Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~6;~
08Cu 03840
~LENDS OF ACRYLONITRILE-BUTADIENE-
STYRENE/POLYSULFONE BLENDS WITH POLYET~ERIMIDES
This invention relates to blends of acrylonitrile-
butadiene-styrene/polysulfone blends (ABS-polysulfone)
and polyetherimides. These blends exhibit improved heat
distortion temperatures and flexural and tensile
properties, as compared to the correspondiny unmodified
ABS-polysulfone polymers.
The blends of the invention include a polyetherimide
of the formula:
~--O-Z-O ~) \N-I~
a
where a represents a whole number in excess of 1, e.g~,
10 to 1~,000 or more, and the divalent bonds of the
-0-Z-0 radical are in the 3,3'; 3,4'; 4,3' or the 4,4'
position; Z is a member of the class consisting of (1)
= - ---.._..
\,
~: \
5~ 0 8CU 03840
CH
CH3 CH3 CH3 CH3
~H3 CH3
CH3 8r Br CH3 Br ~r
and \/~/-- C(CEI3)2
C1~3 Br Br CH3 Br Br
and (2) divalent organic radicals of the general
formula:
~/-(X)q ~-
where X is a member selected from the class consisting
of divalent radlcals of the formulas: ~
\~
\ ' '
\\\\
.: :
~
~' ''
' '
~Z5~3~ o 8Cu 0 3840
O O ''
11 11 .
-CyH 2 y_ ~ -C-, -S -, -O- ancl -S -
where q i5 0 or 1, y i5 a whole number from 1 ~o 5 , and R
is a divalent organic radical selected from the class
consisting of (1 ) aromatic hydrocarbon radicals havin~
from 6 to abou~ 20 carbon atoms and haloqenated
derivatives thereof, (2) alkylene radicals and
cycloalkylene radicals having from 2 to about 2a rarhon
atoms, C ( 2-8 ) alkylene terminated
polydiorganosiloxanes, and (3) dîvalent radicals included
10 by the formula
~\/--Q ~_
where Q is a member 5elected frsm the class consistin~
of
O O
11 11
_o-, -C-, -S-, -S-, and C~:H2x-
O
x is a whole number from 1 to about 5 inclusive.
Particularly preferred polyetherimides for the ourPoses
o the present invention include those in which R is
selected from:
\~' ~} CH2 ~)--
:: ; :
: ., .,. ' ': -
~6~8~
08CU 03840
and
_,~ o ~
The polyetherimides where ~ is metaphenylene are most
preferred.
S The polyetherimides employed in the blends of the
present invention may be prepared by reacting an aromatic
bis(ether anhydride) o~ the formula
O O
1~ 11
O ~ O--O ~ O
Il 11
O O
where ~ is as defined hereinbefore with an or~anic
diamine of the ~ormula
H2N-R-N~2
where R is as defined hereinbe~ore.
Aromatic bis(ether anhydride)s of the above formula
include, for example, 2-bisE4-(2,3-
lS dicarboxyphenoxy)phenyl~-propane dianhydride, 4,4'-
bis(2,3-dicarboxyphenoxy~diDhenyl ether dianhydride 1,3-
; bis(2t3~dicarboxyphenoxy)benzene dianhydride; 4,4'-
bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-
bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,A'-
bis(2,3 dicarboxyphenoxy)diphenyl sulfone dianhydride;
2,2-bis~4-(3,4-dica~boxyphenoxy)phenyl]propane
dianhydride; 4,4'-bis(3,4-dicarboxyvhenoxy)diphenyl ether
dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl
~: sulfide dianhydride; 1,3-bis(3,4-dicarboxyphenoxy~benzene
; 25 dianhydride; 1,4-bis(3,4-dicarboxyphenoxy)benzene
dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone
dianhydride; 4-(2,3~dicarboxy~henoxy)-4'-~3,4-
~: _
.
.
.
~6~ 08CU 03840
dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; etc.
and mixtures of such diar.nydrides.
In addition, aromatic bis(e.~-her anhydride)s included
in the above formulas are shown by Koton, M.M.;
Florinski, F.S~; sessonov, .~.I.; Rudakov, A~Po (Institute
of Heteroorganic Compounds, Academy of Sciences,
U.S~,S.R.), U.S.S.R. 257,010, Nov. 11, 1969, May 3, 1967.
