Note: Descriptions are shown in the official language in which they were submitted.
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POLYETHERIMIDE BLENDS
BACKGROUND
The present invention relates to a class of polyetherimide blends
comprising a polyetherimide, a block copolymer owe a vinyl aromatic
hydrocarbon an a dine hydrocarbon and optionally a polyester.
Certain blends of polyetherimides and other polymers are known.
For example, U.S. Patent 4,14,1927 discloses a polyetherimide-
polyester binary mixture. U.S. Patent 4,259,458 discloses a blend
containing a polyarylate, a polyester, and at least one thermos
plastic polymer selected from the group consisting of an aromatic
polycarbonate, a styrenes resin, an alkyd acrylate resin, a polyp
urethane, a vinyl chloride polymer, a poly(aryl ether), a
copolyetherester block polymer or a polyhydroxyether.
SUMMARY OF THE INVENTION
In accordance with the present invention, a polyetherimide blend
contains from 50 to 95 parts by weight of a polyetherimide, 0 to 45
parts by weight of a polyester and 5 to 20 parts by weight of a block
copolymer of a vinyl aromatic compound and a dine compound.
DETAILED DESCRIPTION
2Q This invention relates to a class of polyetherimide blends
comprised of the following elements: (1) a polyetherimde,
(2) a block copolymer of a vinyl aromatic hydrocarbon and a dine
hydrocarbon and (3) optionally a polyester. These blends exhibit
improved impact strengths, as compared to those of the individual
components. Additionally, these blends show surprisingly
good flexural properties in conjunction with significantly improved
flow characteristics as the levels of either the polyester element
or -the block copolymer of a vinyl aromatic hydrocarbon and a dine
hydrocarbon element are increased.
I Cassius
The blends of the invention include a polyether-
imide ox the formula
a
where "a" represents a whole number in excess of 1, e.g.
10 to 10,000 or more, Z is a member selected Rome the
class consisting of (1):
SHEA C113 SHEA
SHEA SHEA SHEA SHEA
SHEA By By SHEA By By
C ( SHEA ) 2_/0/;
c~3 By By SHEA By Err
and (2) diva lent organic radicals of the general formula:
OWE X ) q Ox
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where X is a Myra selected from eye class consisting
of diva lent radical of the formulas,
. O O
Syria 5-, -ox and -S-,
O
where q is 0 or I y is a whole number prom 1 to S, and
S dival@nt bonds of the ~0-Z-0-radical are situated on the
phthalic android end groups, ego in the 3131, 3,4',
493' or the 4~4' positions and R is a diva lent organic
radical selected f rum the at ass consisting of (1)
aromatic hydrocarbon radicals having from 6 to about 20
carbon atoms and halogenated derivatives thereof, (2)
alkaline radicals and cycloalkylene radicals having from
about 2 to about 20 carbon atoms, C(2_8~ alkaline
terminated polydiorganosiloxane, and (3) diva lent
radicals of the formula:
lo Q I -
where Q is a member selected from the class consisting
of :
O O
_, S- and -CX~2x
o
where x is a whole number from 1 to 5 inclusive.
