Note: Descriptions are shown in the official language in which they were submitted.
~6i39~
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to ethylene copolymers.
More particularly this invention relates to copolymers of
ethylene, carbon monoxide, a flexibilizing monomer, and a
fourth monomer which contains epoxy side groups.
Description of the Prior Art
Ethylene polymers are characterized by a low
polarity and low reactivity. They are like waxes in this
respect, having a low dielectric constant and being
soluble in hot oils, hot wax and hot hydrocarbons.
They also are well known to be very inert. For some
uses it is desirable to modify the ethylene polymers
to make them flexible, to impart more polarity to the
polymers, and to be able to use them in reaction with
other resins. A small degree oE polarity and a certain
amount of flexibility can be imparted to an ethylene
polymer by incorporation therein of unsaturated organic
esters, such as vinyl acetate or acrylates. Howe-ver,
20 to obtain a high degree of polarity high levels of ester ~`
are required which in turn adversely affects the
inherit advantage of the long ethylene chain, e.g.,
low cost, good low temperature behavior, etc. Thus
it is desirable to increase the polarity of an ethylene
copolymer while retaining the hydrocarbon chain as
the major feature of the polymer. Ethylene copolymers,
however, modified to be more flexible and more polar
may still be relatively unreactive.
The art regarding thermosetting resins and
especially blends with other polymers will now be
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considered. Commercially available thermosetting resins
such as phenolics, epoxys, etc., have been found to be
useful because of the retention of their performance
at elevated temperatures. This retention of performance
is associated with the crosslinking or curing action
inherent in the structure of the thermosetting resins
utilized. However, this retention of high temperature
performance is accompanied by high stiffness and ;~
brittleness making it desirable to lower the stiffness of
such material or if some stiffness is desired by providing
a higher degree of toughness. The obvious solution, to
blend a flexible polymer into the thermosetting resin,
has not been successful to the best of our knowledge.
Molecular compatibility has not been achieved; the
desirable properties of the thermoset are lost.
SUMMARY OF THE INVENTION
According to the present invention there are
provided novel copolymers consisting essentially of, by
weight (a) 40 to 90 percent ethylene; (b) 2 to 20 per-
cent carbon monoxide; (c) 5 to 40 percent of a monomer
copolymerizable therewith to provide flexible polymers,
said monomer taken from the class consisting of un-
saturated mono- or dicarboxylic acids of 3 to 20 carbon
atoms, esters of said unsaturated mono- or dicarboxylic
acids, vinyl esters of saturated carboxylic acids where
the acid group has 1 to 18 carbon atoms, vinyl alkyl
ethers where the alkyl group has 1 to 18 carbon atoms,
acrylonitrile, methacrylonitrile, alpha-olefins of
3 to 20 carbon atoms, norbornene and vinyl aromatic
30 compounds; and (d) 0.2 to 15.0 percent of an ethylenically
~96C~32
unsaturated monomer of 4 to 21 carbon atoms containing
an epoxy group.
Preferred novel copolymers, in addition to
(a) ethylene and (b) carbon monoxide, are prepared from
(c) a monomer copolymerizable therewith taken from the
class consisting of vinyl alkanoates, e.g., vinyl
acetate, vinyl propionate, vinyl butyrate; alkyl
acrylates and alkyl methacrylates wherein alkyl is from
1 to 20 carbon atoms; and (d) an epoxy-containing
monomer taken from the class consisting of epoxy esters
of copolymerizable unsaturated organic acids, epoxy
ethers of vinyl ethers and allyl ethers and mono-epoxy
substituted di-olefins of 4 to 12 carbon atoms.
A specific preferred copolymer is prepared
from (a) ethylene, tb) carbon monoxide, (c) vinyl ~ -
acetate, and (d) glycidyl acrylate or methacrylate.
The preferred copolymers contain the fo:Llowing
weight percent of components (a) to (d):
(a) 45 to 90, more preferably, 50 to 70.
