Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
OXAZOLINE/POLYOL/POLYISOCYANATE POLY~ERS AMD ~GCESS
. _ . _ . _ . . _
This invention relates to a process for the
pre~aration of interpolymers of oxazolines, polyols and
5 polyisocyanates, to the novel interpolymers thus
; produced and to some applications for the novel
interpolymers.
The reaction of a mono-oxazoline with phenyl
isocyanate to give a monomeric product has been
0 described in Ann. Chem. 698,167 (1966) by Nehring and
Seeliger. U.S. Patent No~ 3,661,861 discloses the
reaction of an oxazoline with a diisocyanate in a
solvent to produce an air-drying coating material which
forms a film by reaction with atmospheric moisture. No
15 polymer prepared by the interpolymerization of an
ox~zoline, polyol and polyisocyanate has previously
been described.
We have discovered that the interaction of
oxazolines, polyols and polyisocyanates produces
20 thermosetting polymers which are useful in polymer
composites and particularly in reaction injection
molding (RIM) applications. The novel thermosetting
polym~rs produced in this process have good physical
properties.
We have discovered that 2-alkyl oxazolines (mono
or bis~ of general Formula I will react rapidly with
mixtures of polyols and polyisocyanates to give
thermosetting polymers having good physical properties.
_ _
(R'Rn ~ ~ _ m
I
In Formula I n represents 2 or 3 and m represents 1 or
3!; 2 and w~en m is 1, R represents an alkyl group having
from 1 to 20 carbon atoms and an alkaryl group having
~s~
from 7 to 20 carbon atoms; when m i5 2, R rcpresents an
alkylene group having from 1 to 19 carhon atoms and R'
and R" independently represent hydrogen, an alkyl group
having from 1 to 10 carbon atoms or an aryl group
having from 6 to 12 carbon atoms.
; The polyols useful in this invention include those
having at least two hydroxyl groups per molecule and
having equivalent weights falling in the range of from
about 20 to about 5000. Such polyols include butane
diol, cyclohexane dimethanol, tripropylene glycol,
amide diols, urethane diols, polyether polyols such as
poly (tetramethylene ether) diols, poly (propylene
ether) polyols, polyester polyols, and the like.
Polyhydroxy polyethers are suitable and preferably
those having at least 2 hydroxyl groups per molecule
can be used. Polyhydroxy polyethers can be prepared by
polymerization of epoxide~ such as ethylene oxide,
propylene oxide, butylene oxide, tetrahydrofuran,
styrene oxide, or epichlorohydrin either on their own
or by chemical addition to other materials. Suitable
other materials include ethylene glycol, propylene
glycol, trimethylol propanes and 4,4 dihydroxy diphenyl
propane. Sucrose polyethers also may be-used.
Polybutadienes having hydroxyl groups as well as other
known hydroxyl containing vinyl addition polymerized
polymers can be used.
According to this invention, hydroxyl containing
polyesters, polythioethers, polyacetals, polycarbonates
or polyesteramides of the types known for the formation
of polyurethanes may also be used.
Particularly useful polyols for the present
invention include the following representative
aliphatic and aromatic polyhydric alcohols. Ethylene
glycol, propylene glycol, trimethylene glycol,
triethylene glycol, pentaethylene glycol, polyethylene
glycol, l,4-butanediol, diethylene glycol, dipropylene
2~31
glycol, 2,2-dimethyl-1,3-propanediol, he~amethylene
glycol, 1,4--cyclohexane dimethanol, xylene alcohols,
ethyl resorcinol, propylene resorcinol, 2,4-dimethyl
resorcinol, 3,6 dimethyl-1,2,4-benzene triol,
5 dime~hylol toluene, dimethylol xylene, bis hydroxyethyl
or bis-hydroxypropyl ethers of resorcinol, catechol, or
hydroquinones, 1,5-dihydroxy naphthalene,
4,4'--isopropylidene-bis-phenol, and the like.
The polyisocyanates useful in this invention
1~ include organic isocyanates having at least two
isocyanate groups per molecule. The polyisocyanates
can be of low, high or intermediate molecular weight
and can be any of a wide Vd~i~-ty of organic
polyisocyanates including ethylene diisocyanate,
trimethylene diisocyanate, dodecamethylene
diisocyanate, hexamethylene diisocyanate, hexamethylene
diisocyanate trimer, tetraethylene diisocyanate,
pentamethylene diisocyanate, propylene~
2-diisocyanate, 2,3-dimethyl tetramethylene
diisocyanate, butylene-1,2-diisocyanate,
butylene-1,3-diisocyanate, 1,4-diisocyanato
cyclohexane, cyclopentene-1,3-diisocyanate, p-phenylene
diisocyanate, l-methyl phenylene-2,4-diisocyanate,
naphthalene-1,4-diisocyanate, toluene diisocyanate,
diphenyl-4,4'-diisocyanate, xylylene-1,3-diisocyanate,
4,4'-diphenylene methane diisocyanate, 4,4'-diphenylene
propane diisocyanate, l,2,3,4-tetraisocyanato butane,
butane-1,2,3-triisocyanate, polymethylene polyphenyl
0 isocyanate, and other polyisocyanates having an
isocyanate functionality of at least two which are more
fully disclosed in U.S. Patent Numbers 3,350,362 and
3,382,215. Polyisocyanates which are polymeric in
nature including isocyanate prepolymers of all types
are included in this invention.
