CA2014475A1 - Molding compositions comprising carbonate polymer, nitrile-butadiene-vinylaromatic graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions - Google Patents

Abstract

ABSTRACT

Carbonate polymers (PC) such as randomly branched carbonate polymers and blends thereof with linear carbonate polymers are blended with ABS polymers and MBS polymers which enhance the melt strength of polymer composition. The ABS polymers have less than 40 weight percent rubber and greater than 18 percent by weight acrylonitrile. The MBS polymers have greater than 40 weight percent rubber and an outer polymer shell made from alkyl (meth)acrylates. This locates the MBS
rubber modifier in the PC phase and in the PC/ABS
interface so that higher melt elasticity is achieved and the compositions are therefore useful in blow molding and thermoforming applications.

Description

2~47~ :

MOLDING COMPOSITIONS COMPRISING CARBONATE POLYMER, NITRILE-BUTADIENE-VINYL AROMATIC GRAFT COPOLYMER AND
METHYL (METH)ACRYLATE-BUTADIENE-STYRENE GRAFT COPOLYMER
AND BLOW MOLDING AND THERMOFO~MING PROCESSES USING SUCH
COMPOSITIONS

This invention relates to thermoplastic resin compositions and methods of using them and more particularly relates to improved blow moldable or thermoformable polycarbonate/ABS compositions.
More specifically, this invention relates to compositions comprising a blend of carbonate polymers with (1) nitrile-butadiene-vinyl aromatic-type ("ABS- .
type") graft copolymers where a previously prepared rubbery butadiene polymer or a butadiene-vinyl aromatic hydrocarbon copolymer has graft-polymerized therewith a mixture of acrylonitrile and vinyl aromatic hydrocarbon monomers and the ABS graft copolymer containQ less than 40 weight percent rubber and (2) a melt strength enhancingiagent having a Tg lesq than 0C and containing greater than 40 weight percent rubber which is a core/qhell graft copolymer having as a core a polymer of butadiene or butadiene-vinyl aromatic hydrocarbon or butadiene-vinyl aromatic hydrocarbon-alkyl acrylate monomerq with optionally a second inner shell phase of a 36,537A-F -1-ZC~14~

polymer of vinyl aromatic hydrocarbon and an outer shell of an alkyl (meth)acrylate polymer. The melt strength enhancing eore/shell graft copolymers of component (2) above are commonly referred to as MBS resins since they are most often a butadiene rubber core grafted with methyl methacrylate aqd styrene.
Although polycarbonate/ABS blend compositions have been found to be thermoplastically moldable under a broad range of injection molding conditions, only select polycarbonate blends are suitable for blow molding.
This is due to the unique requirements of blow molding operations.
In the conventional blow molding operation, as taught in U.S. Patent Nos. 4,652,602 and 4,474,999, a tube or parison of the heat softened thermoplastic blend may be extruded vertically downward into a mold. The extrudate is then pressed into the mold surfaces with a pressurized ga~ flow (usually air or inert gas), shaping the heat softened resin.
As appreciated by those skilled in the art, the successful molding of a given thermoplastic resin is dependent upon a number of factors, including the characteristics and physical propertie~ of the heat softened resin. The length and diameter of the tube and the quantity of material forming the tube are limiting factors in determining the size and wall thickness of the object that can be molded by this process. The fluidity of the melt obtained from polycarbonate/ABS
blends, or the lack of melt strength as well as the paucity of extrudate swelling, serve to limit PC~ABS
resins in blow molding applications to relatively small, thin walled parts. The above factors alone are of 36,537A-F -2--- _ 2~4475 considerable importance in the successful blow molding of any re~in, particularly in regard to the molding of large articles where the extruded parison weighs at leaqt 0.9 kilograms (2 pounds), and especially where the extruded parison weighs 1.8 kilograms (4 pounds) or more.
It is known from Japanese Patent Publication No. JP 58/59258 ~1983) that resin compositions with good weldline ~trength can be obtained from blends of linear polycarbonate re~ins, acrylonitrile-butadiene-styrene resins (ABS), and rubbery graft copolymer resins (MBS).
However, this reference does not suggest the advantage of controlling rubber placement and in fact is attempting to modify only the ABS phase to improve the weldline by utilizing MBS core/shell resins containing 30 to 50 percent rubber with styrene in the outer shell.
It is further known from U.S. Patent No.
4,677,162 that a moldable blend of linear or branched polycarbonate re~ins (PC), acrylonitrile-butadiene-styrene resins (ABS), and rubbery graft copolymers (MBS) is useful to form articles with good impact and low gloss. However, this reference utilizes only ABS resins with low AN content and does not suggest or achieve the advantage of controlling rubber placement by altering the solubility parameter and/or polarity of the ABS
resin by varying the acrylonitrile content such that the addition of a qecond rubbery graft copolymer will be located at the PC interface or in the PC phase.
The preqent invention is directed to a thermoplastic blend composition useful for blow molding or thermoforming comprising:

