Note: Descriptions are shown in the official language in which they were submitted.
S~
--1--
BLENDS OF GRAFTED ACRYI~TE POLYMERS
AND MAS S -MADE ABS -TYPE RES INS
ABS ( acrylonitrile-butadiene-styrene~ and
ABS-type resins are commercia'ly important and find
widespread usage. They are relatively tough and have
generally good solvent and impac-t resisting qualities.
These plastics have been known for many years and are
described in "ABS Plastics" by Costas H. Basdekis
published in 1~64 as part of its Plastics Application
Series by REINHOLD PUBLISHING CORPORATION of New York.
Another more recent description is set forth in
Touqhened Plastics by C. B. Bucknall, Applied Science
Publishers Ltd., London (1977).
~ BS plastics can be satisfactorily made in a
variety o~ ways.
One good route for ABS manufacture is the
mass technique, wherein the involved rubber (such as
polybutadiene or PBD ) is directly dissolved in an
appropriate mixture of styrene ("S") and acrylonitrile
("AN~) followed by polymeri~ation o~ the monomer( 5 ) in
the presence of the rubber under agitation which is
28, 040~
f~Z~(~5~3~
--2-
continued at least until the occurrence of the rubber
phase inversion. After phase inversion, polymerization
is continued either in mass or in a suitable suspension
of the mass in a liquid medium such as water. Polymer-
ization is allowed to proceed to a desi.red degree ofconversion whereupon, usually with completing devola-
tilization, the desired A~S plastic product is obtained.
Other conven-tional preparations of ABS resins
involve such procedures as: (i) blending any one or
more of various suitable rubber latices with styrene-
acrylonitrile copolymer ("SAN"); and (ii) polymerizing
styrene and acrylonitrile in the presence of a preformed
rubber in latex form.
Typically, mass-made ABS resins have some
inherent limitations. Since the polymerization of SAN
is carried out in the presence of rubber, the viscosity
of the system limits the amount of rubber which may be
used. Accordingly, ABS compositions with relatively
large amounts of rubber are difficult to achieve by
this technique.
ABS and ABS-type resins prepared by the
above-explained mass-made technique typically have
relatively large size rubber particles. The groups of
rubber particles usually have a weight average diameter
in the range of 0.3 to 5 micrometer ("~m"), frequently
0.5~m to 5~m.
Nothing in the prior art appears to concern
itself with a means for providing tough and impact
resistant ABS and ABS-type plastics materials in a way
as advantageous as the present invention.
28,040-F -2~
~z~ s~
~3-
The present invention concerns remarkably
tough polyblends, particularly at low temperatures, and
a simple and direct method for their manu~acture. The
present invention in~olves blends of (A) certain ABS
and ABS-type resins; and (B) certain grafted rubber
concentrates (i.e., "GRCs").
The present i~vention pertains to highly
improved and surprisingly tough ABS. In general the
invention is an impact resistant and tough polyblend
composition that is comprised, in intimate physical
admixture, of: as constituent (~) of the polyblend,
between 65 and 99 percent by weight based on total
weight of polyblend of a mass-made ABS-type resin that
is comprised ofO
(i) from 15 to 35 parts by weight of a cyanoalkene
of the formula:
CH2 = C - CN , (I)
wherein: R is hydrogen or a lower alkyl unit con-
taining not more than 4 carbon akoms therein;
(ii) from 85 to 65 parts by weight of an alkenyl
aromatic monomer of the formula:
CH2 = C-Ar , (II)
wherein G is hydrogen or methyl and Ar is an aromatic
radical (including alkyl- and halo-ring-substituted
28,040-F -3-
lZ~(rS8$~
--4--
aromatic units) containing from 6 to 10 carbon atoms;
and
(iii) between 5 and 18 percent by weight based on
total weiyht o~ constituent (A) of a na-tural or synthetic
rubber ingredient ("rubber"); and
as cons.tituent (B) of the polyblend, between 35 and 1
percent by weight based on total weight of polyblend of
a grafted rubber concentxate ("GRC") component that is
a gra~t copolymerized product of:
(iv) from 40 to 90 percent by weight based on
~o~al weight of constitutent (~) of a rubber substrate
component upon which there is graft copolymerized:
~ v) between 60 and lO percent by weight based on
total weight of constituent ~B) of a superstxate con-
taining, in grafted polymer component form, at least50 percent by weight (based on total weight of grafted
polymer superstrate) of polymerized monomer of the
formula:
R10
' "
CH2=C-C-O-R2 , (IV)
wherein each R1 and R2 is independently hydrogen or a
lower alkyl unit containing not moxe than 4 carbon
atoms, with any balance of said graft copolymerized
superstrate being a di~ferent non-acrylate monomer tha-t
is addition copolymerizable with methylmethacrylate
( "~MA" ) .
