Note: Descriptions are shown in the official language in which they were submitted.
This application is a divisional of co-pending Canadian
Application Serial No. 469,727, filed December 10, 1984.
COMPATIBILIZED BLENDS OF ACRYLIC ESTER COPOLYMER RUBBER
This application relates to improved polymer blends of
olefin polymer and cross-linkable acrylic ester copolymer rubber,
and in particular, blends of enhanced compatibility due to the
presence of a graft copolymer comprising acrylic ester copolymer
rubber compatibilizing segments and olefin polymer
compatibilizing seqments.
BACKGROUND OF THE INVENTION
Compatibilized blends of olefin polymer and
nitrile rubber are known, U.S. Patent 4,299,931. Although these
blends exhibit useful properties, they are not suitable for
applications involving low and high temperature exposures.
Olefin polymers and acrylic ester copolymer rubber are not very
compatible with each other. Their lack of compatibility prevents
the development of optimum properties in blends of these
materials. Thus, if the compatibility of the blend components
can be increased, improved blends may be obtained which can be
used where they are subjected to low and high temperature
environments.
SUMMARY OF THE INVENTION
It has now been discovered that an improved
composition comprising a blend of about 1-99 parts by weight of
an olefin polymer which is an amorphous or crystalline
essentially saturated homopolymer or copolymer of C2-C8 alpha
monoolefins, about 99-1 parts by weight of cured acrylic ester
copolymer rubber and at least 0.1 weight percent of a graft
copolymer which has at least one olefin polymer compatibilizing
segment derived from an olefin polymer
,
- ~ .
-2- 08-51(6465)A
which is an amorphous or crystalline essentially
saturated homopolymer or copolymer of C2-C8 alpha
monoolefins, or from polybutadiene, polyisoprene or a
polyalkenamer, and at least one acrylic ester
copolymer rubber compatibilizing segment derived from
a polymer selected from epichlorohydrin polymers,
nitrile rubber, urethane polymers, vinyl chloride
polymers, polyamides, polyamines, polyesters and
cross-linkable acrylic ester copolymer rubbers.
A preferred composition comprises a blend
of about 10-90 parts by weight of olefin polymer, and
corresponding, about 90-10 parts by weight of acrylic
ester copolymer rubber, and 0.5-25 parts by weight of
a compatibilizing graft polymer. A more preferred
composition comprises a thermoplastic blend of about
20-60 parts by weight of polypropylene, about 80-40
parts by weight of cured acrylic ester copolymer
rubber and 0.5-25 parts by weight of a
compatibilizing graft polymer in which the rubber is
dynamically vulcanized by masticating the blend under
vulcanization conditions. It is believed that when
the blend is dynamically vulcanized that the cured
rubber is in the form of small particles dispersed
throughout the polypropylene.
The term "graft copolymer" means a material
in which olefin polymer compatibilizing molecular
segments and acrylic ester copolymer rubber
compatibilizing molecular segments are chemically
linked to one another. The term, as used herein,
encompasses block copolymers as well. Examples of
ol~fin compatibilizing segments are polybutadiene,
polyisoprene, and polyalkenamer segments, as well as
~3~ 08-51(6465)A
segments of the olefin polymers themselves and any
other segments compatible with the olefin polymer.
Examples of acrylic copolymer rubber compatibilizing
segments are segments of epichlorohydrin polymer,
nitrile polymer, urethane polymer, vinyl chloride
polymer, polyamide, polyamine, acrylic polymer, and
polyester, as well as segments of acrylic ester
copolymer rubber itself and any other segments
compatible with the acrylic ester copolymer rubber.
Compatibilizing segments have chemical or physical
affinity for olefin polymer or acrylic ester copolymer
rubber. The compatibilizing graft copolymer has
affinity for both the olefin polymer and the acrylic
ester copolymer rubber and its presence improves the
compatibility between olefin polymer and acrylic ester
copolymer rubber. Examples of satisfactory graft
copolymers are described in U. S. Patent 4,299,931,
Column 3.
A thermoplastic graft copolymer of acrylic
ester copolymer rubber and olefin polymer is preferred
for preparing the improved compatibilized blends of
the invention. This graft copolymer may be prepared
by causing a reaction to form a bond between the
olefin polymer and acrylic ester copolymer rubber.
Preferably, only one bond is formed for each olefin
polymer molecule and acrylic ester copolymer rubber
molecule. Graft copolymers containing more than one
bond per molecule are satisfactoryi but it is
preferred that prior to vulcanizàtion the number of
bonds is not so high that the resulting graft
copolymer is in the form of a network molecular
structure and is no longer thermoplastic. However,
~- ,
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.
~ / 2.~ ~
during vulcanization of the rubber the graft copolymer
may become extensively cross-linked.
An especially effective class of graft copolymers
used in the composition is one in which the graft
copolymers comprise segments of olefin polymer and
acrylic ester copolymer rubber, said graft copolymer
being prepared from an olefin polymer containing one or
more graft forming functional groups. More preferred
graft copolymers are prepared from olefin polymer and
acrylic ester copolymer rubber each of which contains
graft forming functional groups. Examples of
satisfactory functional groups are carboxy-, halo
(preferably, chloro or bromo-), amino-; isocyanate
groups, groups derived from methylol phenolic material,
hydroxy groups, epoxy groups and sulfonyl, sulfonic acid
or salt groups. Functional olefin polymer and acrylic
ester copolymer rubber may be prepared by known
techniques and some of these materials are commonly
available. For example, functional groups may be
provided during polymerization by copolymerizing an
olefin and a monomer containing functional groups, for
example, an unsaturated carboxylic acid. Alternatively,
functional groups may be introduced by direct reaction
with the polymer by known grafting reactions. The
functional groups may react directly to form a graft
copolymer between the olefin polymer and acrylic ester
copolymer rubber. If the functional groups are such that
they will not react with each other, it will be necessary
to provide another reactant, herein referred to as a
grafting agent, in order to form a graft copolymer. For
A
.