36,537A-F -3-4 2~ 4'~ 7~

A) 20 to 95 percent by weight and preferably 30 to 90 percent by weight of a carbonate polymer selected Yrom:
(i) randomly branched carbonate polymer~, and (ii) blends of randomly branched carbonate polymers with linear carbonate polymer~, B) 5 to 75 percent by weight and preferably 10 to 65 percent by weight of one or more graft copolymer wherein a butadiene polymer rubber or a butadiene-vinyl aromatic hydrocarbon copolymer rubber has graft polymerized therewith a mixture of nitrile and vinyl aromatic hydrocarbon monomers which graft copolymer contains greater than 18 percent by weight of nitrile monomer polymerized therein and less than 40 percent rubber and C) 1 to 20 percent by weight and preferably 3 to 12 percent by weight of a melt ~trength enhancing agent having a Tg less than 0C
and greater than 40 percent rubber which is a core/~hell graft copolymer having a core of a polymer of butadiene or butadiene-vinyl aromatic hydrocarbon or butadiene-vinyl aromatic hydrocarbon-alkyl acrylate monomers with optionally a second inner shell phase of a polymer of vinyl aromatic hydrocarbon and a outer shell of 36,537A-F -4-- 20~

a polymer of alkyl (meth)acrylate monomer(s), wherein said percents by weight are based on components A), B) and C).

The preferred compositions contain A) 50 to 80 percent by weight of a carbonate polymer which is preferably a blend of linear and randomly branched polyc~rbonates, the blend containing at least 20, preferably 20 to 80, more preferably 40 to 80, and most preferably 50 to 75 percent by weight randomly branched carbonate polymers with the balance being linear carbonate polymer(s), B) 10 to 65 percent by weight of the graft copolymer of a butadiene polymer rubber with a mixture of nitrile and vinyl aromatic hydrocarbon monomers graft polymerized therewith, which graft copolymer contains greater than 18 percent by weight nitrile and less than 40 percent rubber and C) 3 to 9 percent by weight of the melt strength enhancing agent.
The articles produced and/or molded by using the compo~ition~ of the invention are useful a~
automotive components, bottles, tool housings and the like.
Figureq 1-5 are tranqmiqsion electron microscope (TEM) photographs of the re~inous compoqitions described herein. Figure 1 is a TEM
photograph of Control Experiment 1 showing that the PC/ABS 213/MBS blend (16 percent acrylonitrile by weight ln the A8S component) has the MBS rubber (small black spheres) totally in the the light gray SAN pha~e of the ABS component. Figure 2 is a TEM photograph of Control Experiment 2 showing that the PC/ABS X21/MBS blend (21 percent acrylonitrile by weight in the ABS component) 36,537A-F -5--6- ~4~7~

has more of the MBS rubber at the interface of the dark gray PC or polycarbonate phase and the light gray ABS
phase. Figure 3 is a TEM photograpn of Control Experiment 3 showing that the PC/ABS Y23/MBS blend (23 percent acrylonitrile by weight in the ABS component) has MBS rubber in the darker gray PC phase and its interface with the lighter gray ABS phase. Figure ~ is a TEM photograph oP Experiment 6 showing that the PC/emulsion ABS/MBS blend (27 percent acrylonitrile by weight in the ABS component) has MBS rubber in the darker gray PC phase. Figure 5 is a TEM photograph of Experiment 1 showing that the PC(branched)/ABS/MBS blend (23 percent acrylonitrile by weight in the ABS
component) has MBS rubber in the darker gray PC phase.