Also contemplated within the scop~ of the
invention is a process for making a tough polyblend
--- 28,040-F -4-
~I~Z~!S89
~5-
composition, such process comprising physically
intermixing from 65 to 99 percent by weight based on
total weight of polyblend of constitutent (A) wlth from
35 to 1 percent by weight based on total weigh-t of
polyblend of constituen-t (B).
As used herein, the terms "graft(ed) polymer
or copolymer", "graft polymerized or copolymerized",
are intended to include the polymeric materials which
are formed when monomeric materials, such as methyl-
methacrylate are polymerized upon and form attachedchain superstrate combinations with preformed, polymer-
izeably-reactive substrates, such as polybutadiene
("PBD").
The present invention involves polyblends of
the following two constituents (A) and (B):
~ A) Between 65 and 99, advantageously from 70 to
85, percent by weight based on total weight of poly-
blend of a mass-made ABS or A~S-type resin. Such ABS
or ABS-type resins contain particles of a rubbery or
elastomeric materiaI ("rubber"), which particles
contain discernable occlusions of polymer which was
polymerized in the presence of the rubber. The group
of rubbex particles typically has an average particle
size from 0.3 to 5~m, more frequently not greater than
3~m.
(B) Between 35 and 1 percent by weigh-t based on
total weight of polyblend, advantageously from 30 to 15
percent by weight~ of a grafted rubber concentrate
component ("GRC"). The GRC comprises particles of
PBD or e~uivalent rubbery elastomer having an average
particle size of from 0.05 to 0.5~m upon which there
28,040-F -5-
S~.3
--6--
is emulsion graft copolymerized methylmethacrylate
("MMA"). The term MMA/ as used herein, includes its
monomeric e~livalen-ts and mixtures thereof with MMA
and/or its equivalents and their own mixtures. The MMA
is copolymerized with up to 50 percent by weight (based
on weight of total graft polymerizable monomeric
component) of another different, non-acrylate vinyl
monomer or monomer mixture that is copolymerizable with
MMA. Such GRC is composed of from 40 to 90 percent by
weight of the rubber substrate component upon which
thexe is correspondingly between 60 and 10 percent by
weight of the graft copolymerized superstrate component.
Polyblends according to the present invention
possess materially increased impact resistance and
toughness. The physical property measurements of these
polyblends are generally at least one-and-one-half-times
~ x), frequently two-times (2x), and frequently much
more, increased over the physical property measurements
of the ABS or ABS-type resin in the novel polyblend(s).
Their general resistance to solvent attack is at least
equal to that of the involved ABS or ABS-type consti-
tuent(s).
To make the polyblends o~ the present
invention, the desired appropriate proportions of
constituents (A~ and (B) are physically admixed in such
a way as will ensure very intimate interblending. Such
blends should be homogeneous at least to the unaided
eye. Most advantageously the polyblends are prepared
by melt blending of the respective constituents by
mechanical admixture using intensive compounding
apparatus (such as extruders, masticating roll
assemblies or the 2-roll mill Banbury mixers) at a
~8,040-F -6-
~z~c1~
--7--
temperature adequate to thermoplasticize the constituents
being mixed but not high enough to cause appreciable
thermal decomposition or degradation of the polyblend
or either constituent thereof.