The equivalent ratio ~f oxazoline to polyol should
be in the range of from 1:99 to 95:5, respectively.
~2~s~
The oxa~oline group should be considered bifunctional
towards isocyanate functionality. Thus, the equivalent
amount of isocyanate functionality with respect to the
combined hydroxyl and oxazoline functionality should be
5 in the range of from 0.8:l to 3:l, respectively~
; Known polyurethane and isocyanurate catalysts such
as organo tin compounds, tertiary amines, and the li~e
can be included in the process of this invention. The
polymers ~btained from the simultaneous or sequential
10 polymerization of oxazolines with polyols and
polyisocyanates have been found to have high
temperature resistance. The process and products of
this invention can be used in the preparation of
composite materials by impregnating a reinforcement
15 such as glass fibers, graphite, etc. with monomeric or
prepolymeric mixtures of these compositions.
~ Although the polymerization process of this
invention can be carried out at room temperature or
slightly below, it is within the scope of the invention
to conduct the reaction at a temperature in the range
of from 20 degrees C. to 200 degrees C. and at
pressures in the range of from about a~mospheric up to
about 50 atmospheres.
Reactions of polyisocyanates with polyols result
in polyurethane formation, whereas oxazoline reaction
with isocyanates results in urea and amide group
contining polymeric material. Thus, in the instant
polymeric system based on interaction of
oxazoline~polyol/polyisocyanate, polymers with
urethane, amide and urea groups are found in the
polymers. In addition to this, isocyanurate groups can
be generated in the polymers by the use of known
isocyanurate catalysts such as hindered tertiary
amin~s, tetraalkyla~onium salts and the like in the
polymerization reaction.
Our invention is further illustrated in the
following representative examples.
EXAMPLES 1-18
Several experiments were caxried GUt in order to
demonstrate the oxazoline/polyol/polyisocyanate
reaction. The reactions were carried out in glass j~rs
with thermocouple for recording the reaction
temperature. The reactants were initially mixed at
lD room temperature and left undisturbed in the jar for
gellation to occur. The gel time was considered to be
the maximum exotherm temperature. As can be seen from
the results summarized in the Table, all the systems
containing some oxazoline reacted at a much faster rate
when compared with controls tExamples 1, 7, 11, 13 and
15 which are outside the scope of this invention3 which
did not contain oxazoline.
3D
TABLE
Oxazo- Iso-
Polyolline cyanate Exotherm Gel Time
Example (Grams) tGrams) Grams) (C.) (Min.)
1 B.D.~3.0) - 10 None in Greater
30 Min. Than 30.0
2B.D.(3.0) 0.2A 10 185 2.5
3B.D.(3.0) 0.3B 10 140 5.0
10 4B.D.(3.0) 0.25C 10 140 5.0
5B.C.(3.0) 0.25D 10 138 4.8
6B.D.(3.0) 0.3E 10 136 5.5
7 T.P.G.(4.8) - 7.4 None in Greater
30 Min. than 30.0
15 8T.P.G.(4.8) 0.25A7.6 129 5.0
9T.P.G.(4.8) 0.25D7.6 128 5.8
10T.P.G.(4.8) 0.4C 7.8 132 4.9
11Teracol 650 - 4.8 None in Greater
(11.2) 30 Min. than 30.0
2012Teracol 650 0.5A 5.6 135 5.5
(11.2)
13 BHED(8.0) - 3.8 None in Greater
30 Min. than 30.0
14BHED(8.0) 0.5A 4.6 138 5.0
2~15Polymeg 1000 - 11.5 None in Greater
~4.9) 30 Min. than 30.0
16 Polymeg 1000 0.5A 12.5 170 3.0
~4.9)
17Teracol 650 0.5F 4.2 150 1.9
B.D.(3.0)
(8.4)
18Teracol 650 0.6G 4.2 79 7.5
(3.4)
~35
In the Table B.D. rnea~s Butanediol; T.P.G. means
tripropylene glycol; Teracol 650 means 334 hydroxyl
equivalent weight poly(tetramethylene ether) diol; BHED
means bis-hydroxy ethyl dimerized linoleic acid;
5 Polymeg 1000 means 492 hydroxyl equivalent weight poly
(tetramethylene ether) diol; A means
2-ethyl-2-oxazoline; B means
2-undecyl-4,4-dimethyl-2-oxazoline); C means mixture of
2,2'-dimethylene bis(4,4-dimethyl-1,2-oxazoline),
10 2,2'-trimethylene bis (4,4-dimethyl-2-oxazoline) and
2,2'-tetramethylene bis(4,4-dimethyl-2-oxazoline); D
means 2,2'-tetramethylene bis
(4,4-dimethyl-2-oxazoline); E means 2,2'-decamethylene
bis(4,4-dimethyl-2-oxazoline); F means
2-hydroxypentyl-4-methyl-4-hydroxy methyl-2-oxazoline
and G means 2-fmethyl propylene~ bis(2-oxazoline). The
isocyanate used was liquid 4,4'-methylene bis(phenyl
isocyanate3.
