CHAPTER 8

SEBACIC ACID BASED POLYESTER

POLYOLS IN MOISTURE CURED
POLYURETHANE

8.1.0 Introduction

Synthetic polyesters represent a group of high molecular

weight compounds. The first members of which were reported to

he synthesized as long ago as 1833 when Gay-Lussac and Pelouze

(1), obtained a solid polymer on heating lactic acid.

In 1861, Heintz (2) obtained a polymer from glycollic

acid by heating it to 240°C . Subsequently the preparation of

polyglycollide was studied by Men shut kin (3), Dessaignes (4),

Kekule (5), Anschutz (6), Bischoff and Walden (7), and others,

Sokolov (8) obtained a three-dimensional polyester by the

polycondensation of glyceric acid.

Polyesters of polybasic acids and polyhydric alcohols

were first synthesized by Berzelius (9), who reported in 1847

that on heating glycerol and tartaric acid there was formed

a non-crystalline pliable mass which, in the heated state,
 240

could be drawn into long filaments. Similar reactions were

carried out by Berthelot (10) between glycerol and sebacic and
camphoric acids, and by Van Bemmelen (11) between glycerol and
succinic and citric acids. Smith (12) investigated the reaction
of glycerol with phthalic anhydride in 1901.

The first report on the preparation of polyesters by

the polymerization of cyclic esters is due to Bischoff and
Walden (7), who observed in 1893 that the cyclic ester glycollic
was converted, under the influence of heat or the action of
traces of zinc chloride, into the polymer polyglycollide,
melting at 200°C . The polymer on distillation in vacuum was
reconverted into the monomer, m.p. 86-87°C . Men shut kin (13)

in 1881 was the first to apply kinetic methods to the investi-

vation of the poly esterification reaction; he studied the
esterification of ethylene glycol by succinic acid and deter­
mined the degree of esterificatioD, the velocity constant and
the initial velocity.

A particularly pronounced development in the investiga­

tion of synthetic polyesters occurred after 1925, when the
work of Tilicheyev (14), Maksorov (15), Carothers (16), Kienle
(17) and others led to the synthesis of a series of new
 241

compounds of this type. They also demonstrated the possibility

of the -wide practical application of the polyesters in industry.
The beginning of the industrial production of the glyptal resins
and, later, of other types of alkyd resins occurred in this .
period. Prom this time down to our own day it is possible"
to record an undiminishing interest in the polyesters.

Polyesterification may be carried out in several ways,

which differ from one another in the nature of the functional
groups of the starting materials and also in their distribution -
that is these groups may be present in -different molecules or
in a single molecule. The first case is represented by the
reaction of glycols with dicarboxylic acids and the second
by the reaction of hydroxy acids.

The polyesterification reaction may be carried out in

three ways, depending on the type of transformation :

(1) Direct esterification.

(2) Transesterification (alcoholysis, acidolysis,

estero lysis).

(3) Double decomposition.

 242

(1) The direct esterification reaction is represented

by the case "where the formation of the polyester proceeds
as a result of the interaction of the hydroxyl and carboxyl
groups of the starting materials and is accompanied by the
elimination of water.

Examples of such reactions are the interaction of

glycols and dicarboxylic acids (18).

zHOR'OH + xHOOCRCOOH-----j>(-0R 00CRC0-)x + 2xH^0

and the polycondensation of hydroxy acids (19) :

H0(CH2)nC00H—>(- 0(CH2)nC0-)x + XH^D

(2) The transesterification reaction proceeds in such a

way that, one of the components of the reaction being an ester,
the ester link of this interacts with an alcohol, an acid or
another ester, forming a new ester link and eliminating the
corresponding alcohols, acid or ester.

xHOR'OH + xr''gocrcoor”----> (- 0R*00CRC00-)v + 2xRu0H

A

Similarly, a dialkyl ester of a dicarboxylic acid may react

 t
J

- 243 -

•with a glycol, -with the elimination of .an alcohol (20-21).

