CA1220589A - Blends of grafted acrylate polymers and mass-made abs- type resins - Google Patents

Abstract

Abstract of the Disclosure A process for preparing polyblend compositions having excellent physical properties is taught. Also disclosed are blends of a major proportion of mass-made ABS-type resins with a minor proportion of a grafted rubber concentrate ("GRC"), which GRC is a graft polymerized product of an acrylate polymer polymerized onto a rubber substrate. Such blends are shown to have excellent physical property combinations including superior impact resistance.

28,040-F

Description

S~

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~

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$~

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:

' "
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 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~

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-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):

,, 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~

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~

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 _ ~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-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~

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~

,_ ,~
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-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-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~

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-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~

~ 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~

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-~Z~?~
--2~--. ~1 a~ O rl ~ ~1 ~ O O O O O ~I

U~ .
OV ~
oo d' O
. d' .-1 [`
~I
O. l Z;
U
O
CO ~ t` ~ ~ ' OD ~1 a~c~ o~ ~ ~ o o ~
~0 Lt) LO ~ ~ ~ O

O
C~
C~
~ P~
E~
~ a~ u a~
ht~ ~) rl ~ t` CO CO ~ O

o 4~
o o a ~,/
~ El o a ~rl ~ ~ ~
i~'~ ~ ~ ~ ;~ a o c~ o o o o v~ ~ -- ~
O ~ ~ ~ ~ O
,3::

s~

~ - ~
~ _ = = - = I~
~ ~ m v ~ ~ ~ O
~ = - = = = = C~
V~ ~C

28, 040-F -24-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-s~

. o Lr) ~ o ~ ~ o ~LI
o o o o o o o o ,~

U
o C` d' ~ ~ ~t ~ ~ ~t 00 ~ 1 0 N ~Y) O Lt :~ . ~ ~ dtd' dl ~ d' ~
.
~Ct l-t Z
O O
r~ ~ V
t~ ~t o ul ~ ~Ir~ N O 11 r~l . Lt) o ~Lr~
O (~ Lt~ D 11~ Il ~ ~D dl ~t 3 ~t ~t ~
~ ,i W ~ t ~:1 a~t h Pq ~ tl~
~t~, ~t h o ~n ~.q ~; ~ ~ ~o ~o ~1 ~ ~ ~ ~O
~) -I't tn,~ U
rl ~ d' ~ 01~ oo ~ o ~1 0~ ~ 3 C~
.,~
tH
o ~n ~ t~
O V
.,~
h 1:~ O
; ~rl ~ ~~~q ~ ~ ~ ~ ~~
o ~ ~ ~ I ~ ~ ~ 0~
v C~ o o ~o mo ~qo ~o O O O

~ ~ ~ ~ ~ I ~ I ~ I ~ ~ ~t~ U~
o ~ a ~ a P ~a~ ~ ~ ~ \~
~ ~0 ~¢0~o ~0 ~o ~:o ~o ~¢o O ~ cct ~;, ~ æ~ ~Ln V ;~ ;-- æ-~ vt--a) ~ - ~ Z
~i ~ ~ H ~ Z O
~ = = = = = - ' = = =
U~t 28, 040-F -26-~Z;~58~

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-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-

Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An impact resistant and tough polyblend composition that is comprised, in intimate physical admixture, of:

as constituent (A) 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 of:

(i) from 15 to 35 parts by weight of a cyanoalkene of the formula:

(I) wherein: R is hydrogen or a lower alkyl unit containing not more than 4 carbon atoms therein;

(ii) from 85 to 65 parts by weight of an alkenyl aromatic monomer of the formula:

(II) 28,040-F -29-wherein G is hydrogen or methyl and Ar is an aromatic radical (including alkyl- and halo-ring-substituted aromatic units) containing from 6 to 10 carbon atoms;
and (iii) between 5 and 18 percent by weight based on total weight of constituent (A) of a natural or synthetic rubber ingredient ("rubber"); and as constituent (B) of the polyblend, between 35 and 1 percent by weight based on total weight of polyblend of a grafted rubber concentrate ("GRC") component that is a graft copolymerized product of:

(iv) from 40 to 90 percent by weight based on total weight of constituent (B) of a rubber substrate component upon which there is graft copolymerized:

(v) between 60 and 10 percent by weight based on total weight of constituent (B) of a superstrate containing in grafted polymer component form, at least 50 percent by weight (based on total weight of grafted polymer superstrate) of polymerized monomer of the formula:

(IV) wherein each R1 and R2 is independently hydrogen or a lower alkyl unit containing not more than 4 carbon atoms, with any balance of said graft copolymerized superstrate being a different non-acrylate monomer that is addition copolymerizable with methylmethacrylate.

28,040-F -30-

2. A polyblend composition according to Claim 1 which contains between 70 and 85 percent by weight of said constituent (A).

3. A polyblend composition in according to Claim 1, wherein the cyanoalkene of formula (I) is acrylonitrile, the alkenyl aromatic monomer of formula (II) is styrene and said monomer of formula (IV) is methylmethacrylate.

4. A polyblend composition according to Claim 1 wherein the rubber in constituent (A) is in the form of particles, which particles contain discernible occlusions of polymer which was polymerized in the presence of the rubber, which particles have a volume average diameter of from 0.3 to 5 micrometers.

5. A process for making a tough polyblend composition, such process comprising physically intermixing:

from 65 to 99 percent by weight based on total weight of polyblend of constituent (A) which is a mass-made ABS-type resin that is comprised of:

(i) from 15 to 35 parts by weight of a cyanoalkene of the formula:

(I) wherein: R is hydrogen or a lower alkyl unit containing not more than 4 carbon atoms therein;

28,040-F -31-(ii) from 85 to 65 parts by weight of an alkeny1 aromatic monomer of the formula:

(II) wherein G is hydrogen or methyl and Ar is an aromatic radical (including alkyl- and halo-ring-substituted aromatic units) containing from 6 to 10 carbon atoms;
and (iii) between 5 and 18 percent by weight based on total weight of constituent (A) of a natural or synthetic rubber ingredient ("rubber"); and from 35 to 1 percent by weight based on total weight of polyblend of constituent (B) which is a grafted rubber concentrate ("GRC") component that is a graft copolymerized product of:

(iv) from 40 to 90 percent by weight based on total weight of constituent (B) of a rubber substrate component upon which there is graft copolymerized;

(v) between 60 and 10 percent by weight based on total weight of constituent (B) of a superstrate containing, in grafted polymer component form, at least 50 percent by weight (based on total weight of grafted polymer superstrate) of polymerized monomer of the formula:

(IV) 28,040-F -32-wherein each R1 and R2 is independently hydrogen or a lower alkyl unit containing not more than 4 carbon atoms, with any balance of said graft copolymerized superstrate being a different non-acrylate monomer that is addition copolymerizable with methylmethacrylate.

6. A process according to Claim 5, wherein between 70 and 85 weight percent of constituent (A) is intermixed with between 30 and 15 weight percent constituent (B).

7. A process according to Claim 5 wherein the physical intermixing is melt blending under the influence of intensive mechanical admixing at a temperature that is sufficiently high to thermoplasti-cize both of said constituents but not high enough to cause appreciable thermal degradation of the polyblend or either constituent thereof.

28,040-F -33-