The polyblends pursuant to this invention
can, if desired, contain other additives that are
oftentimes included in such compositions; these can
include antioxidants, pigments, dyes, fillers (both
pulverulant, particulate or fibrou~), stabilizers,
mineral oil and other plasticizers, and blowing agents.
As is also apparent to those skilled in the
art, the physical properties and other characteristics
of the present polyblends depend on the particular
types of ABS and GRC constituents employed, including
such fac-tors as weight average molecular weight ("Mw")
of the polymers therein, presence or absence of various
additives, the rubber utilized in the ABS and GRC.
Relative to the rubber that is utilized, factors such
as degree of crosslinking, precise composition, and the
included proportion(s), further affect t.he present
polyblends.
The mass-made ABS resin(s) which may be
employed as constituent (A) in practice of the present
invention may b0 obtained according to the teachings of
U.S. 3,627,855. Such resins usually contain inter-
polymerized ther~in in the matrix or continuous phase
from 15 to 35 par-ts by weight AN and from 85 to 65
parts by weight styrene and contain dispersed in the
continuous phase in particulate form between 5 and 18
percent by weight rubber based on total weight of the
ABS .
28,040-F -7
lZZl! S~
Equivalent ABS-type resins can be prepared
with variations in the respective acrylonitrile,
styrene and rubber ingredients.
Thus for the ABS-type resin, other cyano-
alkylenes may be utilized along with or in place ofacrylonitrile. These, such as a-methacrylonitrile,
are of the formula (which includes acrylonitrile):
CH2=C-CN, (I)
wherein R is hydrogen or a lower alkyl unit containing
not more than 4 carbon atoms.
In addition to styrene, other alkenyl aromatic
monomers or mixtures thereo~ may be utilized in place
of and/or mixed with styrene. These are of the formula
~which includes styrene):
CH2=C-Ar, (II)
wherein G is hydrogen or methyl and Ar is an aromatic
radical (including various alkyl and halo-ring-
-substitut.~d aromatic units~ of from 6 to lO carbon
atoms. These include: ~-methyl styrene; vinyl toluene;
vinyl naphthalene; the dimethylstyrenes, t~butylstyrene;
the several chlorostyrenes (such a~ the mono- and
dichloro-variants); the several bromostyrenes (such as
the mono- and dibromo-variants).
. 28,040-F -8-
8~
g
.
Polybutadiene or copolymers of butadiene are
often preferred as the rubber componen-t for the ABS or
ABS-type component of constituent (A) as well as for the
rubbery elastomer substrate component in the constituent
(B)-
However, the rubber utillzed in preparationof both constituents IA) and (B) may also be selected
from a wide variety of generally sulfur-vulcanizable
materials or mixtures thereo. It can, for example, be
natural rubber or as the case with polybutadiene it can
be a synthetic rubber. Suitable rubbers are prepared
from conjugated diolefins preferably 1,3-dienes. The
rubber can be a homopolymer or a copolymer rubber
containing between 25 and 90 weight percent of a
suitable 1,3-diene. Suitable 1,3~dienes are
represented by the formula:
H2C=C-CH=CH2 , (III)
wherein X is a hydrogen, chlorine or methyl radical.
Such conjugated diolefin polymer synthetic
rubbers are polymers, as is above-indicated, of:
butadienes-1,3, e.g., butadiene-1,3; isoprene;
2,3-dimethylbutadiene-1,3. Also suitable are
copolymers of one or more such butadienes in a
proportion of at least 75 percent by weight of such
butadienes. In this case, up to 25 percent by weigh-t
of the rubber can be one or more monoethylenic
compounds which contain a
28,040-F -9-
--10--
CH2=C-R2 (IIIA)
grouping, wherein at least one of the connected Rl
and/or R2 valences is attached to an electronegative
group, that is, a group which substantially increases
the electrical dissymmetry or polar character o~ the
molecule.