Polycondensation of a glycol ester of a dicarboxylic

acid may also proceed as an alcoholysis reaction accompanied
by the elimination of the glycol (22).

xHor'coorcoor' OH —( - or’oogrcoo-) + xhor' OH

Similarly, transesterification of glycol esters with dicarboxy-

i

lie acids, may be accompanied by the elimination of monocarboxy-

lic acids (23) (acidolysis)

xR'bootf OOCR" + xHOOCRCOOH—> ( - OR'OOCRCOO-) + 22R”C00H

(3) The double decomposition reaction represents a very

little studied case of the polyesterification reaction, since
reactions of this type have, as yet, negligible use in
practice. Example of reactions of this type is the interac­
tion of dicarboxylic acid chlorides with glycol (23).

xHOR* OH + XC10CRC0C1 —( - OR* OOGRCO- ) „ + 22&C 1

iX.

and the interaction of dihalogenohydrocarbons "with salts of

 244

dicarbozylic acids (21,23,24-26).

XCIR'CI + xNaOOCR. GOONa—7^ ( - OR1OQCRCO-) •A.

+ 2xNaCl

Several types of polyesters are presently available, both

aliphatic and aromatic saturated and unsaturated. A large
number of glycols and dicarboxylic acids is commercially
used, viz.,

Glycols i

Ethylene glycol, Propylene glycol, Butane diol,

Trimethylene glycol, Tetramethylene glycol,
Pentamethylene glycol, Hexamethylene glycol, Reopentyl
glycol, Triphenylol propane, Glycerol, etc.

Dicarboxylic acids :

Succinic acid, Glutaric acid, Adipic acid, Azelaic

acid, Sebacic acid, Maleic anhydride, Phthalic
anhydride, Isophthalic acid, Terephtfealic acid, etc.
 245

8.1.1 Polyester in polyurethane :

One of the most important applications of polyesters

now-a-days is in the synthesis of polyurethanes. It is possible
to prepare a polyester having terminal hydroxyl groups by con­
trolling the reaction components. Since diisocyanates are
reactive towards any pendant hydroxyl group, polyurethane
products may be easily obtained with such polyesters. Poly­
ester polyol based polyurethanes have been prepared by several
workers - they using poiy(butylene glycol adipates) (27);
poly(ethylene glycol terephthalate), poly(ethylene glycol
isophthalate), poly(ethylene glycol azeloote) (28); poly(ethylene
adipate) (29); poly( 3-methyl-1,5 pentane diol adipate) (30);
poly(l,5-pentane diol terephthalate), poly(l,6-hexane diol
terephthalate) (31); others (32-72).

Sebacic acid based polyurethane has been prepared by

Barcelona (32), Schniepp (51) and Iwakura (66) but excepting
these few limited experiments on sebacic acid based poly­
urethane, no systematic study in this area has been made so
far.

Hence in the present investigation a series of sebacic

acid based hydroxy esters and polyester polyols has been

 246

prepared and reacted -with excess TDI. Moisture cured film

from these prepolymer samples were obtained and the effect
of chain length on the film properties has been observed. The
effect of 3-5% catalysts like triethyl amine, triethanol amine
and 2-diethyl amino ethanol on curing of such films has also
been studied.

Since sebacic acid based polyester polyols do not

give good film, blends with castor oil and acetylated castor
oil have been prepared. Diethanol amide of sebacic acid was
prepared and its reaction with TDI has been noted to observe
the effect of tertiary nitrogen atom in the .prepolymer formation.

8.1.2 Polyester-polyols s

Methods of preparation of sebacic acid based hydroxy

ester and polyester polyol from ethylene glycol, propylene
glycol, diethylene glycol and butylene glycol have been des­
cribed in chapter - 4.

Preparation of Urethane Derivatives:

To ensure that the reaction with TDI takes place in

a homogeneous phase different solvents have been used for the
 247

prepolymer system to get a 15-20$ solution. Solvents like

xylene, toluene, methyl ethyl ketone, ethyl acetate, dimethyl

formamide, trichloro ethylene have been used. In some cases

it has been observed that the urethane prepolymer comes out
from the solvent phase. Effect,of mixed solvents was also
observed viz., xylene/ethyl acetate; xylene/ethyl acetate/DMF;
methyl ethyl ketone/dichloromethane/toluene etc. The best
solvent system found suitable for these poly(ester-urethane)
was xylene/ethyl acetate/DMF = 4s 4:1.