The photographs show the location of the small particles of rubbery impact modifier or melt strength enhancing agent in the polycarbonate and ABS resin phases and in the interfaces. This location of the rubber particles in both phases and the interfaces together with the use of a branched polycarbonate not only gives improved interfacial bonding but also results in higher melt strength, elastic modulus and higher zero shear viscosity. These are properties which are desirable and/or useful in blow molding of large parts since high R* values (a measure of melt elastioity and viscosity) are needed for the blow molding of large parisons weighin~ 0.9 kilograms (2 pounds) or more. The combination of the use of the branched polyoarbonate and the ability to control the placement of rubber, such that rubber now resides in each phase and the phase interfaces of a multi-phase polymer blend, is critical to increase the melt strength and elastic modulus of 36,537A-F -6--7- 2~ 7~

compositions used for large part blow molding applications.
The linear carbonate polymers employed in the present invention are advantageously aromatic carbonate polymers such as the trityl diol carbonates described in U.S. Patent Nos. 3,036,036; 3,036,037; 3,036,038 and 3,036,039; polycarbonates o~ bis(ar-hydroxyphenyl)-alkylidenes (often called bisphenol-A type diols) including their aromatically and aliphatically substituted derivatives such as disclosed in U.S. Patent Nos. 2,999,835; 3,038,365 and 3,334,154; and carbonate polymers derived from other aromatic diols such as described in U.S. Patent No . 3,169,121.
It is understood, of course, that the polycarbonate may be derived from (l) two or more different dihydric phenols or (2) a dihydric phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibasic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired. Also included in the term carbonate polymer are the ester/carbonate copolymers of the types described in U.S. Patent Nos. 3,169,121; 4,156,069; 4,260,731;

4,330,662; 4,355,150; 4,360,656; 4,374,973; and 4,388,455. Of the aforementioned carbonate polymers, the polycarbonates of bisphenol-A and derivatives, including copolycarbonates of bisphenol-A, are preferred. Methods for preparing carbonate polymers for 3 use in the practice of this invention are well known.
For example, several suitable methods are disclosed in the aforementioned patents.
The randomly branched chain polycarbonates used in this invention are also well known to those skilled 36,537A~F -7-- 2~4475 in the art and are prepared by reacting a dihydric phenol with phosgene in the presence of a trihydric and/or tetrahydric phenol as illustra.ed i.. ~.~. ratent No. 3,544,514.
Blow moldable resins and their desired properties are taught in U.S. Patent Nos. 4,652,602 and 4,474,999. U.S. Patent No. 4,652,602 is particularly pertinent since it gives a definition of R* which is a measure of blow moldability that is used in the below Experiments to illustrate the performance of the compositions according to the present invention.
The grafted copolymers of butadiene rubber with nitrile and a vinyl aromatic hydrocarbon monomers used in the compositions of the present invention are generally characterized as having a dispersed elastomeric phase and a rigid matrix phase. These compositions are well known and are typically prepared by emulsion, suspension, or mass polymerization, a well known example of resins of this type being the acrylonitrile-butadiene-styrene resins (ABS). The elastomeric or rubber portion of such composition is usually dispersed as discrete particles in a matrix made up of the rigid, thermoplastic portion. Amounts of the thermoplastic matrix are grafted to the various rubber particles which allows the rubber properties of the elastomeric portion or component to contribute to the toughness and melt strength of the composite. Grafting 3 between the elastomeric component and the thermoplastic matrix allowa the ~hear-yielding tendency of the rubber to assist in the dissipation of the energy of an impact blow, reducing the likelihood of a stress fracture.

36,537A-F -8-~4~7~';
_9_ This grafting also provides higher elasticity and strength in the melt stage.
A suitable acrylonitrile-butadiene-styrene resin (ABS) can be formed by the grafting of a styrene-acrylonitrile (SAN) copolymer onto a polybutadienesubstrate latex. The polybutadiene elastomeric component is grafted with SAN copolymer and dispersed as a discrete phase in a thermoplastic component formed by the ungrafted SAN. These products are often mixed with further amounts of ungrafted SA~ copolymer.
It is also well known to prepare such ABS
resins by one of the known mass, solution, mass-solution, or mass-suspension processes where the styrene and acrylonitrile monomers are copolymerized in the presence of a previously prepared polybutadiene substrate while in a solution in monomers or other organic solvent in which the monomers, rubber and SAN
copolymer are at least partially soluble. In this type of process, the forming styrene-acrylonitrile (SAN) copolymer forms both grafted polymer onto the rubber and the balance of the matrix polymer.

The rubber content of the rubber-modified styrenic thermoplastic resin used in this invention is not more than 40 percent by weight. This aspect of ABS, together with the flexibility of varying the molecular weight of the respective components, the degree of grafting, and rubber particle size and morphology are important, as are the precise vinyl aromatic and nitrile monomer contents, in obtaining desirable properties and can be adjusted accordingly as known to those skilled in the art. It is important to keep in mind that the nitrile content of this component needs to be maintained 36,537A-F -9-.

