Note: Descriptions are shown in the official language in which they were submitted.
7n6
This invention relates to novel resin compo9ition5
and more particularly, to polymer compositions comprising
aromatic polycarbonate resin, and a precompounded blend of
an olefinic resin and a hydrogenated elastomeric block co-
polymer of a vinyl aromatic compound and an olefinic elas-
tomer alone or in further combination with an aromatic poly-
carbonate, a styrene resin, and, optionally, a hydrogenated
elastomeric block copolymer of a vinyl aromatic compound
and an olefinic elastomer.
Background of the Invention. - The brittleness in
thick sections and the relatively poor stress crack resistance
of parts molded from aromatic polycarbonate resins is a
matter of common knowledge and experience. In addition,
polycarbonates per se are difficult to melt process, e.g. to
extrude and mold, because of their high melt viscosity. These
problems have been partially overcome in the art by blending
polyolefins or various rubbers into the aromatic polycar-
bonate resins. See, for example, Goldblum, U.S. 3 431 224,
dated March 4, 1969 and German Patent Publication 2 329 585,
dated January 2, 1975. Unfortunately, these additives are
somewhat limited in scope of use, because at high enough
levels to cause significant advantageous effects, there is
also a tendency to delaminate after molding, indicating a
certain degree of incompatibility.
In applicants' Canadian application, Serial No.
A ~ 9~ filed ~e~9~ ~r ~ 7~, a major
improvement is disclosed in providing high impact strength
combinations of aromatic polycarbonate resins with remarkably
enhanced flowability. The improvement comprises adding to
the aromatic polycarbonate a selectively hydrogenated rubbery
block copolymer.
It has now been discovered that aromatic carbonate
- 1 - ,q~
53~ 7 () li
l~.q~ 4
resins per se can be even more remarkably improvcd in terms
of impact strength, especially in thick walled moldincJs and
processing improved if they are intimately admixed with a
precompounded easily dispersible polymer system comprising
the selectively hydrogenated rubbery block copolymer and a
polyolefin resin, and, if desired, mixing in a further
amount of a hydrogenated block copolymer.
The resulting compositions show no tendency to
delaminate. They also have improved stress crack resis-
]0 tance; high aging resistance; and high heat resistance
during processing.
It is believed that the surprising efficiency of
the system is attributable to the special features of
system (b). System (b) consists of (i) a precompounded
mixture of a selectively hydrogenated vinyl aromatic-olefin-
vinyl aromatic block copolymer and (ii) an olefinic resin,
e.g., polyethylene, polypropylene, ethylene/propylene copol-
ymers, and the like, at a ratio of 20/80 to 80/20, of (i)
to (ii) by weight. In any case, dispersibility in component
(b) can be further improved by adding an aromatic polycar-
bonate or polystyrene as a dispersing aid in an amount of up
to 100 parts by weight of resinous components.
The new compositions may also be reinforced, e.g.,
with fibrous glass, and rendered flame retardant with flame
retardant additives to extend their field of use in molded
products.
According to the present invention, there are
provided high impact strength thermoplastic compositions
comprising an intimate blend of:
(a) an aromatic polycarbonate resin; and
(b) a precompounded composition comprising from 80
to 20 parts by weight of an olefinic resin comprising
polyethylene or a poly-CX-olefin .r~sin, alon~, or in ~urther
combination with an aromatie polyearbonate resin or a
styrene resin and correspondingly from 20 to 80 parts by
weight of a selectively hydrogenated linear, sequential or
radial teleblock copolymer of a vinyl aromatie compound (A)n
and (A)n and an olefinie elastomer (B), of the A-B-A ;
A-(B-A-B)n-A; A(BA)nB; (A)4B; B(A)4; or B[(AB)nB]4 type,
wherein n is an integer of 1 to 10; and, optionally,
(c) a selectively hydrogenated elastomerie bloek
eopolymer of one of the types set forth in (b).
Preferred eompositions will be those in whieh
eomponent (a) comprises from 99 to 60 parts by weight and
eomponent (b) comprises from 1 to 40 parts by weight and
eomponent (c) comprises from 0 to 20 parts by weight of the
total weight of components (a), (b) and (c). In particularly
preferred compositions, component (b) comprises from 80 to
20 parts by weight and component (c) from 20 to 80 parts by
weight of the total weight of (b) and (c).
In the compositions of this invention, the aromatic
polycarbonate component (a), and if used in (b), will be an
aromatic polycarbonate of a dihydric phenol and a carbonate
precursor such as phosgene, a haloformate or a carbonate ester.