Examples of compounds which contain the
formula (IIIA) grouping and are copolymerizable with
butadienes are: the formula (II) monomers, especially
styrene; the unsaturated carboxylic acids and their
esters, nitriles and amides, such as acrylic acid,
methyl acrylate, ethyl acrylate, methylmethacrylate,
acrylonitrile, a-methacrylonitrile, methacrylamide;
vinylpyridines, such as 2-vinylpyridine, 2-methyl-
-5-vinylpyridine; methyl vinyl ketone, and methyl
isopropenyl ketone. Such formula IIIA monomers, in
addition, are also copolymerizahle with styrene and/or
methylmethacrylate.
Examples of such conjugated diolefin polymer
synthetic rubbers are polybutadie~e; polyisoprene;
butadiene/styrene copolymers; and butadiene/acrylo-
nitrile copolymers. The synthetic rubber may be
solution-prepared or emulsion-prepared, be it a
stereo~specific variety or otherwise.
Other conventional unsaturated sulfur-vulcan-
izable rubbers may also be used as the rubber material
such as "EPDM" (a rubbery terpolymer of ethylene,
28,040-F -10-
s~
propylene and a copolymerizable non-conjugated diene
such as 1,4-hexadiene, dicyclopentadiene, dicycloocta-
diene, methylenenorbornene, ethylidenenorbornene,
tetrahydroindene). The analogous fluorocarbon, silicone
and polysulfide rubbers may also be employed as a rubber.
The compositions accordi~g to the present
invention may be blends of two or msre polymeric
ingredients, including, mixtures of one or more
suitable (A) and ~B) constituents.
The methylmethacrylate or equivalent monomers
which are gr~ft copolymerized, as a superstrate, upon
the polybutadiene or other rubber to provide the GRC
constituent (B) for the polyblends of the present
invention are of the general formula (which includes
methylmethacrylate):
R10
,,
CH2=C-C-0-R2 , ~IV)
wherein each Rl and R2 is independently hydrogen or a
lower alkyl unit containing not more than 4 carbon
atoms. Besides methylmethacrylate, ethyl methacrylate
and propyl and isopropyl methacrylate are good
examples of formula (IV) monomers useful to replace or
to combine with MMA for preparation of the constituent
(B) GRC in practice of the present invention.
The graft copolymsrized superstrate in the
GRC for constituent (B) may comprise mixtures of formula
(IV) monomers with different non-acrylate mo~omers that
are copolymerizable with methylmethacrylate. Such
28,040-F -11-
rsg~a
non-acrylate monomers include those identified above as
copolymerizable in the rubber materials. Such
non-acrylate monomers include any of such addition
polymerizable vinyl monomers, or mixtures thereof, as:
(i) vinyl halides, particularly vinyl chloride;
~ii) vinyl organic acid esters such as vinyl acetate,
vinyl ~ropionate; (iii) vinylidene chloride; (iv)
acrylic and methacrylic acid; and (v) maleic anhydride,
as well as (vi) any of the above-mentioned ormula II
and IIIA monomers.
The following examples show the benefits of
the present invention. In the Examples, all parts and
percentages are given on a weight basis and all tem-
perature readings (unless otherwise specified) are in
degrees Celsius, ("C"). Control runs which are not
examples of the present invention are indicated by an
asterisk (*).
First Example
A stirred 3-liter reactor equipped with a
heating bath was employed to carry out an emulsion
grafting reaction of methylmethacrylate ("MM~") onto a
prepared polybutadiene ("PBD") substrate in latex form.