The polyetherimides own be obtained by any of the
methods well known to those skilled in the art including
the reaction of any aromatic bis~ether android) ox the
formula:
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. 4
O O
11 i
o\ ~()J~-Z-o_l~/ o
C 'C
If I
o . o
where Z it as defined above with an organic Damon of
the formula
H~.2N-R-NH2
where R is as defined above
Aromatic bis(ether androids of the above formula
include, for example 2,2-bis[4-(2,3~dicarboxyphenoxy)-
phenyl]-propane dianhydride; 4,4'-bis~2~dicarboxyphen-
oxy)diphenyl ether dianhydride; Boyce dicarboxy-
phenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxy-
phenoxy)diphenyl sulfide dianhydride; 1,4-bis~2-dicar-
boxyphenoxy)benzene dianhydride; 4,4'~bis(2,3-dicarboxy-
phonics) benzophenone dianhydride; 4,4'-bis(2,3-dicar-
~oxyphenoxy )diphenyl cellophane di~nhydride; 2t2-bisl4-
~3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-
bis(3,4-dicarboxyphenoxy~diphenyl ether dianhydride;
4t4'-bisl3,4-dicarboxyphenoxy)diphenyl sulfide Dunn-
drive; 1,3-bis~3,4-dicarboxyphenoxy)benzene dianhydride;
1,4-bis~3,4-di~arboxyphenoxy)benzene dianhydride; 4,4'-
bis(3,4-dicarboxyphenoxy)ben2Ophenone dianhydride; 4-
(2,3-dicarboxyphenoxy)-4'(~,4-dicarboxyphenoxy)dipphenol-
2,2-propane dianhydride; etc. and mixtures of such
dianhydrides .
In addition, aromatic bis~ether androids
included by the above formula are shown by Kitten, MUM.;
- Florinski, So Bessonov, MOE; Rudakov, ASP.
(Institute of Heteroorganic compounds r Academy ox
Science, U.S.S.R.), U.S.S.R. 257,010, Nov. 11, 1969,
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Apply May 3, 1967. Such dianhydrides are also shown by
MUM. Kitten, OOZE. Florins One ; I, 774
lg68) .
Organic dominoes of the above formula include, for
example, m phenylenediamine, p-phenylenediamine, 4,4'-
diaminodiphenylpropane, 4,4'-diaminodiphenylmethane,
benzidine, ~,4'-diaminodiphenyl sulfide, diamond-
phenol cellophane 4,4'-diaminodiphenyl ether, 1,5 Damon-
nap that one, 3, 3 ' -d ire thylbenz id i no, 3, 3 ' -dime thoxyben-
zidine, 2r4-bis(~-amino-t-butyl)toluene, bis~p-~-amino-
t-butylphenyl)ether, bistp-~-methyl-o-aminopentyl~ben-
Zion 1,3-diamino-4-isopropylbenzene, 1,2 basemen-
propoxy)ethane, m-xylylenediamine, p-xylylenediamine,
2,4-diaminotoluene, 2,6-diamino-toluene bis(4-aminocy-
~lohexyl)methane, 3-methylheptamethylenedi~mine, 4,4-
dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2
dimethylpropylenediamine, octamethylenediamine, Matthew
oxyhexamethylenediamine, 2,5-dimethylhexamethylene-
Damon, 2,5-dimethylheptamethylenediamine, 3-methylhep-
tamethylenediamine, 5-methylnonamethylenediamine, 1,4-
cyclohexanediamine, 1,12-octadecanediamine, bis(3-amiilo-
propyl)sulfide, N-methyl-bis ~3-aminopropyl)amine, hex-
methylenediamine, heptamethylenediamine, nonamethylene-
Damon, dec~methylenediamine, bis(3-aminopropyl) twitter-
methyldisiloxane7 bis(4-amlnobutyl) tetramethyldisilox-
anew and the like.
In general, the reactions can be advantageously
carried out employing well known solvents, e.g., o-
dichlorobenxene, m-cresol/toluene, etc. in which to
effect interaction between the dianhydrides and the
dominoes, at temperate of from about 100~C to about
~50C. Alternatively, the polyetherimides can be
prepared by melt polymerization of any of the above
Dan hydrides with any of the above Damon compounds
US while heating the mixture of the ingredients at elevated
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temperatures with concurrent intermixing Generally,
melt polymerization temperatures between about 200~C to
400~C and preferably 230C to 300C can be employed.