Generally speaking, such carbonate polymers may be typified
as possessing recurring structural units of the formula
il
t o A - O - C t
wherein A is a divalent aromatic radical of the dihydric
phenol employed in the polymer producing reaction. Preferably,
the carbonate polymers used to provide the resinous component
(a) have an intrinsic viscosity (as measured in p-dioxane
in deciliters per gram at 30 C.) ranging from about 0.35 to
about 0.75. The dihydric phenols which may be employed to
27n~.
provide such aromatic polycarbonate polymers ar~ mononucle~r
and polynuclear aromatic compounds, containin~ as functional
groups, 2 hydroxyl radicals, each of which is ~ttached
directly to a carbon atom of an aromatic nucleus. Illustrative
dihydric phenols are 2,2-bis (4-hydroxyphenyl)propane
(Bisphenol-A); hydroquinone; resorcinol; 2,2-bis-(4-hydroxy-
phenyl)pentane; 2,4'-dihydroxydiphenyl methane; bis-(2-hy-
droxyphenyl)methane; bis-(4-hydroxyphenyl)methane; bis-(4-
hydroxy-5-nitrophenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane;
3,3-bis-(4-hydroxyphenyl)pentane; 2,2'-dihydroxy-diphenyl;
2,6-dihydroxy naphthalene; bis-(4-hydroxyphenyl sulfone);
2,4'-dihydroxy-diphenyl)sulfone; 5'-chloro-2,4'-dihydroxy-
diphenyl sulfone; bis-(4-hydroxyphenyl)diphenyl sulfone;
4,4'-dihydroxy-diphenyl ether; 4,4'-dihydroxy-3,3'-dichloro-
diphenyl ether; 4,4'-dihydroxy-2,5-diethoxydiphenyl ether;
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane; 2,2-bis-(3,5-
dibromo-4-hydroxyphenyl)propane; 2,2-bis-(3,5-dimethyl-4-
hydroxy phenyl)propane; and the like.
A variety of additional dihydric phenols which may
be employed to provide such carbonate polymers are disclosed
in Goldberg, U.S. 2,999,835 dated September 12, 1961. It is,
of course, known to employ two or more different dihydric
phenols or a dihydric phenol in combination with a glycol, a
hydroxy terminated polyester, or a dibasic acid in the event
that a carbonate copolymer rather than a homopolymer, e.g.,
bisphenol A and tetrabromobisphenol A with flame retardant
properties, is desired for use as component (a) in the
compositions of this invention.
When a carbonate ester is used as the carbonate
presursor in the polymer forming reaction, the materials are
reacted at temperatures of from 100 C or higher for times
varying from 1 to 15 hours. Under such conditions, ester
. . .
8~fl- ~ 7~1fi
interchange occurs between the carbonate ester and the
dihydric phenol used. The ester interchange is advantageous-
ly consummated at reduced pressures of the order of from
about 10 to about 100 mm of mercury, preferably in an inert
atmosphere, such as nitrogen or argon, for example.
Although the polymer forming reaction may be con-
ducted in the absence of a catalyst, one may, if desired,
employ the usual ester exchange catalysts, such as, for
example, metallic lithium, potassium, calcium and magnesium.
Additional catalysts and variations in the exchange methods
are discussed in Groggins, "Unit Processes in Organic Syn-
thesis" (4th edition, McGraw-Hill Book Company, 1952), pages
616 to 620. The amount of such catalyst, if used, is
usually small, ranging from about 0.001 to about 0.1%, based
on the moles of the dihydric phenol employed.
The carbonate ester useful in this connection may
be aliphatic or aromatic in nature, although aromatic esters,
such as diphenyl carbonate, are preferred. Additional
examples of carbonate esters which may be used are dimethyl
carbonate, dlethyl carbonate, phenylmethyl carbonate, phenyl-
tolyl carbonate and di(tolyl) carbonate.
A preferred method for preparing the carbonate
polymers suitable for use in providing the compositions of
the present invention involves the use of a carbonyl halide,
such a phosgene, as the carbonate precursor. This method
involves passing phosgene gas into a reaction mixture con-
taining the dihydric phenol and an acid acceptor such as a
tertiary amine (e.g., pyridine, dimethylaniline, quinoline,
etc.). The acid acceptor may be used undiluted or diluted
with inert organic solvents, as for example, methylene
chloride, chlorobenzene, or 1,2-dichloroethane. Tertiary
amines are advantageous since they are good solvents as well
-- 5
~c~ 7n
as acid acceptors during the reaction.