The initial charge to the reactor comprised: 957 gms.
of 44 pe.rcent solids content PBD latex obtained commer-
cially from THE FIRESTONE TIRE~ RUBBER COMPANY underthe trade designation "SR6747'~with the rubber particles
therein characterized in having a 0.1190 ~m volume
average diameter; 668 gms. of deionized water; 5.62 gms.
of "CALSOFT-40'i~emulsifier ~an alkyl aryl sulfonic acid
salt); and 3.75 gms. of an aqueous ferric nitrate
solution of a strength giving 0.002 gm. of ferric ion.
Immediately after charging, the reactor was purged of
oxygen by three successive cycles of evacuation followed
~ktr~de r~
28,040-F -12-
~aZ~
-13-
by nitrogen flushing. At this point, 0.056 gm. of
"FORMAPON'~(sodium formaldehyde sulfoxylate) dissolved
in 12 gms. of water was added to the charge. The
reactor bath was then heated to 70C.
Reaction was commenced by pump feeding to the
charge in the reactor at a 50 cc/hr. rate a mixture of
140 gms. MMA and 0.7 g~. n-octyl mercaptan. Ten minutes
after start of the MMA feed, a separate feed stream was
begun to incorporate in the charge, at a pump-regulated
rate of 42 cc/hr., a mixture of 117 gms. water, 6.7
gms. "CALSOFT-40" and 0.08 gm. sodium persulfate. The
pumping of the two separate feed streams was continued
for 3 hrs., at which time all of the indicated quan-tities
of both reagent feeds had been delivered.
At this point, 50 ml. of a 1.6 percent solution
of the monomethyl ether of hydroquinone was added to
the reaction mass in order to terminate the reaction.
A dispersion of " IRGANOX~ 076" (a phenol antioxidant
obtained from CIBA-GEIGY CORPORATION) was then incor-
porated in the completed reaction mass in an amount
adequate to provide 0.6 parts by weight ("pbw") of the
antioxidant per each 100 par-ts by weight o~ PBD therein
present.
The completed reaction mass was then steam
stripped leaving a GRC latex product having total
solids content of 28.4 percent (representing an 82.5
percent conversion of MMA in the reaction). This was
coagulated by freezing, after which the crumb obtalned
was thoroughly washed and dried under reduced pressure
at 6Q. The rubber content in the GRC crumb was 77.7
percent.
~ t~de ~n~
28,040-F -13-
~2~0~8S~
-14
Second Example
The dried GRC crumb obtained by the prepara-
tion of the First Example was blended with a mass-made
ABS resin (containing 13.5 percent rubber and obtained
from THE DOW~CHEMICAL COMPANY under the trade designation
.~ "DOW ABS 500"~.
The blending was done on a steam heated, 3 x
8 inch (7.62 x 20.32 centimeter) two-roll mill. The
front roll in the pair was heated by steam under a
pres~ure of 1.59 x 106 Pascal (Pa) to 1.72 x 106 Pa
(230 to 250 psig). The back roll was not heated. The
ABS was first put between the rolls of the mill and
melted. The GRC crumb was then added to the molten
ABS. After the GRC inclusion, the composite was milled
for an additional 5 minutes with frequent folding of
the polyblend blanket being made. After the blending,
the polyblend was compression molded into a 1/8 inch
(0.3175 centimeter) thick sheet from which suitably
sized specimens were made. Testing of the physical
properties of these and other specimens was conducted
by appropriate ASTM procedures. The Notched Izod
Impact resistance is determined by ASTM D 256. The
Melt Flow Rate is determined by D 1238. The Tensile
Strengths at yield and at rupture, Elongation and
Modulus values are determined by D 638. The Vicat heat
distortion temperature is determined by D 1525.
