Note: Descriptions are shown in the official language in which they were submitted.
POLY (ETH~R AMIDE) COMPOSITIONS FROM REACTION OF
. _ _ _ _ _
BIS BICYCLIC AMIDE ACETALS WITH BIS- and POLY-PHENOLIC
. . . _
MATERIALS
This invention relates to a process for preparing
novel polymers containing e~her-amide groups by the
reaction of bis- or poly-bicyclic amide acetals with
bis- or poly-phenolic materials.
Bicyclic amide acetals and some of their reactions
have been described in a review article by R. Feinauer,
SYNTHESIS, pp. 16-26, 1971. Although the Feinauer
article describes the reaction of phenol with bicyclic
amide acetal to give the monomeric hydroxyalkyl
15 amido-ether compound via ring opening, no previous
report of polymer formation by the reaction of
bis-bicyclic amide acetals with bis- and poly-phenolic
matexials has been published.
I have discovered that thermoplastic and thermoset
20 polymers can be prepared by the reactions of di- or
poly-phenolic materials, respectively, with bis- or
poly-bicyclic amide acetals. The process of this
invention can also optionally include the use of
additives such as polyepoxides, polyoxazolines, and the
25 like in the polymerization reactions of bis- or
poly-biclic amide acetals with phenolic materials. The
; polymers which result from the process of this
invention have good thermal properties and are useful
in applications such as in reinforced composites,
30 adhesives, and the like.
The bis-bicyclic amide acetals useful in this
invention include those of Formulas I and II
r ~ J I ~ R ~
wherein R, Rl amd R" independently represent hydrogen',
an alkyl group having from 1 to 20 carbon atoms, an
aryl group having from 6 to 12 carbon atoms, an alkaryl
group having from 7 to 20 carbon atoms and a
hydrocarbon ether group having from 1 to 20 carbon
atoms and Rn' represents an alkylene group having from
1~ 1 to 20 carbon atoms, an arylene group having from 6 to
12 carbon atoms or an alkarylene group having from 7 to
20 carbon atoms.
The bis-phenol and poly-phenol materials useful in
this invention include those having at least two
20 aromatic hydroxyl groups per molecule including the
various benzene and fused aromatic ring diols and
triols, e.g., 1,4-benzene diol (hydroquinone),
1,3-benzene diol lresorcinol), 1,4-naphthalene diol and
1,3,5-benzene triol; the biphenyl diols, e.g.,
25 ~1,1' biphenyl)~2,2'-diol; the alkylene and
cycloalkylene bisphenols, e.g., 2 D 2'-methylene
bisphenol, 4,4'- (phenyl rnethylene~ bisphenol,
4,4'-(cyclohexanediyl) bisphenol,
4~4i-(1,2-diethyl-1,2-ethenediyl) bis phenol, and
30 3,4-bis~4-hydroxy phenyl)-2,4-hexadiene; the arylene
bisphenols, e.g., 4,4l-phenylene bisphenol; the oxy,
thio and sulfonylbisphenols, e.g., 2,3-oxybisphenol,
4,4'-thiobisphenol and 2,2' sulfonyl bisphenol; the
bis(hydroxyaryl) alkanones, e.g., bis(4-hydroxyphenyl)
35 methanone, 1,5-dihydroxy-9,10-anthracene dione and
4-[bis(4-hydroxyphenyl)methylene~ 2,5 cyclohexadiene-l-
-one; the various benzamide and benzoate derivatïves,
e.g., 2-hydroxy-N-(4-hydroxy phenyl) benzamide,
q-hydroxy~-4-hydroxy phenyl benzoate,
2-methyl-2-t4-hydroxy benzoyl)
5 oxymethyl-l,3-propanediyl-4-hydroxy benzoate,
bis-i4-hydroxy benzoate)-l,2-ethandiyl; 2-(4-hydroxy
benzoate) ethyl ether, bis(4-hydroxy
benzamide)-1,6-hexanediyl and bis 14-hydroxy benzamide~
l,4-benzenediyl.
1~ The bis-phenol and poly-phenol materials can also
contain substituents including alkyl, aryl, halo,
cyano, nitro, alkoxy, aryloxy, alkyl sulfides, aryl
sulfides, amine, alkyl or aryl amine, amide, ester and
the like.