-10- ~3 ~7~

at levels greater than 18 percent by weight in order to achieve sufficient polarity to best facilitate the location of .he "nelt s.rength enhancing agent into the carbonate polymer phase and its interface with the ABS-type polymer.

The ABS-type component can be manufactured from nothing other than acrylonitrile, butadiene and styrene, or other monomers can be partially substituted for or mixed in with them. Although alteration of the monomer mix yields a variation in the properties of the composite, usually it does not, nor is intended to, cause a variation in the fundamental substrate-graft-matrix structure which is characteristic of a rubber-modified styrenic thermoplastic resin such as A~S.
However, the monomer mix (especially the nitrile monomer) does influence the solubility parameter of the thermoplastic SAN phase and, as shown in this invention, can be used to direct or place the melt strength enhancing agent in a non-styrenic polymer when tne three are blended.
The ABS used this invention can be made by any of the various methods described in greater detail in Childers, U.S. Patent No. 2,820,773 (U.S. Rubber);
Calvert, U.S. Patent No. 3,238,275 (~org Warner);
Carrock, U.S. Patent No. 3,515,692 (Dart); Ackerman, U.S. Patent No. 4,151,128 (Mobil); Kruse, U.S. Patent No. 4,187,260 (Monsanto); Simon, U.S. Patent No.
3 4,252,911 (Monsanto); and Weber, U.S. Patent No.
4,526,926 (Dow).
The melt strength enhancing agent used in this invention is a core/shell graft copolymer having a core of a rubbery polymer of butadiene or butadiene-vinyl 36,537A-F -10-" 2~ 4~7~

aromatic hydrocarbon monomer or butadiene-vinyl aromatic hydrocarbon-alkyl acrylate monomers with optionally a second inner shell phase u~ a pui-yT~e~ Gf ~.n-yl aromatic hydrocarbon and a outer shell of a polymer of alkyl (~eth)a.crylate. A well known example of these copolymers is methylmethacrylate-butadiene-styrene resin (MBS). Such copolymer should have a Tg less than 0C
and a rubber content greater than 40 percent. These are generally made in stages by first polymerizing a conjugated diene, or by copolymerizing a conjugated diene with a mono-olefin or polar vinyl compound, such as styrene, acrylonitrile or methyl methacrylate to ~orm the rubbery polymer substrate latex. The substrate latex is typically made up of about 50 to lO0 weight percent conjugated diene and up to 50 weight percent of one or more mono-olefin or polar vinyi compound.
A mixture of monomers is graft polymerized to the substrate latex to form the shell(s). A variety of monomers may be used for this grafting purpose, of which the following are exemplary: vinyl aromatic compounds such as styrene, vinyl toluene, alpha-methyl styrene, halogenated styrene, naphthalene; nitriles such as acrylonitrile, methacrylonitrile or alpha-halogenated acrylonitrile: or a Cl to C8 alkyl acrylate such as methacrylate, ethylacrylate or hexyl acrylate, a Cl to C8 alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, glycidyl methacrylate or hexyl methacrylate, unsaturated carboxylic acids such as an acrylic or methacrylic acid including derivatives of such acids such as anhydrides; or a mixture of two or more of the foregoing. The extent of grafting is sensitive to the substrate latex particle size, and particle size may be influenced by controlled 36,537A-F -11-.. . . . ., . , , . ~ .

. ~ . . .

- ~ . : :
-: .. . :, ~ . ; .. .

12- 2~ 75 coagulation techniques among other methods. When the graft level is allowed ~o reach an excessively high level, the melt strength effect of the relative substrate latex content is reduced.
The grafting monomers may be added to the reaction mixture simultaneously or in sequence, and, when added in sequence, layers, shells or wart-like appendages can be built up around the substrate latex, or core. The monomers can be added in various ratios to 0 each other although, when just two are used, they are frequently utilized in equal amounts. A typical weight ratio for an MBS rubber is 60 to 80 parts by weight substrate rubber latex based on solids, 10 to 20 parts by weight first monomer and 10 to 20 parts by weight second monomer. A preferred formulation of an MBS
rubber is one having a core build up from the polymerization of about 71 parts of butadiene, about 3 parts of styrene, about 4 parts of methyl methacrylate and about 1 part of divinyl benzene; a second inner shell phase about 11 parts of styrene; and a shell phase about 11 parts of methyl methacrylate and about 0.1 part of 1,3-butylene glycol dimethacrylate, where the parts are by weight of the total polymer composition. A
product having substantially such content is avail~ble commercially from Rohm and Haas Company as Paraloid~
EXL 3607 core-shell MBS polymer.
The MBS rubber and methods for making same, as 3 described above, are discussed in greater detail in Saito, U.S. Patent No. 3,287,443 (Kanegafuchi); Curfman, U.S. Patent No. 3,657,391 (Borg-Warner); and Fromuth, U.S. Patent No. 4,180,494 (Rohm and Haas).