The results obtained are set forth in the
following Table I, in which Sample "A'l is a milled
control product of the "DOW ABS 500" and Sample "B" is
the polyblend product made from ~he ABS and GRC
composite as above-described.
k
28,040-F -14-
12~?S~9
-15-
_ ~D
o=
~1 '
~ ~o ~ ~ o
C~= o
_,,
H
-
O _ _ O
U~ = C~ 00
~ ~ O
--= r~ co
- ~ ~ ~
O _ ~
-Z ~0
--~
O O O
.,
~¢ P~ H h
E-l o .
~ O U~
I,q ~ t~ o
Z;~ oo o~ ~
P~ ~ ~ ~ ~
~Q ~
O
,1
U~ ~
~ X
3 ~
o
a
=
~ ~ ~ o
- - v
v~
28, 040-F -15-
-- -16-
Third Example
A series of polyblends was prepared to demon-
strate the advantageous flexibility of various products
prepared in accordance with the present invention. It
is shown that product toughness can be varie~ using GRC
components made with varying levels of grafting, from
relatively low amounts of grafting to relatively high
amounts of grafting.
To do this, the grafting procedure described
in the First Example was altered by changing the amount
of MMA introduced into the reaction mass. Also, the
rubber employed was a 90 percen-t:7 percent:3 percent
butadiene/styre~e/acrylonitrile (BD/S/AN) terpolymer in
32.0 percent solids content latex form having a volume
means particle size of 0.1810 ~m. In each case, the
final GRC latex product was coagulated wi-th alum solu-tion,
then washed and dried.
The blending of the involved GRCs with "DOW
ABS 500" was done pursuant to the procedure of the
Second Example. Each of the blends had a total rubber
content of 20 percent. The physical properties of the
several produck polyblends were as is set forth in the
following Table II.
. 28,040-F -16-
12~'S135~
-17-
TABLE II
Comparison of Several Polyblends
Weight % Weight % Composite Properties
Rubber GRC In N.I. M.F.R.
5 Sample In GRC ~ (J/M)(qms/10 min~
"C*" 30.8 37.6 267 1.9
"D" 40.9 23.7 326 2.0
"E" 52.2 16.8 438 1.2
"F" 64.1 12.8 449 1.1
"G" 76.4 10.3 443 1.1
"H" 84.5 9.2 443 0.9
*Control run, not an example of the present invention.
By way of further comparison, a sample of the
freshly coagulated rubber terpol~mer ~without any
grafting thereon) was also blended with the "DOW ABS
500". The resulting product was noticeably non-uniform
and unacceptably brittle in physical character.
Fourth Example
To show the adaptability and capability of
use of various rubber co~ponents in practice of the
invention, a series of polyblends was prepared by
repetition of the Third Example except that di.fferent
rubber matexials were used as the seed rubber material
in the GRC. As in the Third Example, the polyblends
were prepared by blending each GRC with "DOW ABS 500"
to a total rubber content of 20 percnet. The iden~ifica-
tion of the several rubber materials utilized and the
results of physlcal testing of each of the product poly-
blends were as is set forth in the following Table III.
~8,040-F -17-
Js~
18
,_
,~
o ~3
~o
C) ~ \ o ct~ ~ d1co
U~ ~ ~ o o o
u ~
P; ~
~ h
E~
~
H
~Q ~ ~ ~ O U~~1 ~
t` Lrl Lr~ ~ N
t~ . ~ t~ ~ LO d
.,~ ~
h Z
h V
~ .q v
.q ~1~1 d~ N ~ t` t` O
,q 3 ~ ~ Lr~ Lr~ u~ t` t` Ln
P~
HU~ _
_~
O
. _
~:
E~ ~ ~ a)
O O O O
~ ~ 0-~1 ~
.,1 ~ ~ ~O ~ ~ ~ I I
3 ~ h h ~`I r-l ~1 ~ I I
o o o o
:~ E3 h
a) ~1
P~
o
o o o o
t~ -~
O ~ ~ ~ ~ d'u~
O ~ ~ U~
3 u~ ~ _ ,_
~ \o ~
h ~; u~ ~; ~~i -
a) ~ ~1 ~`
~-- \-- I In h
o ' ~ ~9 u~ ~!^ v~ ~~ ~ t)
~ E~ ~ \u~ ~ ~ ~o \_ a
~: m ~r~o m m
o ~ m~ m~
.
