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Rochester Institute of TechnologyRIT Scholar Works
Theses Thesis/Dissertation Collections
5-1-1985
Synthesis and characterization of poly(amide-sulfonamides): new candidates for reverse osmosismembranes.Thevarak Rochanapruk
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Recommended CitationRochanapruk, Thevarak, "Synthesis and characterization of poly(amide-sulfonamides): new candidates for reverse osmosismembranes." (1985). Thesis. Rochester Institute of Technology. Accessed from
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
2. NMR spectrum of monoacetanilide 18
3. NMR spectrum of monoacetanilide 19
4. NMR spectrum of diamine monomer 21
5. NMR spectrum of diamine monomer 22
6. NMR spectrum of diamine monomer 23
7. IR spectrum of monoacetanilide 17
8. IR spectrum of monoacetanilide 18
9. IR spectrum of monoacetanilide 19
10. IR spectrum of diamine monomer 21
11. IR spectrum of diamine monomer 22
12. IR spectrum of diamine monomer 23
13. IR spectrum of polymer 24
14. IR spectrum of polymer 25
15. IR spectrum of polymer 26
16. IR spectrum of polymer 27
17. IR spectrum of polymer 28
18. IR spectrum of polymer 29
19. IR spectrum of polymer 30
20. IR spectrum of polymer 31
21. IR spectrum of polymer 32
22. IR spectrum of polymer 33
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)
^inh. = 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.
Using the low temperature solution polymerization
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)
^inh = 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.
Using the low temperature solution polymerization
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)
^inh. =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.
Using the low temperature solution polymerization
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)
^inh. - 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.
Using the low temperature solution polymerization
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.
Using the low temperature solution polymerization
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
^inh.^ 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)
^inh. =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
Using the general Yamazaki polymerization
procedure, 6.90 g (0.019 mole) of 21 was reacted with
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
Using the general Yamazaki polymerization
procedure, 7.10 g (0.02 mole) of 22 was reacted with
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
Using the general Yamazaki polymerization
procedure, 7.10 g (0.02 mole) of 22 was reacted with
3.32 g (0.02 mole) isophthalic acid to give polymer 2.
yield = 11.90 g (96X)
^inh. -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
Using the general Yamazaki polymerization
procedure, 7.10 g (0.02 mole) of 22 was reacted with
3.34 g (0.02 mole) of 2,5-pyridine dicarboxylic acid to
give polymer 33.
yield = 11.57 g (93X)
^inh. =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)
Using the general Yamazaki polymerization
procedure, 4.82 g (0.02 mole) of 23 was reacted with
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)
Using the general Yamazaki polymerization
procedure, 4.82 g (0.02 mole) of 23 was reacted with
3.34 g (0.02 mole) of isophthalic acid to give polymer
31.
yield = 7.56 g (74X)
^inh. = 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
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6) P.W. Morgan et al . ,J. Polym. Sci. , 1959,XL, 329
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104
8) P.W. Morgan and S.W. Kwolek, J. Polym. Sci. ,Part Al ,
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77
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