EXAMPLE 19
2-Ethyl-2-oxazoline ~40g) and 33g of poly
(tetramethylene ether) diol [hydroxyl equivalent weight
of 492) were mixed and degassed on a rotary evaporator.
This solution was mixed rapidly with 130g of degassed
liquid 4,4'-methylene bis (phenyl isocyanate)
(isocyanate equivalent weight of 149) and the resulting
mixture was poured into a mold formed by two mold
release agent coated parallel glass plates held apart
39 by 1/8 inch spacers. The mold was kept in an oven at
100 degrees C. for one hour followea by postcuring for
one hour each at 145, 165, 180 and 200 degrees C. The
resulting solid opaque po:Lymer sheet was found to have
a notched izod impact strength (ASTM-D256) of 0.5 foot
pounds/inch of notch and a heat distortion temperature
(ASTM-DÇ48) of 220 degrees C.
~2~
EXAMPLE 20
This example is for comparative purposes only and
is outside the scope of the present invention.
Following the procedure of Example 19 a polymer sheet
; 5 was prepared from a mixture of 50g of the oxazoline and
152g of the polyisocyanate. The resulting sheet was
found to be too brittle to be tested for its physical
properties such as izod impact strength and h~at
- distortion temperature.
EXAMPLE 21
The procedure of Example 19 was followed using
29.5g of the oxazoline, 29~5g of bis-hydroxy ethyl
dimerized linoleic acid (hydroxyl equivalent weight of
320) in place of the poly (tetramethylene ether) diol,
0.3g of a tertiary amine catalyst (N,N',Nn-tris-
(dimethyl amino propyl~hexahydrotriazine) and 108.5g of
the polyisocyanate. The resulting polymer sheet was
found to have a notched izod impact of 0.5 foot
pound/inch of notch, a heat distortion temperature of
205 degrees C., flexural strength (ASTM-D790) of 16,431
psi and a flexural modulus of 297,137 psi.
EXAMPLE 22
The procedure of Example 21 was followed using 31g
of the oxazoline, 62.lg of the bis-hydroxy ethyl
dimerized linoleic acid, 0.3g of the catalyst and 116g
of the polyisocyanate. The resulting polymer sheet was
found to have a notched izod impact strength of 0.5
foot pounds/inch of notch, a heat distortion
temperature of 143 degrees C., flexural strength of
11,111 psi and flexural modulus of 201,544 psi~
E~MPLE 23
A mixture of 14,8g c)f the oxazoline, and 14.8q of
the polyol described in l:xample 21 was degassed and
o
;2~
mixed with 54.3g of the polyisocyanate of Example 21.
This solution was used to impregnate 10 layers of a 4
wide and 6" long glass cloth. The ~mpregnated cloth
was placed between the surfaces of a steel mold about 1
; to 2 psi was applied to the mold and the material was-
cured at 100 degrees C for one hour followed by
postcuring in the mold for one hour each at 140, 160,
and 185 degrees C. The resulting reinforced composite
material which contained 62% glass was found to have a
notched izod impact strength of 13.3 foot pounds/inch
of notch (hinged break), heat distortion temperature
greater than 220 degrees C., flexural strength of
42,054 psi and a flexural modulus of 1,872,886 psi.
1~EXAMPLE 24
- A glass reinforced composite was prepared by
following the procedure of Example 23 using 14.8g of
the oxazoline, 13.2g of poly Itetramethylene ether)
20 diol (hydroxyl equivalent weight of 492) as the polyol
and 54g of the polyisocyanate. The resultinq cured
composite which contained 66% glass was found to have a
notched izod impact strength of 15.3 foot poundsfinch
of notch (hinged break~, a heat distortion temperature
of greater than 220 degrees C., a flexural strength of
38,82g psi and a flexural modulus of 1,582,432 psi.
EXAMPLE 25
A solution of 40g of the oxazoline, 33g of the
poly (tetramethylene ether) diol and 135g of the
polyisocyanate was prepared by the procedure of Example
19. This solution was injected onto a glass mat placed
in a steel mold with Teflon liner and was cured for one
hour each at 100, 140, 16CI and 180 degrees C. The
resulting polymer composite which contained 30~ glass
was found to have a notched izod impact strength of 8.3
foot pounds/inch of notch, heat distortion
5~
temperature of greater than 210C, a flexural strenyth of 21,0~2
psi, and a flexural modulus of 601,241 psi.
l~.