~, rS S~
-5- 08-51(6465)A
example, when the functional group of the polyolefin
is carboxy and the acrylic ester copolymer rubber also
contains carboxy groups a polyfunctional reactant such
as a polyamine, preferably a diamine, may react with
the carboxy groups to form a graft copolymer. If
the functionalities on the polyolefin and the acrylic
ester copolymer rubber are hydroxy and amino, a
polyisocyanate grafting agent will be effective to
form a graft copolymer. Graft copolymers which are
derived from methylolphenolic modified olefin polymer
or maleic modified olefin polymer, carboxy- containing
acrylic ester copolymer rubber, and a diamino grafting
agent are especially preferred.
To insure that reaction occurs between
functionalizing agent and olefin polymer, it is
frequently advisable, and sometimes essential, that
the olefin polymer be functionalized in the absence of
rubber, before admixture with rubber in a later
portion of the procedure.
However, an olefin polymer can be
functionalized in the presence of acrylic ester
copolymer rubber by the action of a highly active
curative such as an azide. Here, molecules
of olefin polymer are functionalized by
a very small amount of free radical generator which
form transient "molecules" of functionalized olefin
polymer in which the functional groups are unpaired
electrons of the so-formed polymeric free radical.
The polymeric free radical (functionalized olefin
polymer) then attacks the acrylic ester copolymer
rubber molecules to form the compatibilizing graft
copolymer molecules which contain molecular segments
of both acrylic ester copolymer rubber and olefin
polymer. A reduction in either the molecular weight
-6- 08-51(6465)A
or concentration of acrylic ester copolymer rubber
suppresses the formation of rubber gel. Also, low
molecular weight rubber molecules are mobile and can
diffuse rapidly to the olefin polymer free radical
sites for graft copolymer formation; the resulting
compatibilizing graft copolymer molecules can also
diffuse more rapidly to the olefin polymer- acrylic
ester copolymer rubber interface to exert their
compatibilizing effect.
10Any graft copolymer of olefin polymer and
acrylic ester copolymer rubber is suitable for
preparing compatibilized blends of the invention.
Examples of suitable graft copolymers, methods for
preparing them, and the types of linkages visualized
lS between, for example, polypropylene (PP) and acrylic
ester copolymer rubber containing carboxy groups
(AAR) are shown as follows:
.
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-7- 08-51(6465)A
GRAFT COPOLYMER SYNTHESIS
Treat a molten mixture of
PP and AAR with a small amount
I of radical source such as an
5 1. ~ azide, azo compound, peroxide
or radiation source. For
example, Silane sulfonyl
azide (Hercules~
coupling agent S3076).
o
2. ~ NHRl-R-NR2-C ~ Halogenated polypropylene and
~ AAR were melt mixed and treated
X 0 with a grafting agent containing
amino functional groups. In
general Rl and R2 can be à
Cl 6 alkyl, aryl group (phenyl)
or hydrogen. R is a hydrocarbon
radical of 2-20 carbon atoms, for
example, alkylene, cycloalkylene,
arylene or combinations of them.
Preferred radicals are radicals
of 6-20 carbon atoms. If 4,4-
methylene di-aniline (MDA)
H2N- ~ CN2 ~ 2 were used,
Rl, R2 are H and R is
~CH2~ .
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:: :
-8- 08-5l(6465)A
GRAFT COPOLYMER SYNTHESIS
O
3. ~N-R-NHC ~ First treat molten PP with
maleic acid or anhydride (in
O the presence of peroxide) then
melt mix with MR and a grafting
agent with -NH2 functional
groups. R being the same as in
2. For example, if 4,4'-methylene
bis(cyclohexylamine) were used,
R is ~ CH2 ~ .
r OH~ o
4. ~ CH2 ~ ~ H2-OC ~ First molten PP is treated with
R ¦ a dimethylol phenolic derivative
- - (with a catalyst). The modified
OH PP is then melt mixed with AAR.
5 . ~--C H2_¦ ~3 3C H2 -NR l R NR2 c~i
Dimethylol phenolic modified PP
is melt mixed with AAR and a
grafting agent containing
amino groups.
.
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-9- 08-51(6465)A
GRAFT COPOLYMER SYNTHESIS
O
.. O
6. ~ ~ 0-R3-0c ~ Maleic acid/anhydride modified
~", ~H PP and AAR are treated with a
O grafting agent containing -OH
and/or functional groups above melt
temperature of PP. R3 may
o o be di-, tri-, or tetra-
~O -R 3 -O C ~ alkylene, cycloalkylene or
, , arylene. Preferably, R is
~ ~O-R3-OC--IAARI 3
10o ~--' the same as R above.