(b) 5 to 20, more preferably, 7 to 18.
(c) 10 to 33, more preferably, 20 to 30.
(d) 0.4 to 9, more preferably, 1.5 to 6. ;
The copolymers normally have a melt index within the ~
range of 0.1 to 3,000; preferably 5 to 500. `;
DETAILED DESCRIPTION OF THE INVENTION
The copolymers of this invention consist -~
essentially of the above described amounts of ethylene,
carbon monoxide and monomers (c) and (d) which are co-
polymerizable ethylenically unsaturated organic com-
pounds. Monomers (c) are selected from the class
:~ ,: ,. . ~, , ,:
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consisting of unsaturated mono- or dicarboxylic
acids of 3 to 20 carbon atoms, esters of such un-
saturated mono- or dicarboxylic acids, vinyl esters of
saturated carboxylic acids where the acid group has
1 to 18 carbon atoms, vinyl alkyl ethers where the
alkyl group has 1 to 18 carbon atoms, acrylonitrile,
methacrylonitrile, and copolymerizable unsaturated
hydrocarbons, such as alpha-olefins of 3 to 20 carbon
atoms, ring compounds, such as norbornene, and vinyl
aromatic compounds. Vinyl acetate is preferred monomer
(c) .
Monomers (d) are ethylenically unsaturated
monomers of 4 to ~1 carbon atoms which contain an epoxy
group. Such monomers are taken from the class consisting
of epoxy esters of copolymerizable un~aturated organic
acids, e.g., acrylic or methacrylic; the epoxy ethers
of vinyl ethers and allyl ethers, e.g., glycidyl
vinyl ether, vinyl cyclohexane monoxide, etc., or the
mono-epoxy substituted di-olefins of 4 to 12 carbon
atoms. Glycidyl acrylate and methacrylate are preferred
monomers (d).
In preparing the copolymers of the present
invention, commercially available ethylene, carbon
monoxide and unsaturated monomers (c) and (d) of about
100 percent purity are used initially and in supplying
continuous make-up for the polymerization feed stream.
The reactor vessel used is capable of withstanding high
pressures and temperatures, and is equipped with a high
speed motor-driven stirrer and pressure relief valves,
as well as jacketed walls for circulating heating or
--5--
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6~2
cooling fluids in order to control temperature. Carbon
monoxide and the other monomers are pumped into the
ethylene monomer feed stream at the pressure of the
reactor, and then the mixture of monomers is pumped at
reactor pressure into the reactor, either together or
separately. Catalyst, as necessary, is pumped into
the reactor through a separate feed line.
A mixture of copolymer and monomer exits the
reactor, and the pressure is reduced as the mixture flows
into a separator. Monomers leave the separator and are
either destroyed or pumped for recycle to the reactor ~ -
together with make-up monomers. Molten copolymer
leaves the separator in a stream, from which it is
cooled and further processed, e.g., the copolymer may be
cut into suitable sized particles and put into suitable
containers for shipping.
The flow of ethylene, carboll monoxide, monomers
(c) and (d) and catalyst into the reactor is carefully
controlled so that they enter the reactor in constant
continuous molar ratios and at the same continuous rate
at which product and unreacted monomers are discharged
from the reactor. The rates and molar ratio~ are
adjusted so as to provide in the product copolymer, by
weight, 40 to 90 percent ethylene, 2 to 20 percent carbon
monoxide, 5 to 40 percent of monomer (c) and 0.1 to 15
percent monomer (d). Effective stirring, usually at a
rate of at least 0.25 horsepower per gallon of reactor
volume, is provided in order to keep the reac~ing
monomers in intiMate admixture throughout the reactor.
The reactor temperature should be at least 140C. It
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6(~2
is preferred that the reactor temperature be maintained
within the range of about 155~300C., most preferably
155-225C., and that the reactor pressure be maintained
within the range of 5000-60,000 psi, preferably about
20,000-35,Q00 psi.