36,537A-F -12-., .. , .~ ~ .. ~,. ... . .... . . . .... .. . . . .

- 1 3- 2~4~75 The following Experiments are presented to further illustrate the invention.
Ex~eriment l One thousand two hundred and forty parts by weight of a branched polycarbonate was mixed with 640 parts by weight acrylonitrile-styrene-butadiene copolymer (ABS Y23), containing polymerized therein 23 weight percent acrylonitrile and about 20 weight percent butadiene polymer rubber, the balance being styrene. To this wa~ also added 2 parts by weight epoxidized soybean oil (Plas ChekT~ 775 from the Ferro Company), 4 parts by weight Irganoxr~ 1076 antioxidant (from Ciba Geigy) and 120 parts by weight MBS rubber (Paraloidr~ 3607 from the Rohm and Haas Company). The MBS rubber melt strength enhancing agent having a Tg of about -70C and about 70 weight percent rubber was a core/shell graft copolymer having a core of a polymer of 71 parts of butadiene, about 3 parts of styrene, about 4 parts of methyl methacrylate and about l part of divinyl benzene; a second inner shell phase of about 11 parts of styrene; -and a shell phase of about ll parts of methyl methacrylate and about O.l part of l,3-butylene glycol dimethacrylate.
The mixture wa-~ uniformly blended together in a laboratory tumbler. The blend was introduced into a 30 millimeter Werner-Pfleiderer melt extruder, with heating set points of 270C. The extrudate was pelletized and dried. The pellets were fed to a 70 ton Arburg injection molding machine to mold impact test bars of 12.6 cm x 1.25 cm and tensile bars of 16.3 cm x 1.3 cm with thickness o~ 3.175 millimeter.

36,537A-F -13-: : ~...... . - . ..

The composition of this and several further experimental polycarbonate/ABS blends is given in Table 1 below. Each of the other experimental compositions was made by following the procedure for Experiment 1.
The moldings were subjected to tests to determine their blow moldability (R* value) and 0.025 millimeter (10 mil) notched Izod. The test results are given in Table 2 below.
The blowmoldability was determined by a method generally as described in U.S. Patent No. 4,652,602.
This evaluation is based on the fact that blowmoldable resins need to have two properties, reasonably low viscosity in the extrusion annulus as the parison is extruded (moderate shear conditions) and sufficient melt strength and higher viscosity to allow a suspended part to be formed (low shear conditions). On this basis a value for blowmoldability, R*, is defined as the ratio o~ viscosities at shear rates of 0.1 and 100 reciprocal seconds at a processing temperature that has experimentally been determined to be sufficient to form a reasonable parison or calculated to be the temperature at which the material viscosity is 20,000 poise at a hear rate of 100 reciprocal seconds. According to this method the R* values for this and the other Experimental compositions prepared below are determined.
These compositions may be useful in melt ~orming applications such as injection molding, blow 3 molding or thermoforming applications.
These compositions, a~ shown in the Experiments, may also contain other ingredients such as UV and antioxidant stabilizers, fillers such as talc, reinforcement agents such as mica or glass fibers, 36,537A-F -14-~: . , -, - . . ~ .