.. O
7. ~O-R4-OC ~ Maleic acid/anhydride modified
~ OH PP and AAR are melt mixed and
.- treated with an epoxide wherein
R4 is a substituted ethylene
and/or
~ 0 radical where the substituent
-~4-C - ~ is the residue of the epoxide
~O-R~-OC ~ molecule.,
.. O
~: O
..
8. ~ ~ ,, Maleic acid/anhydride modified
~N-R -NH C~ PP and AAR are melt mixed
0 and treated with a di-
isocyanate, wherein R has the
same meaning as before. For
example, if tolylene 2,4-
diisocyanate were used, R is
' ~ ''
>=~
CH3
:::
::
- 1 0
u ~
The properties of the rubber-plastic blends and
their vulcanizates are improved by the presence of an
appropriate compatibilizing graft copolymer. The
compatibilizing graft copolymer can be formed by the
direct interaction of the functional groups present on
the individual components, i.e. the olefin polymer and
the acrylic ester copolymer rubber, or by an interaction
of these individual components with another bi- or
multifunctional compound (grafting agent). The direct
interaction of functional groups occurs when the
functional group on each component is different, but is
capable of reacting with the functional group present on
the other component. If, for example, an acid or
anhydride group is present on one component, then any
other component with an -OH, - ~ , -NHR, -CH2OH,
o
or -NCO group can interact to form a compatibilizing
graft copolymer. If both the components have similar
groups, such as an acid group, then a di- or poly-
functional grafting agent such as a diol or polyol, for
example, pentaerythritol, a diamine such as a C6 to C20
diamine, e.g. methylene dianiline, an epoxide, di- or
polyisocyanate, etc., can be used to react with both the
functionalized olefin polymer and acrylic ester copolymer
rubber. When dissimilar groups which do not react with
one another, such as an -OH on one component and a
halogen or -NHR are present on the other component, then
the bridging compound should be such that its functional
groups should interact with
- '
. .. . . .
-11- 08-51(6465)A
both the components. To prepare the compatibilizing
graft copolymer in another way, one can mix the
appropriate components together and treat the mixture
with a radical source such as a peroxide, radiation,
S or a bis azo compound. The compatibilizing graft
copolymer may be pre-formed and then added to the
blend or it may be formed in situ.
Generally, the amount of graft forming
functional groups does not exceed 10 weight percent
of the olefin polymer or acrylic ester copolymer
rubber. It can, however, be considerably lower with
amounts of about 1 percent or less being enough to
cause sufficient graft copolymer formation to enhance
the compatibility of a blend of olefin polymer and
acrylic ester copolymer rubber.
The compatibilizing graft copolymer can be
formed from compatibilizing segments provided they
are functionalized so as to mutually interact to form
a link therebetween.
A suitable functionalized olefin polymer
may be conveniently prepared by masticating olefin
polymer, preferably at a temperature above its
melting point, for a period of about 1-20 minutes,
and 0.1 to 20 weight percent methylol phenolic
material, in the presence of an activator ~catalyst)
which promotes reaction between methylol phenolic
material and the olefin polymer. An example of a
satisfactory activator is a Lewis acid. Another
suitably functionalized olefin polymer may be
prepared by causing an unsaturated carboxylic acid
such as acrylic or methacrylic acid, maleic acid,
anhydride, or ester, or N-substituted maleamic acid,
to react in the presence of a free radical generator
,
~: -
-12- 08-51(6465)A
with olefin polymer, by known processes. For
example, see U. S. Patent 2,973,344. The resulting
functionalized olefin polymer is then caused to react
with functionalized acrylic ester copolymer rubber.
olefin polymers suitable for functionali-
zation to give graft copolymer precursors comprise
amorphous or crystalline essentially saturated
homopolymers or copolymers of C2-C8 alpha
monoolefins. Thermoplastic crystalline olefin
polymers are especially preferred. An important
subgroup of olefin polymers comprises high molecular
weight solid products from the polymerization of one
or more monoolefins by either high pressure or low
pressure processes. Examples of such polymers are
the isotactic or syndiotactic monoolefin polymers,
representative members of which are commercially
available. Satisfactory olefins include ethylene,
propylene, l-butene, l-pentene, l-hexene, 2-methyl-
l-propene, 3-methyl-1-pentene, 4-methyl-1-pentene,
5-methyl-1-hexene, and mixtures thereof.
Commercially available thermoplastic polyolefin
.
resins, such as polyethylene, polybutene-1, and
polypropylene, or mixtures thereof, may be
advantageously used in the practice of the invention
with polypropylene being preferred. Also suitable
for the practice of the invention are copolymers of
two or more olefins with copolymers of ethylene and
propylene being preferred.
Any methylol phenolic material which will
form a graft with olefin polymer may be used in the
practice of the invention. Suitable methylol
phenolic material may be prepared by condensation of
unsubstituted phenol, a Cl-C10 alkyl-p-substituted
- : ~
-13- 08-51(6465)A
phenol, or halogen substituted phenol with an
aldehyde, preferably, formaldehyde in an alkaline
medium, or by condensation of phenol dialcohols.
Methylol phenolic material includes polymeric phenols
containing up to 10 benzene rings but preferred
materials contain no more than three benzene rings.
Especially preferred are methylol phenolic materials
derived from dimethylol phenol substituted with
C5-C10 alkyl groups preferably tertiary alkyl groups
in the para position. Examples of satisfactory
dimethylol phenolic materials are described in U.S.