The temperature at which the carbonyl halide reac-
tion proceeds may vary from below 0C to about 100C. The
reaction proceeds satisfactorily at temperatures from room
temperature t25C) to 50C. Since the reaction is exothermic,
the rate of phosgene addition may be used to control the
reaction temperature. The amount of phosgene required will
generally depend upon the amount of dihydric phenol present.
Generally speaking, one mole of phosgene will react with
one mole of the dihydric phenol used to provide the polymer
and two moles of HCl. Two moles of HCl are in turn "attached"
by the acid acceptor present. The foregoing are herein
referred to as stoichiometric or theoretical amounts.
Another method for preparing the carbonate polymers
which may be used to provide the polycarbonate resin
compositions of the invention comprises adding phosgene to
an alkaline aqueous suspension of the dihydric phenol used.
This is preferably done in the presence of inert solvents
such as methylene chloride, 1,2-dichloroethane and the like.
Quaternary ammonium compounds may be employed to catalyze
the reaction.
A fourth method for preparing such carbonate poly-
mers involves the phosgenation of an agitated suspension of
the anhydrous alkali salts of the dihydric phenol used in a
non-aqueous medium such as benzene, chlorobenzene, and toluene.
This reaction is illustrated by the addition of phosgene to
a slurry of the sodium salt of 2,2-bis-(4-hydroxyphenyl)-
propane in an inert polymer solvent such as chlorobenzene.
The organic solvent should preferably be a polymer solvent
but need not necessarily be a good solvent for the reactants.
Generally speaking, a haloformate such as the bishalo-
formate of 2,2-bis-(4-hydroxyphenyl)-propane may be substituted
7~r.
for phosgene as the carbonate precursor in any oE the
methods described above.
In each of the above solution methods of preparation,
the carbonate polymer emerges from the reaction in either a
true or pseudo solution whether aqueous base or pyridine is
used as an acid acceptor. The polymer may be precipitated
from the solution by adding a polymer non-solvent, such as
heptane or isopropanol. Alternatively, the polymer solution
may be heated to evaporate the solvent.
With respect to components (b) and (c) the hydro-
genated block copolymers are made by means known in the art
and they are commercially available.
Prior to hydrogenation, the end blocks of these
copolymers comprise homopolymers or copolymers preferably
prepared from alkenyl aromatic hydrocarbons and particularly
vinyl aromatic hydrocarbons wherein the aromatic moiety may
be either monocyclic or polycyclic. Typical monomers
include styrene, alpha methyl styrene, vinyl xylene, ethyl
vinyl xylene, vinyl naphthalene, and the like, or mixtures
thereof. The end blocks (A) and (A) , may be the same or
different. They are preferably selected from styrene,
~-methyl styrene, vinyl toluene, vinyl xylene, vinyl naph-
thalene, especially styrene. The center block (B) may be
derived from, for example, butadiene, isoprene, 1,3-penta-
diene, 2,3-dimethyl butadiene, and the like, and it may have
a linear, sequential or teleradial structure.
The selectively hydrogenated linear block copoly-
mers are described in Haefele et al, U.S. 3,333,024, dated
July 25, ]967.
The ratio of the copolymers and the average molecular
weights can vary broadly although the molecular weight of
center block should be greater than that of the combined
7n~i
terminal blocks. It is preferred to ~orm termin~1 hlocks A
having average molecular weights oE 2,000 to 100, ono ~nd
center block B, e.g., a hydrogenated polybutadiene block
with an average molecular weight of 25,000 to 1,000,000. Still
more preferably, the terminal blocks have average molecular
weights of 8,000 to 60,000 while the hydrogenated polybuta-
diene polymer blocks have an average molecular weight between
50,000 and 300,000. The terminal blocks will preferably com-
prise 2 to 60% by weight, or more, preferably, 15 to 40~ by
weight, of the total block polymer. The preferred copolymers
will be those formed from a copolymer having a hydrogenated/
saturated polybutadiene center block wherein 5 to 55%, or
more, preferably, 30 to 50% of the butadient carbon atoms, are
vinyl side chains.
The hydrogenated copolymers will have the average
unsaturation reduced to less than 20% of the original value.
It is preferred to have the unsaturation of the center block
B reduced to 10%, or less, preferably, 5% of its original value.
The block copolymers are formed by techniques well
known to those skilled in the art. Hydrogenation may be
conducted utilizing a variety of hydrogenation catalysts
such as nickel or kieselguhr, Raney nickel, copper chromite,
molybdenum sulfide and finely divided platinum or other nobel
metals on a low surface area carrier.