In addition to the phenclic materials noted above,
a variety of oligomers containing a plurality of
phenolic groups constitutes an important class of
materials for this invention. Particularly
representative of such oligomers are the base or acid
20 catalyzed phenol and formaldehyde condensation products
such as the novalaks. Besides the conventional
resoles, the phenolic resins characterized in having
benzylic ether linkages preparéd by metal ion catalysis
such as disclosed in U.S. Patent No. 3,485,797 are
25 applicable. Other suitable polyphenoi oligomers
include the addition polymers and copolymers of a vin~l
substituted phenol such as 4-ethenyl phenol~
The process of this invention can be illustrated
in the following equation:
_ _ CHO
~ ~ ~ ArlOH)~ - -Rn~-~H-oAocH2cH2~H
_ - 2--~ n ~ C 2 2~C 2CH 2 ~ H 2
35 wherein Rn ~ has the above desig nation and Ar represen s
an aromatic hydrocarbon diradical.
In the process of this invention, the bicyclic
amide acetal functionality in relation to phenol
functionality is considered to be l:l. Thus, in the
absence of other reactive additives, the equivalent
5ratio of bicyclic amide acetal to phenolic hydroxyl is
l:l for high molecular weight polymer. However, it has
been found that under high reaction temperature
conditions, the thermoplastic polymer obtained in the
l:l reaction of a bis-bicyclic amide acetal with a
diphenol can be converted to a thermoset material.
This may be caused by the hydroxyl groups remaining
which may be involved in the cross linking reaction~
The amounts of additives ~e.g. epoxides, oxazolines,
etc.) to bis-bicyclic amide acetal used in the process
15 of this invention can be in the range of O:lOO to 95:5%
by weight. If an additive of this type is used the
amounts of phenolics used in any one case are adjusted
in order to keep the equivalents within the preferred
range~
The process of this~invention is preferably
carried out in the absence of a solvent or diluent.
The process is preferably carried out in the melt phase
which usually constitutes the mode of choice in the
preparation of matrix resins in the production of
25 composites which represents a prime utility of the
materials of this invention. In some cases it may be
desirable to carry out the initial polymerization
- reaction in solution employing a high boiling aprotic
solvent such as, for example, N,N-dimethylacetamide~ .
30 N,N-dimethylformamide, l-methyl-2-pyrrolidone, dimethyl
sulfoxide, and the like. The polymerization product in
such a case can then be isolated and curing completed
in a subsequent molding operation.
The process of this invention is preferably
3~ carried out at a temperature in the range of from about
2~
80 degrees C. to about 200 degrees C. at from about
atmospheric pressure up to about 50 atmospheres.
This invention is further illustrated in the
following representative examples.
EX~MPLE 1
A bis-bicyclic amide acetal was prepared in ~he
following manner. In a 250 ml round bottom flask
equipped with a magnetic stixring bar, a thermometer
with a temperature controller, nitrogen inlet and a
reflux condenser, 62.6g of 2-ethyl-2-oxazoline and
46.4g of 1,2,7,8-diepoxy octane were added. The
reaction mixture was heated under a nitrogen atmosphere
with constant stirring for about 47 hours during which
lS time the reaction temperature was maintained between
140 and 170 degrees C. The GLC analysis of the mixture
indicated the complete consumption of the
1,2,7,8-diepoxy octane. The mixture was then subjected
to fractional distillation under reduced pressure which
20 afforded approximately 52g of the bis-bicyclic amide
acetal of Forrnula I in which R and R' are hydrogen, R"
is ethyl and Rn' is C2H4 This product was found to
boil at 160-170 degrees C./0.03 mm of Hg.
EXAMPLE 2
The bis-bicyclic amide acetal of Example 1 (3.4g)
and resorcinol (12.lg) were mixed under nitrogen and
heated at about 155 degrees C. for about 2 hours to
give a thermoplastic polymer which was soluble in
30 dimethyl formamide (DMF) and l-methyl-2-pyrrolidone
(NMP). The PMT (pol~mer melting temperature) was
about 93-95 degrees C. and the infrared spectrum
for this material showed the presence of strong
bands at 3400 cm-l (hydroxyl group3 and 1625-35
35 cm-l (amide group). By TGA (thermogravimetric
analysis) 10% weight loss for the polymer in nitrogen
occurred at 329 degrees C. The polymer upon
further hea~ing at 160 degrees C. for 2 hours became
infusible. The Tg of DSC (Differential Scanning
Calorimeter) was 44.6 degrees C. and 10% weight loss in
nitrogen by TGA occurred at 356 degrees C,
EXAMPLE 3
The procedure of Example 2 was followed using 1.8g
of the bis-bicyclic amide acetal of Example 1 and l.Og
of a polyphenolic resin obtained by phenol-formaldehyde
condensation (Alnovol from American Hoechst) having an
equivalent weight of 90-100. The thermoset polymer was
obtained within two minutes of mixing the bis-bicyclic
amide acetal and polyphenolic resin at 160 degrees C.