Patents 2,972,600; 3,093,613; 3,287,440; 3,709,840;
and 3,211,804, Column 5.
Halogenated, for example brominated, methylol
phenolic materials are also suitable. These
halogenated materials release, at elevated
temperatures, hydrogen halide, which in the presence
of a metal oxide such as zinc oxide, serves as an
acidic activator. Suitable methylol phenolic
materials are commercially available; for example,
they may be purchased under the trade names of
SP-1045,* SP-1055,* SP-1056*, CRJ 352*, and certain
Arofene*resins.
Any activator (catalyst) which promotes the
graft formation between olefin polymer and methylol
phenolic materials is suitable for the practice of
the invention. Preferred activators are Lewis acids
which include the acid-acting metal halides such as
boron trifloride, stannous chloride, zinc chloride,
titanium tri- or tetrachloride, aluminum chloride,
ferric chloride, ferric bromide, zinc bromide,
aluminum bromide or complexes thereof. Suitable
Lewis acids are described in U. S. Patent 4,121,026,
* Trade mark
- ' , . ' '
... . . -:
- .. - .
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Columns 5-6,
Suitable acrylic ester copolymer rubbers
comprise rubbery, cross-linkable acrylic ester
copolymers. The rubbers of the invention are
copolymers of one or more Cl-C4 alkyl acrylate
or methyacrylate ester with one or more C2-C8 alpha
olefins or dissimilar C1-C4 alkyl acrylate or
methacrylate ester, and are cross-linkable by virtue
of having reactive groups such as carboxy, hydroxy,
epoxy, halo, amino, isocyanates, sulfonyl or sulfonate
groups. These rubbers may be prepared by
copolymerizing an alkyl ester of an unsaturated
carboxy acid with another such ester or with an alpha
olefin and a third monomer containing any of the
reactive groups referred to above. Or, a
cross-linkable acrylic ester rubber can be prepared by
the process of U. S. Patent 4,415,710.
Preferred rubbers include acrylic acid-acrylic
ester-alpha-olefin terpolymers which are essentially
non-crystalline and have glass transition temperatures
(Tg) below room temperature. The rubber may be
prepared by partial hydrolysis of a polyacrylate
rubber to obtain the required acid groups.
Polyacrylate rubbers suitable for this
preparation are described in Rubber World Blue Book,
1975 Edition, pages 399-400. Suitable acidic
copolymer rubbers are preferably prepared by
polymerization of alkyl acrylate, acrylic acid or
methacrylic acid and an alpha olefin of 2-8 carbon
atoms. A preferred rubber is a polymer of ethylene,
Cl-C4 alkyl acrylate and acrylic acid. A more
preferred acrylic acid rubber is a polymer comprislng
-15- 08-51(6465)A
at least 50 mole percent of ethylene, about 0.5 to 10
mole percent acrylic acid and about 10 to 49.5 mole
percent of alkyl acrylate.
The improved blends of the invention may be
prepared by mixing olefin polymer, acrylic ester
copolymer rubber, and graft copolymer, preferably
above the melting point of the olefin polymer by use
of conventional masticating equipment, for example, a
rubber mill, Brabender Mixer, Banbury Mixer, or twin
screw continuous mixer. Mixing times should be
sufficient to obtain homogeneous blends.
Satisfactory mixing times depend upon the types of
olefin polymer and acrylic ester copolymer rubber and
upon the type and amount of graft copolymer.
Typically, mixing times of about 0.5-30 minutes are
satisfactory. If the polymer blend i8 obviously
non^homogeneous, additional mixing is required. When
the blend components are thoroughly mixed, improved
properties are obtained.
The compatibilized blends of the invention
are further improved by cross-linking, or curing
acrylic ester copolymer rubber by- conventional
techniques. Cross-linking agents (curatives) are
incorporated into the blends and the blends are
heated to effect cure. The characteristics of the
blends containing cured acrylic ester copolymer
rubber depend upon the relative proportions of olefin
polymer and acrylic ester copolymer rubber and
whether the compositions are statically or
dynamically cured. Static curing can give thermoset
compositions when the blend contains more than 30
parts by weight of cured acrylic ester copolymer
rubber per lO0 parts by weight of total polymer;
.
,
.
;: ,~. ~ :
-16- 08-51(6465)A
whereas, dynamic curing can give thermoplastic
compositions even when the blend contains 80 or more
parts by weight of cured acrylic ester copolymer
rubber per 100 parts by weight of total polymer.
Generally, compositions comprising about 50 parts or
more of cured acrylic ester copolymer rubber per 100
parts by weight of olefin polymer are elastomeric.
The effect of the relative proportions on blend
composition characteristics cannot be defined with
precision because the limits vary dependinq upon a
number of factors, such as, the kind of olefin polymer
and acrylic ester copolymer rubber, the presence of
fillers, plasticizers and other ingredients, and the
extent the rubber is cùred. When preparing graft
copolymer in situ, it is not necessary that the
grafting agent and the rubber curative are the same
material, however, often it is convenient and
sometimes preferred that they are the same.
Generally, the graft copolymer forms prior to or
simultaneous with curing (cross-linking) the rubber.