Hydrogenation may be conducted at any desired
temperature or pressure, from atmospheric to 300 psig, the
usual range being between 100 and 1,000 psig at temperatures
from 75 F to 600 F for times between 0.1 and 24 hours, pre-
ferably, from 0.2 to 8 hours.
Hydrogenated block copolymers such as Kraton G - 6500,
Kraton G - 6521, Kraton G - 1650, Kraton G - 1651 and Kraton
G - 1652 from Shell Chemical Company, Polymers Division, have
~3t:~lt-27n~,
been found useable according to the present inventlon. Kraton
G - 1650 is preferred. Also useable are the so-called hydro-
genated Solprenes of Phillips, especially the product desig-
nated Solprene - 512.
The radial teleblock copolymers of which the Solprenes
are typical examples can be characterized as having at least
three polymer branches with each branch of the radial block
polymer comprising terminal non-elastomeric segments, e.g. (A)
and (A ) as degined hereinabove. The branches of the radial
block polymer contain a terminal non-elastomeric segment
attached to an elastomeric polymer segment, e.g. (B) as de-
fined above. These are described in Marrs, U.S. 3,753,936
dated August 21, 1973 and in Zelinski, U.S. 3,281,383, dated
October 25, 1966, and they are selectively hydrogenated by
procedures known per se. In any event, the term "selective
hydrogenation" is used herein to contemplate polymers in which
the elastomeric blocks (B) have been hydrogenated but the non-
elastomeric blocks (A) and (A ) have been left unhydrogenated,
i.e., aromatic.
As is mentioned above, other additives may be present
in the compositions, such as pigments, e.g., titanium dioxide.
With respect to component (b), a variety of polyolefins
can be used with the block copolymer to form the premix. In
general, it is preferred to use polyethylene or a poly--olefin
or a copolymer of ~-olefins, the ~-olefin having from 3 to 8
carbon atoms. These can be made by known procedures and are
readily available from a number of sources. ~specially pre-
ferred are polyethylene or polypropylene and their copolymers
and block copolymers, e.g., ethylene-propylene copolymer, etc.
With respect to one aspect of component (b), the
styrene resins most suitable are polymers of vinyl aromatic
hydrocarbons prepared by polymerizing at least one alkenyl-
_ g
aromatic hydrocarbon of the benzene seri~s and incl~lde th~
polymers of styrene and ring-substituted styrenc whercin th~
aromatic nucleus is substituted with one or more alky] groups
preferably containing from 1 to 4 carbon atoms such as methyl
or ethyl or with a halogen group such as a chloro group.
Examples of such monomers are styrene, vinyl toluene, vinyl
xylene, vinyl ethyl benzene, and divinyl benzene. Suitable
monomers also include chain-substituted styrenes such as
alpha-methyl styrene. Preferably, these polymers have an
intrinsic viscosity of from 0.5 to 1.5, especially in the range
of 0.6 to 1.0 dl./g., as determined using a 0.25 g./100 ml
solution in toluene at 30C.
The styrene resins most preferred are those having
at least 25% by weight polymer units derived from vinyl
aromatic monomer having the formula
RC = CH2
( Z) p
wherein R is hydrogen, alkyl of 1 to 4 carbon atoms or halogen;
Z is a member selected from the class consisting of vinyl,
hydrogen, or alkyl of from 1 to 4 carbon atoms; and p is from
1 to 5. The preferred styrene resins for purposes of this
invention are polystyrene homopolymers.
The amount of elastomeric block copolymer and poly-
olefins or polystyrene or polycarbonate dispersing agent, if
used, combined, then added to the aromatic polycarbonate
resin will vary from 1 to 40% by weight of the composition.
Of course, other additives may be present in the
compositions, such as plasticizers, pigments, flame retardants,
and the like, in amounts varying between about 1 and 100 parts
by weight of the total resinous components (a), (b) and (c) in
the composition. The above-stated ranges for amounts of the
-- 10 --
B ~ ! 7 (1 fi
aromatic polycarbonate resin (a), the precompounded blend of
polyolefin styrene and the hydrogenated elastomeric block co-
polymer resin (c), if present, is based solely upon such
resinous components in the polymer blend and excludes other
additives.
Among the features of this invention are reinforced
compositions containing reinforcing amounts of reinforcements,
such as powders whiskers, fibers or platelets of metals, e.g.,
aluminum, bronze, iron or nickel, and non-metals, e.g., carbon
filaments, acicular CaSiO3, asbestos, TiO2, titanate whiskers,
glass flakes, and the like. Such reinforcements will be
present in an amount of, e.g., 2 to 90% by weight, preferably
10 to 60% by weight. Especially preferred as a reinforcement
is fibrous glass.