The conditions of the reaction and the proportions of
5 ingredients can be varied widely depending on the
desired molecular weight, intrinsic viscosity, and
solvent resistance. In general, equimolar amounts of
Damon and dianhydride are employed for high molecular
weight polyetherimides, however, in certain instances, a
slight molar excess (about 1 to 5 mole percent) of
Damon can be employed resulting in the production of
polyetherimides having terminal amine groups.
generally, useful polyetherimides have an intrinsic
viscosity [I] greater than 0.2 deciliters per gram,
preferably 0.35 to 0.60, or 0.7 deciliters per gram or
even higher when measured in m-cresol at 25C.
The second component of the blends of this invent
lion is a block copolymer of a vinyl aromatic hydrocar-
bun and a dine hydrocarbon. These block copolymers are
well known and are describer for instance, in
Chemistry of Synthetic Elastomers, edited by Kennedy et
at., Intrusions Publishers, Vol. 23, Part II (1969),
pages 553-55g. Such block copolymers are also
described, for example, by æelinskir U.S. Patent No.
3,251,905, and Holder et at., U S. Patent No.
3,23~,635.
In general, the block copolymer is represented by
the formula, -A-B A, in which terminal blocks, A, which
can be the same or different, are thermoplastic home-
polymers or copolymers prepared from a vinyl aromatic
compound wherein the aromatic moiety can be either moo-
cyclic or polycyclic. Examples of such vinyl aromatic
compounds include styrenes alpha-methyl styrenes vinyl
Tulane, vinyl zillion, ethyl vinyl zillion, vinyl napth-
thalene and the like, or mixtures thereof.
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.
The center block, I, is an elastom~ric polymer
derived from a dine hydrocarbon, such as ethylene and
battalion and conjugated dines, e.g., 1,3-butadiene,
2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and the
S like, or mixtures thereof.
The ratio of the copolymers and the average mole-
ular weights of each can vary broadly. Frequently
however the molecular weight of center block, B, will
be greater than that of the continued terminal blocks,
which appear to be necessary for optimum impact strength
and solvent resistance. The molecular. weigh of terming
at block A, will preferably range from about 2,000 to
about 100,000, while the molecular weight of center
block, 8, is preferably from about 25,000 to about
1 outyell.
If desired, the block copolymers own be post-
treated to hydrogenate the rubber portion of the Capella-
men. Hydrogenation can be accomplished using convent
tonal hydrogenation catalysts and reaction conditions.
With respect to the hydrogenated A-B-A block
copolymers, it is preferred to form terminal block A
having average molecular weight of from about 4,000 to
about 115,000 and center block B having an average
molecular weight of from about 20,000 to about 450,000.
Still more preferably, the terminal block A will have an
average molecular weight of from 8,000 to 60,000 while
center block B still have an average molecular weight of
prom S0,000 to aye.
The terminal block can comprise from 2 to 48~ by
weight, preferably from 5 to 35~ by weight of the block
copolymer.
Particularly preferred hydrogenated block Capella-
mews are thus having a polybutadi~ne center block
wherein from 35 to 55%, more preferably from 40 to 50
of the buttondown carbon atoms are vinyl side chains.
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Hydrogenated okay copolymers are described further
by Jones, USE Pat. No. 3j431,323 and Delaware et at.,
U.S. Pat No. 3,670,054, which issued
June 13, 1972.
S In preferred blends t the second component will key
an A-B-A block copolym~r of the polystyrene-polybuta-
diene-polystyrene or polystyrene-polyisoprene~polysty-
none type wherein the polybutadiene or polyi~oprene
portion Jan be either hydrogenated or non-hydrogena~ed.
Particularly preferred are the A-B-A block copolymers
of the ~tyrene-ethylene-butylene-styrene (SUBS) type.
The above block copolymers of a vinyl aromatic
hydrocarbon and a dine hydrocarbon are well known in
the art. They are commercially available from Shell
Chemical Company of Houston, Texas, under the trademark
CRETAN Particularly preferred are the CREATING grades
that are of the SUBS type. The KOWTOWING grades are
available with varying styrene/rubber ratios, for
example CREATING has a 14/86 styrene/rubber ratio
while CREATING 1 has a 33/67 styrenes to rubber
Russia .