Of course, it is understood that the properties of
the compositions of the invention may be modified by
the addition of ingredients which are conventional in
the compounding of olefin polymer, acrylic ester
copolymer rubber, and blends thereof. For additional
information concerning compounding and dynamic
vulcanization, refer to U. s. Patent 4,104,210,
issued August 1, 1978. Compositions prepared by
dynamic vulcanization comprising a blend of about
20-60 parts by weight of olefin polymer, preferably
polypropylene, and correspondingly, about 80-40 parts
by weight of cured acrylic ester copolymer rubber in
the form of small particles (preferably 50 microns or
-17- 08-51(6465)A
less) dispersed throughout the olefin polymer, in
which the blend has been compatibilized, before or
after vulcanization, with a graft copolymer
comprising olefin polymer compatibilizing segments
and acrylic ester copolymer rubber compatibilizing
segments are especially preferred. Elastomer
compositions generally contain no more than 55 parts
of polypropylene per 100 parts of the composition.
Improved blend compositions of the
invention can be used to form a variety of molded,
extruded, or calendered articles. The properties of
the blend depend upon the proportions of the
components in the blend with .a wide range of
properties being available simply by varying the
proportions of the blend components.
The stress-strain properties of the
composition are determined in accordance with ASTM
test procedure D-638. True stress at break (TSB) is
the tensile strength at break multiplied by the
extension ratio also at break, extension ratio being
the length of a tensile test specimen at break
divided by the original, unstressed length of the
test specimen. Alternatively, extension ratio is
1.00 plus 1/100 of the percent ultimate elongation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Modified (Functionalized) Olefin Polymers
Polypropylene having maleic acid groups
grafted thereto is prepared by feeding a blend of 100
parts of polypropylene (Profax~ 6723), 2.5 parts of
maleic acid and 2 parts of an organic peroxide,
2,5-dimethyl-2,5-bis(t-butylperoxy)hexane ~40% active
on clay), Luperco~ 101X to a Reedco twin-screw mixing
extruder at 200C with a feed rate of 200 g/min. All
parts are by weight in this and the following
.:
- ,;
:
: ::
.. ::
'? Q ' ~
-18- 08-51~6465)A
examples. The product, maleic acid modified
polypropylene, is designated MA-PP~
Polyethylene, having maleic acid groups
grafted thereto, is prepared by masticating lO0 parts
5 of high density polyethylene (~arlex~ EHM 6006), 2.5
parts of maleic acid and 0.05 parts of
2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (90%
active), Lupersol~ lOl at 80 rpm in a Brabender
mixer. The batch size is 50-55 grams and cam type
rotors are used. The polyethylene and maleic acid
are first melt mixed at 150C and then the peroxide
is added and mixing is continued for about 5 minutes
at 160-165C. The mass is then removed and cooled in
a press. The product, maleic acid modified
polyethylene is designated MA-PE-l.
The same procedure is followed except low
density polyethylene (Dowlex~ 2476) and 0.1 part of
peroxide are used. The product, maleic acid modified
polyethylene is designated MA-PE-2.
Polypropylene having methylol phenolic
groups grafted thereto is prepared by masticating 100
parts polypropylene (Profax 6723) and 2 parts of
dimethylol-p-octylphenol (SP-1045) at 80 rpm and
190C in a Brabender until a molten homogeneous
mixture is obtained. 0.2 parts of SnC12.2H2O are
added and mixing is continued for 3 minutes. The
mass is then removed and cooled in a press. The
product is designated Ph.Mod.-PP.
Polypropylene having amino groups grafted
thereto is prepared by first preparing a maleic acid
modified polypropylene and then reacting it with
excess diamine. To a Brabender mixer at 180C and
100 rpm, there are charged 100 parts of polypropylene
I J
-19- 08-51(6465)A
tProfax 6801) and 2.5 parts of maleic acid. After
the mass is molten and mixed, there is added 0.15
parts of organic peroxide, Lupersol 101, and mixing
is continued for five minutes. Five parts of
4,4'-methylene bis(cyclohexylamine) is then added and
mixing is continued for five minutes at 190C. The
mass is removed, cooled, crushed and then dissolved
in boiling xylene. The product precipitates from the
solution upon cooling. The unreacted 4,4'-methylene
bis(cyclohexylamine) and any by-products are removed
by washing with acetone. The product, amine-modified
polypropylene, is designated DA- mod.-PP.
A graft copolymer is prepared by melt
mixing at 190C for 4-5 minutes in a Brabender*mixer,
parts of DA- mod.-PP and 60 parts of acidic
acrylic ester copolymer rubber, Vamac*G (described in
greater detail below). The product designated Graft
Copolymer-l is a graft copolymer comprising
polypropylene compatibilizing segments and acidic
acrylic ester copolymer rubber compatibilizing
segments.
ComPatibilized-polvmer-compositions
Compatibilized polymer compositions are
prepared by melt mixing olefin polymer, acrylic ester
copolymer rubber and a graft copolymer
(compatibilizing agent). Usually, the graft
copolymer is made in situ by melt mixing a
functionalized olefin polymer and acrylic ester
copolymer rubber with a difunctional grafting agent.
Since usually the grafting agent is also a curative
for the rubber, it is convenient to use enough
grafting agent ~rubber curative) to form the graft
copolymer and to cross-link the rubber. Preferably,
* Trade mark
- .,
. . .
~ : .:
.: - :~-- -:: .
~ .
-20- 08-51(6465)A
the rubber is dynamically vulcanized, i.e., the mass
of molten olefin polymer and rubber are masticated
until the rubber is cured.