It is important in preparing the copolymers of -
the present invention that the contents of the reactor
be kept uniform with respect to the weight ratios of
ethylene, carbon monoxide and monomers ~c) and (d) to
produce the solid copolymers of the present invention.
None of the monomers should be depleted so that not less
than all of the monomers are reacting. Since the various
monomers react at different rates, a larger percentage of
faster reacting monomers will react in a given time. -~
Consequently, the ratio of feed rate for the monomers will
be different from the desired ratio of those monomers in
the copolymer produced. Thus, carbon monoxide reacts at a
rate about five times that of ethylene, so that when 10
percent of the ethylene has been incorporated in polymer,
about 50 percent of the carbon monoxide present is in poly-
mer. Conditions required to produce specific copolymers
vary, depending on the reactivity of monomers (c) and (d), ;
e.g., vinyl acetate reacts at about the same rate as
does ethylene, whereas other monomers such as methyl
methacrylate react about as fast as or faster than
carbon monoxide. The epoxy-containing monomers (d)
may react at rates which vary between the speed of
reaction of ethylene and carbon monoxide.
The free-radical polymerization catalyst
employed in the process can be any of those commonly
6æ~
used in the polymerization of ethylene, such as the perox-
ides, the peresters, the azo compounds, or the percarbonates.
Selected compounds within these groups are dilauroyl perox-
ide, ditertiary butyl peroxide, tertiary butyl peri~obuty-
rate, tertiary butyl peracetate, ~,~'-azobisisobutyronitrile
and other compounds of comparable free-radical activity.
Usually the catalyst will ~e dissolved in a suitable inert
organic liquid solvent such as benzene, kerosene, mineral
oil or mixtures of solvents. The usual catalyst level
is used, i.e., about 25 to 2500 ppm, preferably about
75 to 500 ppm, based on the weight of the monomers fed
to the reactor.
For the purpose of this invention it is
desirable to understand the nature of thermosetting resins
and the molecular character of blends of high polymers.
Thermosetting resins, such as the phenolic resins, are
produced as low molecular weight polymers for processing
into the desired form prior to the curing step. (These
resins are not formable after curing.) The low molecular
weight resins may be liquids, or if solid at room
temperature, they become fluid upon melting. This is in
contrast to the very high molecular weight and high melt
viscosity of the conventional thermoplastic resin. When
one attempts to disperse a high molecular weight thermo-
plastic resin in the low viscosity thermosettable resin,
the blend can only be achieved if the thermoplastic resin
is truly soluble in the low molecular weight liquid.
Otherwise the thermoplastic resin remains in the liquid
as relatively large particles. The first requirement
in this invention, then, is the discovery of the molecular
~ ~ ,
structure which will provide a thermoplastic resin ~hich
is soluble in the liquid thermosettable resin.
The curing of a thermosetting resin occurs by
the chemical linking of the thermosettable molecules
through sites which occur on the average at more than
two per moleculeO T~hen a nonreactive thermoplastic
polymer is dissolved in the thermosetting resin, these
thermosettable molecules move around rapidly during curing
to exclude the thermoplastic polymer. The thermoplastic
polymer is thereby forced out of the solidifying thermo-
setting composition. As a result a two phase system is
formed. One phase is the rigid brittle thermosetting matrix.
The second phase consists of the previously dissolved
thermoplastic resin. The second requirement of this
invention, then, is the incorporation of a reactive
epoxy group in the thermoplastic copolymer which will
provide a site through which the thermoplastic copolymer
parti~ipates in the curing step. The thermoplastic
copolymer is thereby intimately bound into the matrix
Z of the cured thermosetting resin. ~-
To summarize, the thermoplastic resin is
intended to act as a useful modifier for the thermosetting
resin. To be effective, it must be dispersed on a
molecular scale, i.eO, dissolved in the thermosetting
resin before the cure; and it must remain substantially
dispersed in the thermosetting resin after cure.