The polyesters that can be employed in the blends
of this invention are conventional or known polyesters
made according to convent tonal or known methods. The
polyesters include polymers formed from dicarboxylic
acids containing a total of from about 2 to about 16
carbon atoms reacted with polyhydric alcohols such as
glycols or dills containing from 2 to 12 carbon atoms.
Aliphatic dicarboxylic acids may contain a total ox from
2 to 16 carbon atoms Preferably, the acids are aureole or
an alkyd substituted aromatic acids containing from 8 to
16 carbon atoms. Specific examples of linear aliphatic
dicarboxylic acids include oxalic acid, Masonic acid,
succinic acid! glutaric acid, adipic acid, plmelic acid,
sub Eric acid azelaic acid, sebacic acid, anal the like.
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Specific examples of an aureole acid include the various
isomers of phthalic acid, such as paraphthalic acid
(terephthalic acid and naphthalic acid Specific
examples of alkyd substituted aureole acids include the
various isomers of dimethylphthalic acid such as
dimethylisoph~halic acid,. dimethylorthoph~halic acid
dimethylter~phthalic acid, the various isomers of
diethylph~halic acid such as diethylisophthalic acid,
diethylorthophthalic acid diethylterephthalic acid, the
various isomers of dimethylnaphthalic acid such as 2,6-
dimethylnaphthalic acid and 2,5-dimethylnaphthalic acid,
and toe various isomers of dimethylnaphthalic acid such
a 2,6-dimethylnaphthalic acid and 2,5-dimethylnaph-
thalic acid, and the various isomers of diethylnaph-
thalic acid. Particularly preferred is terephthalicacid. When two or more dicarboxylic acids are used, it
it particularly preferred that at least 90 mole percent
of the total acid moiety be terephthalic acid.
Generally an excess of 95 mole percent terephthalic is
the most preferred.
It is well known to those skilled in the art that
in lieu of the various dicarboxylic acids, the various
divesters thereof may be utilized. Thus, alkyd divesters
containing a total of from 2 to about 20 carbon atoms as
well as alkyd substituted aureole divesters containing from
about to to about 20 carbon atoms may be utilized.
Examples of divesters include the divesters of oxalic
acid, Masonic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid, sub Eric acid, azelaic acid, or
sebacic acid, and the like Specific examples of
various alkyd substituted aureole divesters include the
various isomers of dimethylphthalate such a dim ethyl
terephthalate, a preferred compound, the various isomers
of diethylphthalate, the various isomers of dim ethyl-
-
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naphthala'ce, and the various isomers of die~hylnaph-
thalate .
The dills or glycols may ye straight chain or
branched The dills may Allah be aliphatic or cycloali-
phatic. Specific examples include ethylene glycol,
propylene glycol, trim ethylene glyoolO 1,2-butanediol,
1, 3-butanediol, 1, 4-butanedioL, 2 utanediol,
neopentyl gly~ol, cy~lohexanedimethanol, and the like.
Of the various glycols, those having from 2 to 8 carbon
atoms are preferred with ethylene glycol being portico-
laxly preferred. In lieu of the various glycols,
another class of polyhydric alcohols, such as the glycol
ethers containing from 4 to 12 carbon atoms, can be
utilized as for example dim ethylene glycol and Dow-
droxyethoxy ozone
The polyesters employed in the blends of this
invention can generally be made according Jo convent
tonal melt polymerization, or melt and solid state
polymerization technique.
The polyetherimide blends of the present invention
can contain a broad rang of relative proportion of the
polymer compounds These blends generally include come
positions comprising:
1. polyetherimide.......... .5-95%
I polyester. Do 0-45
3. block copolymer of a vinyl
aromatic hydrocarbon and
a dine hydrocarbon.......... 5-20~
the percentages being by percent by weight of the total
polymer weight
By varying the relative proportions of the polyp
etherimide blend, one can produce a broad spectrum of
resins each having their respective properties For
example, impact strength notched Issued values can
range as low as 39 to greater than 180 joules per meter.