1 5- ;~L4~7~

ignition resistant additives, pigments. antistatic agents, and mold release additives.
As used in the Tables below: "Lin. PC" is a linear polycarbonate having a melt flow rate (MFR) of 10 grams per 10 minutes commercially available from The Dow Chemical Company as Calibre~ 300-10; "Bran. PC" is a randomly branched polycarbonate with a 3 MFR
commercially available from The Dow Chemical Company in the Calibre'~ 600 series; "ABS 213" is acrylonitrile-~tyrene-butadiene graft copolymer from the Dow Chemical Company containing 16 percent acrylonitrile by weight and about 7 percent rubber by weight; "ABS X21" is acrylonitrile-styrene-butadiene graft copolymer from Dow containing 21 percent acrylonitrile by weight and about 16 percent rubber by weight; "ABS Y23" is acrylonitrile-styrene-butadiene graft copolymer from Dow containing 23 percent acrylonitrile by weight and about 21 percent rubber by weight; "Cycolac~ TE-1000" is emulsion ABS
20 from Borg-Warner containing 25 to 29 percent acrylonitrile by weight and about 16 percent rubber by weight; "Para 3607" is Paraloid~ 3607 methylmethacrylate-styrene-butadiene (MBS) core/shell graft copolymer from Rohm and Haas having as a core a rubbery polymer of butadiene with an inner shell of a styrene polymer and an outer shell of a styrene-me~hylmethacrylate polymer, containing about 70 percent rubber by weight and having a Tg of about -70C; "Izod l" refer~ to notched Izod impact resistance values measured according to ASTM D-256 in ~oules/meter perpendicular to the direction of polymer flow at the given temperatures and "Izod 11" refers to valueY
measured parallel to the direction of polymer flow.
"R*" refers, as mentioned above, to a viscosity ratio :: .

36,537A-F -15-- 1 6- 2~ 75 which give~ a measure of blowmoldability, higher values indicating better blowmoldability.
All Experimental compositions contained 2 grams of epoxidized soybean oil and 4 grams of Irganoxr~ 1076 a high molecular weight, sterically hindered phenolic antioxidant from Ciba Geigy.
Table 1 PC/A8S Compositions ABS ABS ABS Para Lin.Bran. 213 X21 Y23Cyclolac3607 PCPC (wt twt (wtTE-1000 ~wt (wt pts/ (wt pts/ pts/ pts/ pts/ (wt pts/ pts~

wt %) wt %) wt %) wt %) wt %) wt %) wt %) Control 1 1240/62 0 640/32 0 0 0 120/6 Control 2 1240/62 0 0640/32 0 0 120/6 Control 3 1240/62 0 0 0 640/32 0 120/6 Control 4 0 1240/62640/32 0 0 0 120/6 Experiment 0 1240/62 0 0 640/32 0 120/6 Experiment 620/31 620/31 0 0 640/32 0 120/6 Experiment 930/46.5 310/15.5 0 640/32 0 0 120/6 Experiment 620/31 620/31 0 640/32 0 0 120/6 Experiment 310/15.5 930~46.5 0 640/32 0 0 120/6 Control 5 1300/65 0 0 0 0 700/35 0 Experiment 620/31 620/31 0 0 0 640/32 120/6 36,537A-F -16-, 1 7- 2~4~75 Table 2 PC/ABS Compositions 1 Izod III~od R* by 23C -29C 23C -29C wei~ht Control 1 4.2 422 91 593 433 16 Control 2 4.8 41~ 201 577 438 21 Control 3 5.0 443 215 588 423 23 Control 4 ~.9 310 48 587 256 16 Experim~nt 1 8.3 418 112 594 420 23 Experiment 2 6.1 435 157 592 422 23 Experiment 3 4.9 438 112 577 352 21 Experiment 4 5.7 401 128 566 438 21 Experiment 5 6.6 433 75 657 459 21 Experiment 6 4.5 442 106 538 252 27 Control 5 2.4 470 100 576 134 27 Controls 1 and 4 are examples of PC/ABS/MBS
resin compositions where the ABS contains only 16 percent AN in the rigid phase. Controls 1 through 3 are example_ of PC/A8S/MBS resin compositions which contain only a linear polycarbonate. Experiments 1 through 5 show exampleq where the ABS portion contains 21 percent or 23 percent AN. Table 2 shows that higher R* values and better low temperature perpendicular izod values are obtained over Control Experiments 1 and 4 when the MBS
rubber is located at the'PC interface or in the PC phase or over Control Experimentq 2 and 3 where no branched polycarbonate is u~ed. The location of the MBS rubber i3 dictated by the solubility parameter of the ABS resin which at higher AN level~ drive~ the rubber to the PC
phase.