Another point which must be recognized is that
~here are two useful degrees of dispersion in terms of
the description above. One is when the thermoplastic
resin is so well dispersed, after cure, that the
~336~
resultant blend is clear. A molded cured film from such
a blend is more flexible than the unmodified thermosetting
resin. It has a modest and useful degree of elongation
before the sample fails; but when the sample does fail, it
fails in a brittle fashion without much absorption of
energy. It is well known in the art, however, that
rubbery impact modifiers for rigid thermoplastic resins
should be finely dispersed as a separate phase which is
intimately bonded to the rigid phase.
Thermosetting resins, on the other hand, are
much more difficult to toughen. The present invention
embodies the discovery of adjusting the structure of
the copolymers to achieve the same type of effect; i.e.,
the copolymers of the present invention can ~e adjusted so
they dissolve only partially in the uncured thermosetting
resin. Then, after curing, the tiny agglomerates of the
thermoplastic resin of the present invention are capable
of absorbing impact energy, but do so, in fact, only be-
cause they are also bonded through reactive sites to the
molecules of the cured thermosetting matrix.
The copolymers of the present invention can be
used to make curable blends with effective amounts
of solid organic thermosetting resins ~aken from the
class consisting of phenolic resins, e.g., phenol
formaldehyde resins; epoxy resins, and melamine formaldehyde
resins. The term l'phenolic resins" is meant to include
thermosetting phenol-aldehyde resins, e.g., those made
from phenol, cresol, e.g., m-p-cresol mixturel p-cresol or
cresylic acid, resorcinol with aldehydes such as
formaldehyde and ~urfural. The one-step type (resoles) or
--10--
, .
the two-step type (novalaks) are useful (U.S.P. 3,~38,931).
Also useful are phenol-formaldehyde resins modified with
alkyl phenols (e.g., cresols), polyhydric phenols (e.g.,
resorcinol, hydroquinone, etc.), or polyphenols (e.g.,
Bis~henol-A).
These curable blends may comprise 1 to 99 per-
cent of the above copolymers and 1 to 99 percent of the
thermosetting resins. Preferably the copolymer is present
in the blend in a percent of 5 to 95 and the thermosetting
resin i5 present in the blend in a percent of 5 to 95. A
particularly preferred percentage range for the co-
polymer is 10 to 50 percent, and the thermosetting resin
is 90 to 50 percent.
The above curable blends may be formed into a
sheet, a block for molding purposes, or a fiber before
~he blends are cured. The curable blends can be a solid
form which is grindable into a powder and then formed
into a molding or shaped article, into a film, a coat-
ing, or into a fiber before curing.
Cured compositions, in the forms described
above, result from heating, e.g., oven, mold, etc.,
the above curable blends.
The curable blends described herein may be
filled with the conventional fillers used in thermosetting
systems. These fillers may be wood flour, asbestos,
silica, fiberglass, cotton flock, mica, macerated fabric
and cord, rag, carbon black, or metal, such as iron,
lead, copper, etc.
The curable blends may be used to produce
flexible, semirigid or rigid films, coatings, fibers,
molded articles, foamed articles and adhesives.
EXAMPLES OF THE INVENTION
,.~
Th~ following Examples illustrate the invention
wherein the percentages are by weight unless indicated.
EX~,~LES 1 to 1~
Copolymers of ethylene, carbon monoxide, vinyl
acetate, and a fourth comonomer as specified in Table I
were prepared by mixing the respective monomers at the
feed rates shown in Table I, then feeding the resultant
18 mixture into a 700 cc highly stirred reaction vessel
together with a catalyst of the type and amount given
in Table I.
The reactor pressures and temperatures and
the conversion of monomer to polymer are also given in
Table I. The reactor residence time was ~.5 minutes.
The melt index of the polymer reportied in Table I was
determined according to ASTM D123~-65T, Condition E.