In addition, dianhydrides are shown by M.M. Koton, FoS~
Florinski, Zh. Orq. Rhin, 4(5), 774 (1968).
Organic diamines of the above formulas include, for
example, m-phenylenediamine, p-phenylenediamine, 4,4'-
diaminodiphenylpropane, 4,4'-diaminodiphenylmethane,
benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-
diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-
diaminonaphthalene, 3,3'--dimethyl~enzidlne, 3,3'-
dimethoxybenzidine, 2,4-bis(B-amino-t-butyl)toluene~
bis ( p~~ ~amino-t-butylphenyl)ether, bis(p-~methyl-o-
aminopentyl)benzene, 1,3-diaminotoluen~, 2,6-
diaminotoluene, bis~4-aminocyclohexyl)methane, 3-
methylheptamethylenediamine, 4,4-
dimethylheptamethylenediamine, 2~t1-dodecanediamine, 2,2-
dimethylpropylenediamine, octam2thylenediamine, 3-
methoxyhexamethylenediamine, 2,5-
dimethylhexamethyl~nediamine, 2 r 5~
dimethylheptamethylenediamine, 3
methylheptamethylenediamine, S-
methylnonamethylenediamine, 1,4-cyclohexanediamine, 1,12-
octadecanediamine, bis(3-aminopropyl~sulfide, N-methyl-
bis(3-aminopropyl)amine, hexamethylene~iamine,
heptamethylenediamine, nonamethylenediamine,
decamethylenediamine, bis(3-
aminopropyl)tetramethyldisiloxane, bis(4
aminobutyl)tetramethyldisiloxane, etc.
In general, the reactions can be advantaqeously
carried out employing well-known solvents, e.g., o-
-
,
:
~25i~
6 08CU 03840
dichlorobenzene, m~cresol/toluene, etc. in which to
effect interaction between the dianhydrides and the
diamines, at temperatures of from about 100C to about
250C. Alternatively, the polyetherimides can be
prepared by melt polymerization of any of the above
dianhydrides with any of the above diam:ino compounds
while heating the mixture of the ingredienks at
elevated temperatures with concurrent intermixing.
Generally, melt polymerization temperatures between
10 about 200C to 400C. and preferably 230C to 300C.
can be employed. The conditions of the reaction and
the proportions of ingredients can be varied widely
depending on the desired molecular weight, intrinsic
viscosity, and solvent resistance. In general,
e~uimolar amounts of diamine and dianhydride are
employed for high molecular weight polyetherimides~
however, in certain instances, a slight molar excess
(about 1 to 5 mole percent) of diamine can be employed
resulting in the production of polyetherimides having
terminal amine groups. Generally, useful
polyetherimides have an intrinsic viscosity 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.
Included in the many methods of making the
polyetherimides are those disclosed in U.S. Patent to
Heath et al. 3,847,867, Williams 3,847,869, Takekoshi
et al. 3,~50,885, White 3,852,242 and 3,855,178, etc.
by way o~ illustration, general and specific methods
for preparing polyetherimides suitable ~or the blends
of this invention.
The ABS-polysulfone component of the present novel
blends is a blend of a thermoplastic polysulfone plastic
and an acrylonitrile-butadiene-styrene (ABS) plastic.
~1
5~3~
7 08CU 03~40
The ABS plastic is a copolymer prepared by graft
copolymerizing resin-forming monomers, namely, styrene
and acrylonitrile, on a previously prepared
polybutadiene rubber spine, or a butadiene-styrene
copolymer rubber spine; in the final graft copolymer the
resinous portion and the rubbery portion are believed to
be in large part chemically combined.
Since the ABS material has both a rubbery component
(e.g., polybutadiene or butadiene styrene spine or
butadiene-acrylonitrile copolymer component) and a
resinous component (styrene-acrylonitrile), it may
therefore be regarded as a "gum plastic" type of
material~ Usually the proportion of the rubbery
component in the ABS is from 5 to 35~, while the
proportion of resin is correspondingly from 95 to 65%.
The overall proportion of acrylonitrile, butadiene and
styrene usually falls within the ranges: 10 to 40%
acrylonitrile; 5 to 65~ butadiene; and 25 to 85%
styrene.