s~ a
~ = = = _
o
C~ Ul
28, 040-F -18-
--19--
Fifth Example
Following the foregoing procedures, a GRC of
100 percent MMA on 53.6 percent terpolymer rubber ~the
same rubber as employed in the Third Example) was
prepared. To give Sample "O", 21.0 parts by weight of
the GRC was blended with 113.1 parts by weight of "DOW
ABS 500" so that the resultant polyblend contained 20
percent overall rubber in its total composition.
Sample "P", having 30 percent total rubber therein, was
made by blending 55.5 parts by weight of the GRC and
79.5 parts by weight of the ABS. The physical testing
results of these Samples are set forth in the following
Table IV.
28,040-F -19-
--20--
hl o
,~
~U
~t
~ ~ ,~
r N ~
R R
H -r-l
~ ~ d'
D o ,~
. ~ .R
-,~
a~
~ P
h ~ ~ a~ L~
rq E-l 11`~
_ ~ a
,~ o ~ ,~
3 P~ oo
. . ,~
u~ ,~ o
~ t~ h a~ PC
R R ~ ~ ~ a
d ~ ~ a
. o t~ o u~
H (~ ~ ,C', ~ ~
. ~ r~ ~ ~ ~ r~
z .. ,~
o
o~,q o
o r~
O ~r~t~ rl t71 ~r~
= ~ ~ o ~ o
= * o a),~
~ 0 ~4 V E~
2 8, 040-F -2 0 -
t~
-21
Sixth Example
To demonstrate similar results obtainable in
the practice of the present invention when other mass~made
ABS resins are utilized in place of -the l'DOW ABS 500"
type, another series of polyblends was prepared with a
GRC prepared generally as in the First Example (containing
52.9 percent combined polybutadiene) blended: (i) for
Samples "R'l through 'IUl', inclusive, with a mass-made
ABS-containing 12 percent butadiene rubber and having a
volume average particle size of 0.85 ~m; and (ii) for
Samples "W" through "Z"', inclusive, another mass-made
ABS-containing 8 percent butadiene rubber and having a
volume average particle size of 2.2 ~m. Sample "Q" was
the unblended 12 percent rubber ABS and Sample l'V" was
the unblended 8 percent rubber ABS.
The test results of these Samples are as set
forth in Table V which follows.
28,040 F -21-
--22--
v
o u ) ~ D O tY~
~ OOOOOOOOOOO
C~
.
P~ N 00 ~0 N -1 r` ~I tr~ N t`
.
U~ ~1 In --I 0 ~ r3~ r--I O O
~r~ ~
U~
a~
V~
~q
1) H r--I 0U ) r~ r31 ~ 0 Lf ) 0
.~ , r~ ~dlU~ Ll~ ,~ ,~ ~ ~ ~ d
t~
0
~ U~
m ~a~ . .
,.q N Lt)1~ ~ 1 CO O N ~ ~D 0
~1 ~ ~ O .C ~ t N
r
a~
O
O ~ t`') ~1r-l O Lnc~ ~ 0 ~ ~
U~~ C) ~ O C~ Nt~`N O r~ 0 ~ t~ N O
~ 1 N r-l r-l N
ta 30 ~t
~P~
O
V
0 t~ COcr~ O Lr) r-l ~ N t~
.... .....
r4 O N r~N CD O Lll r-l ~ N [~ O
rl a~ ~ o ~ ~ o ai~ ~ ~ 0 1~ ~
3 0 ..
~ O
~ h
,1 = = = ~
* = = = ~
~ 0~ P:; U3 E~ 3 X ~ N N O
tl~ ====__--_~_ V
U~ K
28, 040-F -22- .