-12-
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EXAMPLE 15
A blend eontaining 15% of the eopolymer of Example
2 with a novalak phenolic resin (supplied by Durez Division
of Hooker Chemical Company as Durez~ 14000, a powdered
2 step type phenol formaldehyde resin containing about 7%
hexamethylenetetramine) was made by dissolving both pol~mexs
in tetrahydrofuran. The blend was dried on a steam plate
and then pressed into a 2 mil film. The film was eured for
15 minutes at 165C. in the press at a pressure of 20,000
psi. The eured film from this blend was elear, indieating
good eompatibility, and could be bent almost 180 before
breaking.
This result is in contrast to the behavior of a
film from the straight cured novalak phenolic resin, which
is very ~rittle and breaks under a very small strain.
The compatible nature of this blend is in contrast
to that encountered using an ethylene/vinyl aeetate/glyeidyl
methaerylate eopolymer, into whieh no earbon monoxide was
eopolymerized. An opaque incompatible blend was obtained
when this second eopolymer was used, indieating the essential
nature of the carbon monoxide constituent. The comonomer
ratio of this copolymer was 71f22/7.
EXAMPLE 16
A solution blend was made containing 35~ of the
polymer of Example 2 and the novalak phenolic resin of
Example 15O The blend was pressed into a 3" x 3" x
l/g" bar and cured for 10 minutes at 150C. This bar was
cut into bars 2 1/2" x 1/2" x l/g". The Izod impact `~
strength of these bars was 0~39 ft. lb./inch compared
to a value of 0.25 ft. lbO/inch for the unmodified
phenolic resin.
EXAMPLE 17
A 50/50 blend was made from solution using the
copolymer of Example 3 and the novalak resin of Example 15.
The unçured film, cast from the solution, was clear, in-
dicating compati~ility. This film was cured in an air
oven at 110C. for 20 min. to give a clear, flexible film.
The film could be bent double and creased without cracking.
This cured film was placed in a beaker containing
boiling acetone. This sample stayed as a film after stirring
for 30 minutes, indicating a complete cure.
EXAMPLE 18
A 50/50 blend was made on a ~-roll mill at a
temperature of 75C. 15 Grams of the polymer of Example 3
was blended with 15 grams of a powdexed l-step type phenolic
resin (resole) supplied as Durez~ 26L64. A 10 mil film
was melt pressed from this blend and found to be hazy,
indicating only partial compatibility. This blend was
pressed into a bar and cured. The I~sod impact strength
of this bar was 2.5. This is a very high value for a
cured polymer.
EXAMPLE 19
15 g. of the polymer of Example 3 was milled
with 15 g. of a powdered two-step phenolic resin
(novalak) Durez~ 22091 sold by Hooker Chemical Co., which
contained no curing agent. The blend was pressed into a
10 mil film and then held in the press at 150C. for one
(1) hour to cure. The film was clear, showing compati-
bility and was insoluble in boiling tetrahydrofuran show- ~ ;
ing a cure.
-15-
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EXAMPLE 20
A solution 50/50 blend was made from the
polymer of Example 3 and the novalak phenolic resin
described in Example 15 containing ~ percent of hexa-
methylenetetramine. A 10 mil film was pressed at 100C.7
the temperature was raised to 150C. for 30 minutes.
The film was clear.
The tensile properties of this film were:
tensile strength, 2150 psi; elongation, 60 percent;
tensile modulus~ 1~,000 psi. When the broken specimens
were returned to the original positions, the elongation
above was found to be >95~0 elastic (ASTM D-170~ 66
[0.2"/min. crosshead speed]).
EXAMPLE 21
A solution blend in tetrahydrofuran was made
using 0.5 g. of the polymer of Examp:le 1 and 1.5 g.
of liquid diglycidyl ether of bisphenol A with an
epoxy equivalent weight of about 190 and a viscosity of
about 13,000 cps. at 25C. (Epon~ ~2~ sold by Shell).