A calculated amount of this solvent blend to make a

15-20$ solution of the resulting urethane prepolymer was taken
in a three-necked flask, and the required amount of toluene
diisocyanate (polyol/TDI = 1/2) was added. The flask was
heated to 60-70°G, and polyol solution was added dropwise for
30 minutes. Reaction was conducted for 3-4 hours with good
stirring. Finally the product was cooled to room temperature.
In case of castor oil polyols blend castor oil polyol was
reacted at first with TDI for one hour and then the polyester
polyol was reacted.
 248

8.1.3 Evaluation of polyurethane film :

In case of Is2(polyol/TDI) reaction product moisture-

cured films were obtained by directly casting the prepolymer
solution obtained as above on to mercury, following the method
described in chapter - 6.

Since DMF (dimethyl formamide) is a less volatile

solvent it does not evaporate as rapidly as the other two
solvents. Hence the cured film obtained from prepolymer may
still contains some solvent, since DMF,is highly soluble in
water. The cured film was washed several times with water to
remove any solvent like DMF. The film was then dried under
atmospheric pressure and at room temperature.

In case of 1:1 (polyol/TDI) reaction product, the

prepolymer was poured into water and the solid mass was
isolated by filtration and dried under vacuum.

8.1.4 Film properties :

The tensile and elongation properties were observed

on films, which are 6-8 weeks old. The testing methods is
 249

the same as described earlier. Melting points were determined

on a Fischer Johns melting point apparatus, using a heating
rate of about 15-20 degrees per minutes.

8,2.0 Results and Discussion

Table-In indicates the softening point and appearance

of urethane samples obtained when polyester polyols reacted
with toluene diisocyanate in the ratio of 1:1 eq. (polyol/TDI).
These are similar to those of the parent polyester polyols,
and reaction with TDI shows no significant change in properties.

Table-II illustrates the effect of catalyst on the

moisture cured poly (ester-urethane) of sebacic acid hydroxyl
esters and polyester polyols.

In general it has been observed that triethyl amine

is a good catalyst for curing these systems. Triethanol amine,
although containing tertiary nitrogen atom, which'helps the
water isocyanate reaction during moisture curing, gives a
pasty mass. This may be due to the three hydroxyl groups of
catalyst also taking part in the reaction during curing; as a
 250

result less NCO is available for curing by reaction -with

atmospheric water. It has been observed that lower molecular
weight esters give polyurethanes having higher melting points
than the corresponding polyester. This may be due to the fact
that high percentage of aromatic ring presents in lower mole­
cular weight polyCester-urethane); impa.rt s .high melting point.
In general, sebacic acid based esters or polyesters give poly­
urethanes having brittle film characteristics except in case
of poly(butane diol sebacate).

In Chapter - 6 it has been noted that acetylated castor

oil is a good plasticizer for castor oil based moisture cured
polyurethane. Hence in.the present study the effect of 10-25^
acetylated castor oil on polyester based urethane has been
noted. It has been observed that the plasticizing effect of
acetylated castor oil is not so pronounced for polyester based
urethane as in the case of castor oil based polyols (Table-III).
Comparatively better moisture cured films can however be obtain­
ed -when (Table -IV) castor oil was blended with polyesters in
the ratio of 4:1. This can be explained by the fact that high
molecular weight of castor oil chain imparts flexibility.
Although these films have lower tensile strength and percentage
 251

elongation values, they have high melting point. High melting

point of the castor oil "blend may "be due to the long ricinoleic
acid chain, present in castor oil glyceride.

In this connection effect of amide type polyol, in

polyurethane formation was observed. Diethanol amide of
sebacic acid causes gellation during the progress of the reac­
tion. This may be attributed to the fact that diethanol amide
is a high functional polyol as well as having tertiary nitrogen
atom which catalyze the urethane reaction resulting gellation
within 15 minutes.

Reaction :

1) SR^WGOJg + H ■OR1OOCR .COOR * - 0

nH 17

Dii socyanate Polyester

OCNRi-NH. OR1 OOCR .COOR1 -0 •RH“ R^NCO

n
Urethane prepolymer
 252

2) 4E1(WG0)2 + 2(H0CH^H2)N0C.(GH2)8.G0N(GH2.CHg0H52

Diisocyanate Diethanol amide

>2(ochr1.hh .OGH2CH 2) .IOC (GH2)8 .QOI(CH g,CH qO

(OCN R-jNH

8.2.1 Gonclnsion :

From the above discussion it may he concluded that

ester linkage does not impart flexibility in the final poly­
urethane structure. Polar acetylated group of acetylated
castor oil also does not show any plasticizing action on
polyester urethane unlike in the case of ricinoleic acid
based esters.
 253