Materials used to illustrate the invention
are as follows: acidic acrylic ester copolymer
rubber (AAR) in the tables) is purchased under the
trademark Vamac, believed to be a terpolymer of about
73 mole percent of ethylene, about 26 mole percent of
methyl acrylate and about one mole percent of a
carboxylic acid. Vamac* G is the neat terpolymer.
Vamac*123 is a masterbatch of 100 parts of rubber and
23 parts of fumed silica, stabilizers and processing
aids which, for convenience, are shown separately in
the tables and designated S,S, PA. An amine
antioxidant, Naugard*445, is designated in the tables
as N-445. Polypropylene (PP) is Profax~ 6723. Low
density polyethylene (LDPE) is Dowlex~ 2476, high
density polyethylene (HDPE) is Marlex~ EHM-6006.
4,4'-methylene dianiline, is designated MDA. 4,4'-
methylene bis(cyclohexylamine) is designated MCA.Hexamethylenediamine carbamate is DIAK-l.
4,4'-methylene bis(cyclohexylamine)carbamate is
DIAK-4. MDA, MCA, DIAK-l and DIAK-4 act both as
grafting agents and rubber curatives. All parts are
by weight in the tables.
Compositions of the invention comprising
improved compatibilized blends are illustrated in
Tables 1-8. Table 1 illustrates compositions
prepared from pre-prepared graft copolymer
compatibilizing agent and from graft copolymer
compatibilizing agent prepared in situ. The acidic
acrylic ester copolymer rubber (AAR) is Vamac*G. The
DA modified-PPl and Graft Copolymer-l are as described
* Trade mark
~J: ~ ,~1 ... ~ .
-21- 08-51(6465)A
above. Compositions of Stocks 1, 3, and 5 are
prepared by melt mixing at lO0 rpm at 190C for five
minutes in a Brabender mixer. The stocks are
removed, then returned to the mixer and remixed for
one additional minute. Compositions 2, 4 and 6-9
were dynamically vulcanized by masticating in the
presence of curatives. After melt mixing the AAR and
PP for two minutes, the stabilizer and curatives are
added. The MDA is added before the MCA or DIAK-4 is
added. Mixing (at 190C and 100 rpm) is continued
for 3 minutes after maximum consistency is reached.
In Stocks 3, 4 and 8, the Graft Copolymer-l is added
before the curatives. In Stock 9, the Graft
Copolymer-l is added after vulcanization is complete
as indicated by maximum consistency of the Brabender
mixer. The stocks are removed, then returned to the
mixer and re-mixed for one addit-ional minute. All
compositions are compression molded at 210C.
Tensile properties of specimens are evaluated on a
T-500 Tensometer at a speed of 20 inches (50.8 cm)
per minute. Stocks 1, 2 and 3 are controls f
unvulcanized and vulcanized compositions,
respectively, of a blend of acidic acrylic ester
copolymer rubber and unmodified polypropylene. The
data shows that tensile properties are improved by
vulcanization. Stock 3 shows that the addition of a
- graft copolymer has little effect in the absence of
curatives while Stock 4 shows that tensile properties
are about double when the rubber is cured in the
presence of the graft copolymer. It should be noted
that the compositions are nearly the same as the
controls since the graft copolymer contains 60% AAR
and 40% polypropylene. Stock 6 illustrates the
.
-22- 08-51 (6465)A
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-31- 08-sl(6465)A
preparation of a graft copolymer in situ by the
reaction of modified PP, AAR and grafting agent
(curative). The curative, MDA, serves both as a
grafting agent to form a graft copolymer comprising
polypropylene compatibilizing segments and rubber
compatibilizing segments and as a rubber curative.
The data shows that blends containing graft copolymer
prepared in situ exhibit superior properties. The
data of Stocks 8 and 9 show that improved
compatibilized blends are obtained when the graft
copolymer is added either before or after dynamic
vulcanization.
The effect of the relative proportions of
polypropylene and acidic acrylic ester copolymer
rubber is illustrated in Table 2. The acidic ester
copolymer rubber, polypropylene, stabilizer and
curatives are the same as in Table 1. A maleic acid
functionalized polypropylene is used as an
intermediate for the in situ formation of a graft
copolymer compatibilizer. The proportions of rubber
and polypropylene are varied from lO-90 and 90-10
parts by weight, respectively, in steps of 10 parts
by weight. For each composition, there is a control
(a) comprising unmodified polypropylene. In
compositions of the invention (b), 10 percent of the
polypropylene is replaced by maleic acid modified
polypropylene. The compositions are melt mixed and
dynamically vulcanized by the procedure of Table l.
Specimens are compression molded at 220C. Tensile
properties are determined as in Table 1, except for
Stocks 1-3 which were pulled at 2 inches (5.08 cm)
per minute. The data show that each composition
containing maleic acid modified polypropylene (in situ
. '`'- ~ :,
.
-32- 08-51(6465)A
graft copolymer formed) exhibit substantially
improved tensile strength and ultimate elongation.
The data show that the true stress at break is two or
more times greater when the graft copolymer is
present.
A study of curatives is shown in Table 3.
The acidic acrylic ester copolymer rubber is Vamac
123 which is a masterbatch containing 13.8 part
silica, stabilizers and processing aids (S,S,PA).
The compositions are prepared and tested by the
procedures of Table 1. The data show that excellent
compositions are obtained with each of the curative
systems. The data indicate that MDA is superior,
especially upon aging.