~0 0.15 g. of a curing agent triethylenetetramine was
added. The solution was evaporated to dryness to form
a film. The film was cured by heating over a steam bath
for one (1) hour. The film was clear and could be bent
double with no indication of brittleness. This
behavior was contrast to the brittle behavior of a
control film made in the same fashion~ but without the
polymer of Example 1.
~16
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EXAMPLE 22
A solution blend was made in-tetrahydrofuran
of 50 percent of the polymer of Example 2 and 50 percent
of a melamine-formaldehyde resin, hexamethoxymethyl-
melamine sold by American Cyanamid (Cymel~ 301). p-
toluene sulfonic acid was added to give 0.25 percent by
weight~ exclusive of the solvent, as a catalyst for cure.
This solution was coated on aluminum, dried and cured at
150C. for 1 hour. The film was very slightly hazy,
flexible, and could ~e bent double without cracking.
A similar film containing only the melamine-
formaldehyde resin and catalyst was also coated on
aluminum and cured. In contrast, this film was very
brittle and cracked when the aluminum was bent.
EXAMPLES 2 3 to 29
Following the procedure of Examples 1 to 14 a
series of tetrapolymers were prepared. Polymer composi-
tions and reaction conditions are summarized in Table II.
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CONTROL EXAMPLE 1 A~D
EXAMPLES 3 0 AND 31
Blends of phenolic resins, based on a 50/50
blend of wood flour and a two-step (novalak) phenolic
resin,-were made. 8 parts of hexamethylenetetramine
were added in the blending step to provide a cure catalyst.
All blends contain 40% wood flour for comparative pur-
poses. The polymer of this invention was added to re-
place a portion of the phenolic, except for Control
Example 1 where additional amount of the novalak phenolic `
resin was used in place of the tetrapolymer of the
present invention. Bars lf8" x 1/2" x 5" were molded at
100C. and cured at 160C. for 10 minutes.
From the results shown in Table III, it can be
seen that one can obtain a higher tensile strength and
higher flexural strain at failure with only a minor de-
crease in modulus (Example 30); or one can obtain a marked
increase in flexural strain at failure, a large reduction
in modulus with a relatively minor decrease in flexural
strength (Example 31).
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CONTROL EXAMPLE 2 AND
EXAMPLES 32 AND 33
Blends of phenolic resin containing wood flour
similar to Examples 30 and 31 were molded into 1/8" thick
plaques and cured as previously described. The plaques
were tested by a falling dart weighing 1/4 lb. (Gardner
Tester) to determine *he height at which a crack appeared
on the reverse side of the plaque. The results in
Table IV show that the energy to break can be increased
2-3 fold, depending on the structure of the polymer
added.
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CONTROL EXAMPLE 3 AND
EXAMPLES 34 AND 35
.
A commercial grade of a phenolic resin is
compounded specifically with medium length glass fiber
filler^and various additives for use in electrical
applications. This composition is coded Durez~ 23570.
Two tetrapolymers of the present invention were added
to be 20% of the total composition. For comparison,
20% of a pure novalak phenolic resin was added to provide
a control having the same amount of filler and additives.
Samples were molded, cured and tested for electrical
properties. In Table V, it is shown that the electrical
properties are not seriously impaired. The volume resis-
ti~Titv, h~w~v~r, ;s imnrnVQ~ at lea~t 5-fold.
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EXAMPLE 36
Elastomeric, cured products can be made when
the phenolic resin is less than 50~ of the blend.
Examples of such behavior are given in Table VI. Note that
the % elongation to failure is 10~-200%, and the elastic
re~overy of this elongation after failure is about 90%.
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CONTROL EXAMPLE 4 AND
EXAMPLES 39 to 41
A commercial epoxy resin is filled with glass
fibers and pelletized for injection molding uses
~Fiberite~ E Z748). Blends were made and evaluated
as shown in Table VII.
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