36,537A-F -17-- 1 8~ 4~75 Control Experiments 2 and 3 use only linear PC
which has fairly low melt elasticity, thus directing a rubber into the PC phase can increase the meit elasticity but not aq much as in the case of branched polycarborates which are required for improved blow molding reqins. As seen in Experiments 1 through 6, the melt elasticity of a PC blend resin can be increased by uqing a branched polycarbonate.As expected, Control 4 shows a large increase in R* values by switching to a branched resin, however in doing so impact properties drop substantially. Experiment 1 shows that by directing the rubber to the PC phase, large improvements in R* and impact values are achieved. This rubber placement is dictated by the AN content of the second phase i.e., the ABS phase.
Experiments 2 through 6 show that a blend of linear and branched polycarbonates give a good overall balance of high R* values and high impact values when the AN content of the ABS resin is greater than 20 percent. AN contents greater than 18 percent help direct the MBS to the PC phase which enhances the melt elasticity and impact of the overall blend.
The preferred ABS iq mass produced, however, aq seen in Control Experiment 5, blends of PC with emulsion produced ABS have lower R* valueq, but can be greatly enhanced with the addition of MBS and branched PC as indioated in Experiment 6.
Ex~eriment 7 The composition of Experiment 4 waq blow molded u~ing a Hartig blow molding machine with a 13.6 kilogram (30 pound) accumulator head having a 35.6 centimeter (14 36,537A-F -18-: ~ .
' ' ~

-19- ~ ~ ~ ~ 4.

inch) tooling diameter and a tooling angle of 30 degrees. This head employed a 8.9 centimeter (3.5 inch) extruder witn a L:D ratio of 24:1 with a barrier screw running at 14 rpm and with set temperatureq at 199C
(390F) for each zone. Melt ~emperatures were measured at approximately 218C (425F)and mold temperatures were set at 77C (170F). A parison having a length of 132 centimeters (52 inches) was extruded weighing 4.6 kilograms (10.2 pounds)and it had a 40.6 centimeter (16 inch) lay flat at both the top and bottom. Pinch bars to support the parison were ~ot required because of the high melt strength nor was pre-blow required because of reduced sag. Excellent blow molded parts with uniform wall thicknes~ were obtained. These were tested to give the following value~.

Instrumented Dart Impact 66.4 J at 22.8C
(ASTM 3673) (586 in-lbs at 73F) 56.8 J at -29C
(501 in-lbs at -20F) DTUL 1.8 MPa (264 psi) io4Oc (220F) Flexural Modulus 2270 MPa (329,000 psi) 25 Tensile Strength 52 MPa (7500 p~i) Izod Impact - 0.025 Millimeter 14.2 J at 22.8C
(10 mil) notch (10.6 ft-lbs at 73F) 13.1 J at -29C
(9.8 ft-lbs at -20F) Experiment 8 The procedure of Experiment 1 was repeated to make specimen bars using 40 parts by weight of a branched polycarbonate, 60 parts by weight of acrylonitrile-36,537A-F -19-, . , .. . ~ ~ : :

-20- 2~ 7~

styrene-butadiene copolymer (ABS Y23) and 8 parts by weight MBS rubber (Paraloid~Y 3607 from the Rohm and Haas ~ompany). Tne predried tensile bars were suspsnded for 5 minutes by one end in a Porced air oven at the approximate blow molding proce3sing temperature of 190C
for PC/ABS blends with increa~ing weights being suspended from the other end. In Experiment 8, the maximum weight added in grams without any sagging is reported in Table 3 as 25 grams (the maximum support weight). This is a measure o~ the melt strength of the blend at the approximate blow molding processir.g temperature.
Experiments 9 through 11 and Control Experiments 6 and 7 w6re prepared and tested in a similar manner to Experiment 8 and the results are set forth in Table 3.
Control Experiments 6 and 7 illuqtrate the invention ~et forth in Japanese Patent No. 58-59258 and these controlq show that the resins compositions of that patent have much lower melt strengths as compared to the examples oP the present invention. Experiment 11 is a substantial duplicate of Experiment 2 and the high R*
value of 6.1 qhown in Table 2 for Experiment 2 correlateq well with the maximùm qupport weight of 40 grams ~hown in Table 3 Por Experiment 11. In Table 3 below all abbreviation~ are as given above with the addition that "B-11" is an MBS resin Prom the 3 Kanegefuchi Chemical Induqtry, having a core/shell structùre and containing about 50 percent rubber by weight.

36,537A-F -20-. . . .