The product after it had been postcured at 160 degrees
15 C. for three hours was found to be insoluble in DMF and
NMP. The Tg by DSC was 44.2 degrees C. and 10% weight
loss in nitrogen by TGA occurred at 339 degrees C.
EXAMPLE 4
The procedure of Example 2 was followed using O.9g
of the bis~bicyclic amide acetal, l.9g of liquid
diglycidyl ether of Bisphenol-A (epoxy equivalent
weight 185-195) and 1.5g of the polyphenolic resin
described in Example 3. A clear solution resulted
25 within two minutes after mixing the ingredients and
heating the mixture at 150 degrees C. and gellation
occurred within five minutes, The resulting polymer
was postcured at 160 degrees C. for about 2 hoursr The
Tg by D5C for this polymer was 104.2 degree~ CO and 10%
30 weight loss in nitrogen by TGA occurred at 406.3
degrees C.
EX~MPLE 5
The procedure of Example 2 was followed using 1.8g
35 of the bis-bicyclic amide acetal, 2.2g of resorcinol
and 3.24g of the bis-oxazoline of isophthalic acid.
The thermoplastic polymer obtained within five minutes
of heating at 16Q degrees C. was postcured at 160
degrees C. for three hours. The Tg by DSC was 75.4
degrees C. and 10% by weight loss in nitrogen by TGA
5occurred at 332 degrees C.
EXAMPLE 6
The proce~ure of Example 2 was followed using
0.45g of the bis-bicyclic amide acetal, 2.25g of the
polyphenolic resin described in Example 3 and ~.2g of
isophthaloyl bis-oxazoline. The thermoset polymer
obtained showed a decomposition temperature (TGA) of
368 degrees C.
EXAMPLE 7
The procedure of Example 2 was followed using O.9g
of bis-bicyclic amide acetal, 2.5g of the polyphenolic
resin of Example 3, l.9g of liquid diglycidyl ether of
Bisphenol-A and l.lg of isophthaloyl bis-oxazoline.
20 The resulting mixture, upon heating at 150 degrees C. t
became a clear solution within two minutes and gelled
within five minutes. The infusible polymer which
resulted was found to have a Tg by DSC of 110 degrees C
and 10% weight loss occurred in nitrogen by TGA at 374
25 degrees C.
EXAMPLE 8
A mixture of bis-bicyclic amide acetal (1.8g), the
polyphenolic resin of Example 3 (2.0g) and
30 terephthaloyl bis-oxazoline (1.12g) was heated at 200
degrees C to give a gelled polymer within five minutes.
The resulting polymer was postcured at 190 200 degrees
C. for one hour to give an infusible polymer which was
insoluble in DMF and NMP. The 10% weight loss in
35 nitrogen ~y TGA for this polymer occurred at '80
degrees C~
EY~MPLE 9
The procedure of Example 1 was followed using 4.3g
of isophthaloyl bis-oxazoline and 7.6g of liquid
diglycidyl ether of bis-phenol-A and the mixture was
5 heated under nitrogen for 2 hours at 155-160C. to give
a viscous paste. This resulting material which is
believed to be a poly-bicyclic amide acetal was mixed
with 2.lg of resorcinol and heated at 160C. Gellation
occurred within 15 minutes and the polymer was
10 post-cured at 160C. for 2 hours, The resulting solid
polymer was found to have a Tg of 139C. and a 10%
weight loss by thermogravimetric analysis (TGA)
occurred in the polymer at 352C.
EXAMPLE 10
This is a comparative example demonstrating that
when the reactants of Example 9 are mixed at once (no
bicyclic amide acetal present) and polymerized, the
resulting polymer which is outside the scope of this
20 invention has poor physical properties. The mixture of
4.3g of isophthaloyl bis-oxazoline, 7.6g of diglycidyl
ether of bis-phenol-a and 2.lg of resorcinol was heated
at 160C. for 4 hours to give a polymer which was found
to have a Tg of 113.6C. and had a 10% weight loss by
2~ TGA ~t 333C,