~2~qrls~
-23-
Seventh E~ample
To show the effect of variation of the gra~ted
polymer in GRC composition(s~, a series of GRCs made
with the same polybutadiene as used in the First Example
was made. Table VI reports the results of testings on
polyblends of these materials with "DOW ABS 500". The
compositions had 23 percent total rubber therein and
contained approximately 15 percent of the particular
GRC.
28,040-F -23-
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28, 040-F -24-
-25-
Eighth Example
To demonstrate the effects of using other
polymers in the graft portions of GRCs, GRCs were made
with combinations of MMA and (in one instance) styrene
with other acrylate monomers including n-butyl acrylate
("n-BuAc"). A series of polyblends having an overall
rubber content of 20 percent was prepared using the
mass ABS components, the polybutadiene rubber substrate
for the GRC component and the preparation techniques
described above using other monomers besides ~-BuAc in
the preparations such as: methyl acrylate ("MA"), sec-
-butyl acrylate ("s-BuAc") and tert~butyl acrylate
("t BuAc"). The GRC compositions and the results of
testing of the indicated polyblends are included in the
following Table VII.
28,040-F -25-
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28, 040-F -26-
~Z;~58~
-27-
Ninth Example
In order to show the value of utilizing vari-
ous commercial acrylic impact modifiers in practice of
the present invention, three different "ACRYLOID'i~pro-
ducts ~Samples "QQ", "RR" and "SS") were blended with
"DOW ABS 500" and tested in comparison with the ABS
alone (Sample "PP"). "ACRYLOIDS", available commercially
from ROHM & HAAS COMPANY, are believed to be emulsion
made, spray-dried S/BD/MMA modifiers (generally utilized
for polyvinylchloride) containing about 40-55 percent
butadiene as styrene/butadiene rubber (25 percent:-
75 percent) which is grafted with MMA/ethyl acrylate
copolymer. "ACRYLOID KM-611" used in Sample "QQ"
contained 24.5 percent MMA (calculated by oxygen
analysis) and contained 94.4 pexcen-t gel with Tg for
its rubber phase of -68. In Sample "TT" the
"ACRYLOID-607N" contained 38. 9 percent MMA and had a
gel percent of 94.2 with a rubber phase Tg of -52 and
a rigid phase Tg of 67.
The physical testing results obtained with
the involved Samples are set forth in Table VIII.
TABLE VIII
"ACR~LOID" Blends
ABS to
"ACRYLOID"
Ratio (in
Sample ~arts by wel~ht? N.I. M.F.R.
"PP*" 100:0 166 2.4
"QQ" 69: 31 320 0.1
IIRRII 69.31 251 0.2
*Control run, not an example of the present inventlon.
~ t~CI ~ ma,~k
. 28,040-F -27-
39
-28-
Althouyh of lesser relative magnitudes than
those presented with other GRCs in the preceding
examples, the results with Samples "QQ" and ItRR''
do illustrate the significant and unexpected improvement
in important physical properties realizable in practice
of the present invention even when relatively high
polymeri~ed MMA content GRCs are being utilized.
Tenth Example
Two additional polyblends in accordance with
the present invention were prepared following the
above-explained procedure from a commercial graft
copolymer of MMA and "HEVEATUFF~ 1350" rubber and "DOW
ABS 500". Sample "SS" contained 95 weight percent of
the ABS while Sample "TT" contained 85 weight percent
of the ABS.
The results are shown in Table IX.
TABLE IX
"HEVEATUFF" Polyblends
Sample N M.F.R.
"SS" 235 2.4
"TT" 379 1.1
Many changes and modifications can be made in
accordance with the present invention without m~terially
departing from its scope. Therefore, the foregoing is
intended to be merely illustrative and not limiting the
scope of the present invention.
~ tr~e rna,~k
28,Q40-F -28-