, .
, :

::

-21- 2~4~

Table 3 PC/A8S Compositions Lin. Bran. ABS Para Max.
PC PC Y23 B-ll 3607 S~pport (wt Dts) ~wt pts)(wt otsL (wt ots) twt ots) wt. tqms) Control 640 0 60 8.0 0 10 Control 760 0 40 3.0 0 15 Experiment 8 0 40 60 0 8.0 25 Experiment 9 0 60 40 0 3.0 48 Experiment 10 0 85 lS 0 5.0 81 Experiment 11 33 33 34 6.0 40 36, 537A-F -21-

Claims (9)

1. A moldable carbonate polymer blend composition comprising.
A) 20 to 95 percent by weight of a carbonate polymer, B) 5 to 75 percent by weight of one or more graft copolymer wherein a butadiene polymer rubber or a butadiene-vinyl aromatic hydrocarbon copolymer rubber has graft polymerized therewith a mixture of nitrile and vinyl aromatic hydrocarbon monomers, which graft copolymer contains greater than 18 percent by weight of nitrile and less than 40 percent by weight rubber and C) 1 to 20 percent by weight of a melt strength enhancing agent having a Tg less than 0°C and greater than 40 percent rubber which is a core/shell graft copolymer having a core of a polymer of butadiene or butadiene-vinyl aromatic hydrocarbon or butadiene-vinyl aromatic hydrocarbon-alkyl acrylate monomers with optionally a second inner shell phase of a polymer of vinyl aromatic hydrocarbon and a outer shell of a polymer of alkyl (meth)acrylate, wherein said percents by weight are based on components A), B) and C) characterized in that the carbonate polymer is selected from (i) randomly branched carbonate polymers, and (ii) blends of randomly branched carbonate polymer with linear carbonate polymers.

2. A composition according to Claim 1 comprising A) 30 to 90 percent by weight of randomly branched carbonate polymers, B) 10 to 65 percent by weight of one or more graft copolymer of butadiene rubber with nitrile and vinyl aromatic hydrocarbon monomers and C) 3 to 12 percent by weight of melt strength enhancing agent.

3. A composition according to Claim 1 comprising A) 30 to 90 percent by weight of a blend of randomly branched carbonate polymer with linear carbonate polymers, B) 10 to 65 percent by weight of one or more graft copolymer of butadiene rubber with nitrile and vinyl aromatic hydrocarbon monomers and C) 3 to 12 percent by weight of melt strength enhancing agent.

4. A composition according to Claim 3 comprising A) 50 to 80 percent by weight of a blend of randomly branched carbonate polymer with linear carbonate polymers.

5. A composition according to Claim 1 wherein amounts of the melt strength enhancing agent are located in the carbonate polymer phase and in the interface between the carbonate polymer phase and the phase containing the graft copolymer of butadiene rubber with nitrile and vinyl aromatic hydrocarbon monomers.

6. A process for the preparation of a blow molded or thermoformed article comprising the steps of A) providing a composition having high melt viscosity and melt strength comprising (I) 20 to 95 percent by weight of a carbonate polymer;
(II) 5 to 75 percent by weight of one or more graft copolymer wherein a butadiene polymer rubber or a butadiene-vinyl aromatic hydrocarbon copolymer rubber has graft polymerized therewith a mixture of nitrile and vinyl aromatic hydrocarbon monomers, which graft copolymer contains greater than 18 percent by weight of acrylonitrile and less than 40 percent by weight rubber, (III) 1 to 20 percent by weight of a melt strength enhancing agent having a Tg less than 0°C and greater than 40 percent rubber which is a core/shell graft copolymer having a core of a polymer of butadiene or butadiene-vinyl aromatic hydrocarbon monomer or butadiene-vinyl aromatic hydrocarbon-alkyl acrylate monomers with optionally a second inner shell phase of a polymer of vinyl aromatic hydrocarbon and a outer shell of alkyl (meth)acrylate wherein said percents by weight are based upon components (I), (II) and (III) and B) blow molding or thermoforming said composition to form an article characterized in that the carbonate polymer is selected from the group consisting of (i) randomly branched carbonate polymers, and (ii) blends of randomly branched carbonate polymers with linear carbonate polymers.

7. The process as set forth in Claim 6 wherein said carbonate polymer is a blend of randomly branched carbonate polymer With one or more linear carbonate polymer.

8. The process as set forth in Claim 7 wherein said carbonate polymer is 50 to 80 percent by weight of a blend of randomly branched carbonate polymer with one or more linear carbonate polymer.

9. The process according to Claim 6 wherein a blow molded article is prepared from an extruded parison which parison weighs at least 0.9 kilograms (2 pounds).