Table - I

Urethanes from TDI and Sebacic Acid Polyesters (TDI J Polyol = I)

Polyesters
i---------- r
5 Softening $ Appearance
IS point
$ °G

Poly (ethylene glycol sebacate) 48 Wasy solid

Poly (propylene glycol sebacate) - Soft mass

Poly(diethylene glycol sebacate) - Soft mass

Poly(butylene glycol sebacate) 52 Waxy solid

 254

Table - II

Efleet of Catalyst on Pifferent Moistare Cured Poly(ester-

urethane) of Sebaoic Acid

T“
T T T
Hydroxyl Terminated 5 TDI/Polyol $ Catalyst ^Melting$ Appearance
Esters $S ( eq/eq ) 5 3-5$ point
5 . 5 °C $
1----- -y

Ethylene glycol 2 Tri ethyl 285 Brittle,

sebacate amine opaque

-Do- 2 Tri ethanol - Pasty mass

amine

Poly(ethylene glycol 2 Tri ethyl 270 Brittle, a

sebacate) amine opaque

-Do- 2 Triethanol - Pasty mass

amine
-Do- 1.5 No 265 Brittle,
opaque

Propylene glycol 2 No 270 Tough,

sebacate brittle,
opaque
-Do- 2 Triethyl 255 Soft,
amine opaque
-Do- 2 Tri ethanol - Pasty mass
amine
 255

Table - Ii (Contd.)

X X 5 "1------------------------
1 5 2 5 3 5 4 5 5
f II 5 $

Poly(propylene 2.4 No 270 Opaque, brittle '

glycol sebacate)

-Do- 2 Tri ethyl 287 -Do-

amine

Diethylene glycol 1.8 Tri ethyl 268 -Do-

sebacate amine

Poly( di ethylene 2 T riethyl 256 -Do-

glycol sebacate) amine

-Do- 1.5 Tri ethanol - Pasty mass

amine
Poly (butylene 2 Tri ethyl 250 Hard, opaque^
glycol sebacate) amine

a Tensile strength - 45 kg/cm2

% Elongation at break - 50

k Tensile strength - 38 kg/cm2

% Elongation at break - 20
 - 256 -

T able - III
E ffe c t o f A c e ty la te d C a sto r O il on M oisture C ured P o ly (e s te r-u re th a n e ) o f S ebacic A cid

1- - - - - - - - - - - - - 5 5 S 5
-------------- ------------ ------------ ---------- 5
5TDI sP o ly o l 5 $
P o ly o ls
TC a- -ta- -ly- - st- - - - -
A cetylatediS T e n sile £ E lo n g atio n {M elting 9 Appearance,
g(eq /eq ) $ (3-5$) 5 c a s to r o il$ stre n g th g a t break jS p o in t 5
$ (fa) 5 (kg/cm 2 ) | (%) ji (OC) {
_________ ___ 8 S
_ _ _ _ _ _ _ _ 1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _
r T
P o ly (eth y len e g ly co l 2 T rie th y l 25 1 .8 10 255 Opaque,
seb acate) amine
E th y len e g ly c o l seb acate 1 .5 -Do- 25
i 272
b rittle
Opaque,
b rittle
PolyC propylene g ly c o l 2 Wo 17 30 26 5 Opaque,
seb acate) so ft
-Do- 1 .5 Wo 10 26 2 Op aque ,
b ri t t le
P ropylene g ly co l sebahate T ri eth an o l 25 P a sty mass
amine
P oly( d ieth y len e g ly co l 2 Wo 25 20 25 27 5 fyp aque ,
seb acate) e la s tic
D ieth y len e g ly co l seb acate 1 .8 T rie th y l 25 262 Opaque,
amine b rittle
 - 257

Table - 17

Effect of Sebacic Acid Polyesters on Castor

Oil Based Moisture Cured Polyurethane

5 5 5 5
Components 5 Tensile 5 Elongation5 Melting0 Appearance
5 strengthjS at break 5 point 5
5 kg/cm2 | | °C $
5 ' 5 5 5 _____ _

Castor oil +Poly(ethy­ 25 108 285 Britt le,

lene glycol sebacate) opaque

Castor oil + Polypro­ 30 100 290 Soft,

pylene glycol sebacate) elastic,
opaque

Castor oil +Poly(di­ 33 60 290 Elastic,

ethylene glycol opaque
sebacate)
 258 -

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