The method of forming the polymer composition is
not critical, so long as component (b) is precompounded. Any
prior art blending technique is generally suitable. The
preferred method comprises blending the polymers and any addi-
tives, such as reinforcements in powder, granular and filamen-
tous form -- as the case may be -- extruding the blend and
chopping into pellets suitable for molding to shape by means
conventionally used to mold normally solid thermoplastic
compositions.
The following examples are set forth as further
description of the invention, but are not to be construed as
limiting the invention thereto.
The formulations are produced by a general procedure
comprising mechanically blending then co-extruding in a twin
screw Werner Pfleiderer (WP) extruder at 300 C and molding
into test pieces in a reciprocating screw injection molding
machine at about 300 C (cylinder) and 105 C (mold). To make
component (b), the block copolymer and the olefinic resin or
~C~ 7nf,
styrene resin are master-batched by precompoundiny at 290 C
in a twin screw WP or in an adequate rubber proCeSsinCJ machine
first. The physical tests are carried out by the following
procedures: Izod impact strength on 1/8" notched specimens;
tensile strength and stiffness on DIN tensile bars, drawing
rate 0.5 cm./min.; E modulus with an extentiometer on DIN type
bars, heat distortion temperature at 264 psi on 1/8" bars;
flow length at 280 C and at 300 C cylinder temp. at 100 C
mold temperature at 75% of maximum injection rate plus injec-
tion pressure under constant control. Environmental stresscracking resistance is measured under flexural loading with
0.25~ strain and full immersion in carbon tetrachloride.
Dispersion quality is determined by visually inspecting broken
DIN tensile bars (Drawn at a rate of 50 cm./min.). Stress
rela~ation is visually determined in air under a constant
tensile deformation of 2.8% for 24 hours on DIN tensile bars.
EXAMPLES 1-4
The following formulations are prepared, molded and
tested:
Table. - Compositions of Aromatic Polycarbonate Resin
and Premix of Hydrogenated Block Copolymer
and Polyolefin
.
Example lAa 1 2 3Aa 3
Composition (parts by weight)
poly(2,2-diphenylpropane)
carbonateb 100 95 90 -- -- --
poly(2,2-diphenylpropane)
carbonateC -~ - 100 95 90
7()~
Table (con't.)
Example lA 1 _ 3A 3
~Hydrogenated styrene-
~butadiene styrene block
¦ copolymerd -- 1.25 2.5 __ 1.25 2.5
f~ polyethylene resine -- 1.25 2.5 -- 1.25 2.5
~poly(2,2-diphenyl-
~propane)carhonateb -- 2.5 5.0 -- 2.5 5.0
Properties
Heat distortign temp.
at 266 psi., C 137 134 135 139 137 135
Flow length, cm
at 280C 38 47 47 29 34 38
at 300C 44 52 54 33 40 44
Izod impact strength,
J/cm2 7.9 7.4 6.9 9.1 8.4 7.6
Tensile yield strength,
kgf./cm2 615 580 565 610 575 555
E modulus, kgf./cm2 26,200 25,000 22,60026,000 23,000 23,000
Stress cracking,
initiation after 31 4 N.D. 45 6 N.D.
sec. min. sec. min.
catostrophic failure 1 4 N.D. 50 6 N.D.
min. min. sec. min.
a Control
b General Electric Co., Lexan 125
c General Electric Co., Lexan 100
d Shell Chemical Kraton G 1650
e D.S.M. Co., PE 1100
f Premix
Flowability and stress crack resistance are markedly
improved. In addition, with Examples 1 and 2 there is no lami-
nation, and with 3 and 4 there are only a few coarse laminations.
In contrast to controls lA and 3A which had many crazes and
some crazes, respectively, after the stress relaxation tests,
- 13 -
7 ~) fi
Examples l and 3 showed no crazes.
The following additional compositions within the
scope of this invention can be prepared and will have advan-
tageous properties, especially improved impact resistance,
environmental stress crack resistance, and greatly improved
flowability.
Composition (parts by weight)
.
poly(2,2-diphenylpropane)
carbonate 97 95
~hydrogenated styrene-
butadiene styrene block
copolymerb 0.750.75
d polyethylene resinC 0.750.75
~styrene homopolymer 1.5 1.5
hydrogenated styrene-butadiene-
styrene block copolymerb -- 2
a See Examples 1-4, footnote c
b See Examples 1-4, footnote d
c See Examples 1-4, footnote e
d Premix
Many variations will suggest themselves to those
skilled in this art in view of the above, detailed description.
All such variations are within the full intended scope of the
appended claims.