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1 1
A large number of resins can be produced with varying
flexural properties Resins have been produced having
an initial modulus ranging from 1.50 gegapasca1s to
about 3~0 gegapascals.
Particularly preferred blends owe this invention
contain polyetherimide to polyester to block copolymer
in weight ratios of from about 75:20:5 to about 80:15:5.
Methods for forming the polyetherimide blends of
the present invention may vary considerably. Prior art
blending techniques are generally satisfactory. A
preferred method comprises blending the polymers, extra-
ding the blend, and chopping the extradite into pellets
suitable for molding by means conventionally used to
mold normally solid thermoplastic compositions.
The polyetherimide blends of the present invention
enable one to more specifically tailor a resin to its
end use. These blends permit the manufacturer to make a
less expensive product as well as make new products that
were not previously envisioned
The invention is further illustrated by the lot-
lowing example, which is not intended to be limiting.
Example
Blends were extruded in a 28 mm Werner Pfleiderer
twin screw extrude. The temperature ranges were from
330C at the feed throat to 325~C at the die. After
equilibrium had been achieved, the extradite was chopped
into pellets. The pellets were injection molded at a
temperature of 315~C and a mold temperature of 95C.
The molded specimens were then evaluated to determine
standard mechanic eel properties.
Thy tables below list the proportions ox each come
potent of the polyetherimide blend as well as the
resulting properties. The Issued impact data was deter-
mined from tests based on ASTM Method D-256. The heat
deflection temperature (HUT) was determined from tests
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I .
based on ASTM Method ~-648, The flexural data was
determined prom test based on ASTM Method D-790. the
tensile data was based on STYMIE Method ~-63~. ~ardex
Impact data was based on ASTM Method D~3029.
S The polyester that was used was CLEARTUFF~ 7202
This polyester it a polyethylene terephthalate resin
having an intern to visc05ity of .72 and is currently
available from The Goodyear Tire and Rubber Company of
Akron, Ohio.
The block copolymer was CREATING 1651 which is a
styrene-ethylene-butylene-styrene (SUBS) block copolymer
and is commercially available from Shell Chemical
Company of octane, Texas.
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16
Referring to the above test results, when SUBS is
blended with polyetherimides in a weight ratio of 5 to
US of SEWS to polyetherimide~ typical notched Issued
values of 224 joules per meter, an initial modulus of
1.96 gegapascals and a tensile modulus of 2.53 gegapas~
eels are obtained. When the SUBS level was 5 weight
percent, polyetherimide was 72~5 weight percent and PET
was at 22.5 weight percent, the notched Issued value was
57 joules per meter, the flexural modulus was 2.995
gegapascals and the tensile modulus was 2.79 gegapascals. Roy
partial substitution of PET for the pol~ether~nide yields a
resin which not only exhibits excellent notched Issued
values but maintains desirable tensile strengths and
flexural modulus
The polyetherimide blends of the present invention
are graphically illustrated in figure 1.
Figures 2-6 are enlargements of the area of the
graph of Figure 1 which depicts the present invention.
Figure 2 illustrates the relationship between the
relative proportions of components and notched Idea test
results. The shaded area depicts blends having rota-
lively high notched Issued values.
Figure-3 depicts the area of proportions associated
with high heat distortion temperatures (HUT).
Figure 4 depicts the area of proportions associated
with relatively high flexural modulus.
Figure 5 depicts the area of proportions associated
with relatively high ~lexural strengths.
Figure 6 depicts the area of proportions associated
with relatively high tensile strengths.
Modifications and variations of the present invent
lion will be apparent to those skilled in the art in
light of the above teachings. It is, therefore, to be
understood that changes may be made in the particular
" .
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embodiments of the invention described -which are within
the full intended Hope of the appended claims.
,