The effect of the amount of functionalized
polypropylene on blend properties is shown in Table
4. The rubber is Vamac 123. The curative level is
held constant with 3 parts of MDA and 0.5 DIAK-4 for
100 parts of rubber. The compositions are prepared
and tested by the procedures of Table 1. The amount
of maleic acid modified polypropylene is varied from
replacing one percent of the unmodified polypropylene
to replacing it completely. The data of Stock 2
indicates that improved compositions are obtained by
replacing one percent of the unmodified
polypropylene with MA-modified polypropylene. The
data of Stock 4 indicates that replacing ten percent
of the polypropylene with MA-modified polypropylene
results in compositions exhibiting optimum
properties. This suggests that the optimum amount of
graft copolymer has been formed. Stock 7 shows that
all of the polypropylene can be replaced by modified
polypropylene, but that lower tensile properties
-33- 0~-51(6465)A
result. Stocks 9 and 11 illustrate compositions with
different rubber/polypropylene ratios.
Compositions of the invention comprising
polyethylene and the effect of the amount of
functionalized polyethylene are illustrated in Table
5. The compositions are prepared and tested by the
procedures of Table 1. The amounts of curatives and
stabilizer for all compositions are 1.2 parts of MDA,
0.3 parts of DIAK-4 and 1.2 parts of N-445. The data
indicate that larger quantities of functionalized
polyethylene are required for optimum properties (as
compared to PP compositions) and that high density
polyethylene compositions exhibit better tensile
properties than corresponding compositions containing
low density polyethylene.
Compositions of the invention in which the
graft copolymer compatibilizing agents are made in
situ from methylol phenolic modified polypropylene
are illustrated in Table 6. The compositions are
prepared and tested by the procedures of Table 1.
Stock 1 is a control with unmodified polypropylene
and no curative. Stock 2 is a composition
corresponding to Stock 1 except the polypropylene is
replaced with phenolic modified polypropylene. Stock
3 is a composition corresponding to Stock 1, but is
dynamically vulcanized. Stock 4 is a composition
corresponding to Stock 2, but a graft copolymer is
formed in situ and the composition is dynamically
vulcanized. The true stress at break of Stock 4
indicates that this composition is 4 or more times
better than the controls. Stock 5 illustrates a
composition comprising a 50/50 mixture of unmodified
polypropylene and phenolic modified polypropylene.
,
-34- 08-51(6465)A
Compositions of the invention comprising
graft copolymers made in situ from various grafting
agents (curatives) are illustrated in Table 7. The
compositions are prepared and tested by the
procedures of Table l. The odd numbered stocks are
controls and the even numbered stocks are
illustrative of compatibilized blends of the
invention. Stock 2 contains chlorinated poly-
propylene, 26% Cl, m.p. 100C, Polycoat CP26P.
Stocks 3 and 4 contain as grafting agent/curative
gamma-aminopropyltriethyloxysilane, Silane~ A-1100.
Stocks 5 and 6 contain as grafting agent/curative
gamma-glycidoxypropyltrimethoxysilane, Silane~ A-187:
Stocks 9 and lO contain as grafting agent/curative a
bisphenol-A/epichlorohydrin-based epoxy curing resin,
Epon 828. The data show that superior compositions
are obtained by the presence of a graft copolymer
prepared in situ from a functionalized
polypropylene. The data also show that compositions
comprising chlorinated polypropylene (Stock 2),
pentaerthyritol (Stock 8) and tolylene
2,4-diisocyanate (Stock 12) exhibit extraordinarily
good tensile properties.
Compositions of the invention containing
plasticizers are illustrated in Table 8. A base
composition containing the same components as Stock
6(b) of Table 2 plus 24 parts of silica (HiSil*210),
0.24 parts of silane coupling agent (A-1100) and 0.36
parts of lubricant (Zelec~ UN) is prepared by dynamic
vulcanization in a "B" Banbury mixer. The additional
components are masterbatched with the rubber (Vamac*
G) before adding the other ingredients prior to
dynamic vulcanization. Plasticized compositions are
* Trade mark
: .
~ . ? ~ ~
J ~
-35- 0~-51(6465)A
prepared by melt mixing at 180-1~5C the` base
composition with various plasticizers. The amount of
plasticizer is 20 parts per 100 parts rubber in the
base composition. Stock 1, a control, is melt mixed
without any plasticizer under the same conditions as
the plasticized stocks. The plasticizers of Stocks
2-9, respectively, are (2) methyl phthalyl ethyl
glycolate, Santicizer M-17, (3) Cl-Cg trimellitate,
Santicizer 79 TM, (4) butyl phthalyl butyl glycolate,
Santicizer B-16, (5) polymeric polyester, Santicizer
429, (6) diundecyl phthalate, (7) isodecyl diphenyl
phosphate, Santicizer 148, (8) mixed C7, Cg, C11
dialkyl phthalate, Santicizer 711, and (9) mixed
C7-Cg dialkyl adipate, Santicizer 97. The data show
that different types of plasticizers are effective
and that the addition of plasticizer reduces the
Shore D hardness 5-7 units and oil swell 21-29%.
If softer compositions are desired, more
plasticizer may be added. For example, a composition
as above but containing 120 parts of Santicizer 97
exhibits a tensile strength of 5.6 MPa, ultimate
.
elongation of 250%, tension set of 15% and a Shore A
hardness of 64.
