tg = 273C

IR data <film):\>= 3320 cm"* (N-H)

V= 1660 cm-i (C=0)

>)= 1155 cm-i (S=0)

PDT = 370C

Synthesis of poly ( imino-1 ,4-phenylenesulfonylimino-1

phenylene-oxy-1 , 4-phenyleneiminoisophthaloyl )

(OBSI). 28



3.32 g (0.02 mole) isophthalic acid to give polymer 2.

yield = 11.90 g (96X)

înh. -1.21 dL/g

Tg = 26BC

IR data (film): >J 3320 cm-* (N-H)

N> = 1660 cm-i (C=0)

0 = 1155 cm-* (S=0)

PDT = 370C

72

Synthesis of poly ( imino-1 , 4-phenylenesulfonylimino-1 ,4-

phenylene-oxy-1, 4-phenyleneiminocarbonyl-2 , 5-pyr

idine-

diylcarbonyl) (OBSP) . 33



3.34 g (0.02 mole) of 2,5-pyridine dicarboxylic acid to

give polymer 33.

yield = 11.57 g (93X)

înh. =0.22 dL/g

Tg = 238C

IR data (KBr): ^ = 3400 cm-i (N-H)

N)= 1660 cm-* (C=0)

"v1

= 1150 cm-i (S=0)

PDT = 360C

Synthesis of poly ( imino-1 , 4-phenylenesulfonylpiperazi-

nyleneterephthaloyl) (PBST). (30)



3.34 g (0.02 mole) of terephthalic acid to give polymer

30.

yield = 8.24 g (BIX)

'J.inh. = 0.22 dL/g

15

Tg = 200C

IR data (KBr): y)= 3450 cm i (N-H)

>) = 1660 cm * (C=0)

N) = 1160 cm i (S=0)

PDT = 375C

Synthesis of poly ( imino-1 ,4-phenylenesulfonylpiperazi-

nyleneisophthaloyl) (PBSI). (31)



3.34 g (0.02 mole) of isophthalic acid to give polymer

31.

yield = 7.56 g (74X)

înh. = 0.21 dL/g

Tg = 273C

IR data (KBr): \) = 3440 cm** (n-h)

V= 1680 cm-* (C-0)

>)= 1160 cm'i (S=0)

PDT = 370C

74

REFERENCES

1) H.I. Mahons and B.J. Lipps, Encyclopedia of Polymer

Science and Technology, 1971,15,258

2) C.J. Ried and E.J. Breton, J. Appl. Polym. Sci . ,

1959, 1(2), 133-147

3) C.S. Fuller et al . , J. Amer. Chem. Soc., 1942 , 64 , 776

4) 0. Vogl and D. Tirrell, J. Polym. Sci., Polymer

Chem. Ed. , 1977,15,1889

5) H.Z. Friedlander, Encyclopedia of Polymer Science

and Technology, 1971,8,620

6) P.W. Morgan et al . ,J. Polym. Sci. , 1959,XL, 329

7) P.W. Morgan and S.W. Kwolek, Macromolecules, 1975,2,

104

8) P.W. Morgan and S.W. Kwolek, J. Polym. Sci. ,Part Al ,

1964,2,2693

9) R. McKinney Jr. and J.H. Rhodes, Macromolecules,

1971, 4(5), 633

10) M.A. Kraus, M. Nemas and M.A. Frommer, J. Appl.

Polym. Sci., 1979,23,445

11) L.H.Gan et al , J. Appl. Polym. Sci., 1975,11,69

12) M.H. Panar, H.H. Hoehn and R.R. Herbert,

Macromolecules , 1973,6,777

13) N. Yamazaki et al . , J. Polym. Sci., Polymer Chem.

Ed. , 1975,13,1373

14) S.A. Sundet, W.A. Murphy and S.B. Speck, J. Polym,

Sci. , 1959,XL, 389

15) C.S. Marvel, F.E. Arnold and S. Cantor, J. Polym.

Sci. , 1967,_5,553

16) Y. Imai et al . ,J. Polym. Sci . , Polym. Chem. Ed. ,

1979,17,1483

17) H.K. Hall Jr., J. Amer. Chem. Soc, 1956,78,2717

76

18) J.D. Albright et al ., J. Chem. Soc, Chem. Comm. ,

1965,413

19) L.A. Paquette, J. Amer. Chem. Soc, 1965,87,5186

20) Y. Imai, M. Ueda and T. Iizawa, J. Polym. Sci.,

Polymer Letter Ed., 1977,15,207

21) N. Chan, Y. Okawa and Y. Iwakura, J. Polym. Sci.,

Polym. Chem. Ed., 1980,18,3499

22) R.C. Evers and G.F.L. Ehlers, J. Polym. Sci.,

1967^5,1797

23) Y. Imai and H. Okunoyama, J. Polym. Sci .,Part Al,

1972,10,2257

24) Y. Imai, M. Ueda and K. Okuyama, J. Polym. Sci.,

Polymer Chem. Ed. , 1979,17,1901

25) N. Kinjo et al . ,Ger.Offen. 2,729,847; Chem. Abstr.

197B,88,122123e

26) N. Kinjo et al , Jpn, Kokai Tokkyo Koho, 79 89,982

(C1.B01D13/00); Chem. Abstr. , 1980,92,23779z

27) J.M. Adduci et al., J. Polym. Sci., Polym. Chem.

Ed., in preparation.

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Figure 23: TGA curve of polymer 24,

jm>

jju i >-\<

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-- T*^ "_

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Figure 24: TGA curve of polymer 25.

'

f * ,J

m If Wyi -17-

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I 1

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.igure 29: TGA curve of polymer 30

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re 31: TGA curve of polymer 32.

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ii

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109

Documents

Synthesis and characterization of poly(amide-sulfonamides