The second component of the ABS-polysulfone is a
polysulfone resin component which may be described as a
polyarylene polyether polysulfone, which is a linear
thermoplastic reaction product of an alkali metal double
salt of a dihydric phenol and a dihalobenzenoic
compound, either or both of which contain a sulfone
linkage -SO~- between arylene groupings, to provide
sulfone units in the polymer chain in addition to
arylene units and ether units. Such polysulfones are
included within the class of polyarylene polyether
resins described in U.S. Pat. 3,264,536, Robinson et
alO, Aug. 2, 196.
These ABS-polysulfone and methods for their prepara-
tion are described for sxample by Inguili et al., U.S.
Patent 3,555,119. A preferred ABS-polysulfone for use in
the blends o~ this invention is commercially available from
:.,
.
':
,.~ ,:
~ j 08cu 03840
U.S.S. Chemicals Co , Pittsburgh, Pennsylvania, under the
trademark, Arylon~T.
Any proportion of polyether-imide can be employed,
and the above-mentioned improvements in physical
S properties are generally observed in the entire ranqe of
polyetherimide concentrations. Thus/ modified ABS-
polysul~ones containing from about 1% to about 99% by
weight polyetherimide (based on the weight of the ABS-
polysulfone-polyetherimide blend) are included within the
present invention. For economic reasons, blends
containing less than about 50~ by wei~ht polyetherimides
are generally preferred. Particularly preferred blends
contain from about 5% by weight to about 30% by weight
polyetherimide.
It has also surprisingly been found that impact
strengths can be improved over those of either the ABS-
polysulfone or polyetherimides alone~ Such improved
impact strengths are observed over a relatively narrow
range of concentrations, wherein the ratio of ABS-
polysulfone to polyetherimide is from about 1:99 by
wt. to abou~ 7:g3 by wt.
- The blends of this invention can be made simply by
mixin~ the solid components and extruding them at
elevated temperatures. Extrusion temperatures in excess
of the glass transition temperatures of each of the
components are typically employed. Such temperatures can
range from about 310C to about 330C. The blends of the
present invention may be injection molded at temperature
of about 315C and mold temperatures o~ about 80C.
Example
Several samples of polyetherimide and ABS-
polysulfone were blended and extruded. For samples 1, 2
and 8, ~he extruder profile was set at
332/332/330/3~7/32?~C with the die temperature at 327C.
~or samples 3, 4, 5, 6 and 7, the extruder pro~ile was
~ ~ 6~ 5 ~j 08CU 03840
set at 316/321/316/313/310C., with the die temperature
at 310C. The extrudates were chopped into pellets and
subsequently injection molded at 316~C and subjected to a
series of tests as indicated by the fo:Llowing chart.
.
.
:
,
:: , ; , :
: , :
~ 6~5~; 08CU 03840
.
D t~ ~ O ~ ~
t~ ~ ~ ~ t~ ts-
ô ~ ô
tY~ - o ~ ~9 o ~
o V _ ~
Q 1~1 ~ t`l u:l co o al tS
.U ~, ~t~
Ia--
.~ ~ O t~
N ~ C~--~ ~ t~ t~
~1~ O o o o o o ,_
. ;~5 .
'C ~ O OO O
V~ .
~ ~
~J
a~
8 ~t~' o ~, t~
. : : ~ :
U~
~ :~
2~ 08CU 03840
a)
.~
V h
~P~
~5 0 1~ W ~ ~
S~ ~ .
U~
U~
~ _
U~----_ _ _ ._ _ ~ _
~ O ~
a) !~ x ~ , o c~ w ~ ~ tO
~ C
~ .
V--
~ U~ ~
X C~ 0
~ ~,~
~:L 0 _ ~ a~
0 o ~ ~
~ 7c o o ~ ~ r ~ o
UV~
:: :
~ D O
~1 x o~
~ C~ ~ ~ ~ 0 2
. ~ ~
r
~ ~ U~ ~ ,
: ~ 0:
_~
O ~ ~ U~
~ O o
C
: : ` :
,
.
.
: ' '
,,
" ~ ... : ' "~ `:
. ,. : " :
: : ,
~'. ::
~ 2~i~5~t~ 0 8CU 0 3 840
12
~ ' O
c:~ o o r~ In ~D U~
X r--~ a~ ~r~
~ _ . O ~ C~
_ ~ o .
)J Q~
'~ ~
,_
~;
~o 2 cn ~ o
x .
In ~ o ~ ~ ~ u~
a) _I
.~ Q)
a
~ ~ .
C
g æ~
:
: .
-.. .
.. ..
.
.. ..
.
.~
- . ~