A compatibilized composition of the
invention is prepared by dynamically vulcanizing by
the procedure of Table 1 a blend comprising 60 parts
of Vamac G, 40 parts of polypropylene, 3 parts of
coupling agent (Hercules S3076, a silane sulfonyl
azide of the formula (CH30)3-Si-R-S02N3). These
ingredients were melt mixed 4-5 minutes to form a
graft copolymer before the curatives were added.
Then 0.9 parts of MDA, 0.3 MCA and 1.2 parts of N-445
were added and mixing is continued until dynamic
- .
~ ~ 2 ~
-36- 08-51(6465)A
vulcanization is complete. The compatibilized
composition has a tensile strength of 19.3 MPa,
ultimate elongation of 365%, tension set of 40% and a
true stress at break of 90 MPa. A control
5composition without coupling agent has a TSB of only
MPa.
To illustrate the invention as it applies
to the use of rubbers having functionalities other
than carboxy, a series of compositions was prepared
10and tested, in which polypropylene was melt-mixed
with acrylic ester copolymers having hydroxy, epoxy
and chlorine functionalities.
One compatibilizer graft copolymer was
prepared by charging 2 weight parts of MA-PP-l maleic
15acid modified polypropylene (preparation described
above) and one weight part of an amine-terminated NBR
rubber (sold under the trademark Hycar 1300 X 21) to a
Brabender Mixer and mixing 5 minutes at 190C. The
graft copolymer was removed, cooled in a press, and
20identified as "Compatibilizer-A."
Another compatibilizer graft copolymer was
prepared in the same manner as Compatibilizer A,
except that three weight parts of MA-PP-l and two
weight parts of a hydroxy-terminated acrylic ester
25copolymer (Hycar 4004-1) were used. The resultant
graft copolymer was identified as "Compatibilizer X."
The functionalized acrylic copolymer
rubbers used were Hycar 4004-1 (described above and
referred to in Table 9 as AR-OH), an epoxy-functional
30acrylic ester copolymer rubber (Hycar 211-60-16-3,
referred to as AR-Epoxy) and an active chlorine
functional acrylic ester copolymer rubber (Hycar
4043, referred to as AR-CL). Curatives used were
. . .
: ~ i
.' :' .
:. :
,: ,
-' . ~ -
_37_ 08-51(6465)A
DIAK-4 and tolylene diisocyanate (TD1). The stocks
were mixed as in previous examples; the rubber,
compatibilizer and polypropylene (PP) were melt mixed
in the Brabender at 80 rpm for two minutes at a set
temperature of 180C, and the curatives were then
added. After dynamic vulcanization was completed the
stocks were remixed for 1-2 minutes, compression
molded at 210~C and tensile tested at 20 in/min.
Proportions and test results are set forth
in Table 9. The results show that, in all cases,
presence of compatibilizer gave tensile properties
improved over the controls.
In order to demonstrate the invention when
acrylic ester copolymers are used which contain no
functionality other than the ester, a series of
compositions were prepared based on polypropylene (PP)
and a copolymer of ethyl acrylate and methyl acrylate
(80/20) sold by Gulf under the designation "PE 2205"
(AR). Compatibilizers used were Compatibilizer A,
described above and Compatibilizer B, made by the
following procedure: First a modified polypropylene
was prepared by reacting 100 parts of Profax 6801 with
2.5 parts of maleic acid and 0.15 parts of Lupersol
101 peroxide in a Brabender Mixer at 100 rpm at 180~C.
Mixing was continued five minutes after peroxide
addition. The product was then mixed five minutes
after addition thereto of S parts by weight of
4,4'-methylenebis-cyclohexylamine. After cooling and
crushing, the mass was suspended in boiling xylene,
cooled, and washed with acetone. The purified modi-
fied polypropylene product was then mixed in the Bra-
bender Mixer with Vamac G in a weight ratio of 60
Vamac to 40 modified polypropylene The product of this
- ~ ' '~ ... - ,
.
.
,. ' ~
-38- 08-51 (6465)A
N
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t` co a~ o ~ ~CD O O
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~: N
~ ~ O ~
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o o
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u~ I I 0 I~1 I~1 ~ IJ N
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X U~
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39- 08-5~6~ A ~
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o
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O
O O 1~1 1 0~r~ O ~ ~ N _I
O
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' l` O ~ O O
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~ m
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O 0 0 . 1` . U~ ~ ~ O
N I ~ 1~
D O
O O O ~ ~ ~
~a ~ ..
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ra ,a I ~ QJ ~ ` ` ` CJ
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-40- 08-51(6465)A
mixture was designated "Compatibilizer B."
Curatives used were LICA-44, described by
its manufacturer, Kenrich Petrochemicals, Inc., as
having the formula: RO-Ti(O-C2H4-NH-C2H4-NH2)3, and
Titanate-A,* made by the procedure of U. S. Patent
4,415,710. The proportions of the stocks and the
results of physical tests are shown in Table 10.
Tensiles were measured at 2 in/min. The results show
that the compatibilizers increased the modulus of
compositions containing both the cured and uncured
acrylate ester copolymer.
Although the invention has been illustrated
by typical examples, it is not limited thereto.
Changes and modifications of the examples of the
invention herein chosen for purposes of disclosure
can be made which do not constitute departure from
the spirit and scope of the invention.
* Trade mark
.. . . ~ . - ~ .
