CA2123080A1 - Process for making polyamide/polyolefin blends having superior improved toughness and stiffness - Google Patents
Process for making polyamide/polyolefin blends having superior improved toughness and stiffnessInfo
- Publication number
- CA2123080A1 CA2123080A1 CA002123080A CA2123080A CA2123080A1 CA 2123080 A1 CA2123080 A1 CA 2123080A1 CA 002123080 A CA002123080 A CA 002123080A CA 2123080 A CA2123080 A CA 2123080A CA 2123080 A1 CA2123080 A1 CA 2123080A1
- Authority
- CA
- Canada
- Prior art keywords
- polyamide
- polymer
- nylon
- blend
- polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Abstract
A process for melt-blending a polyamide with a crystalline polyolefin incompatible therewith in the presence of a rubbery compatibilizing polymer capable of chemically or physically associating with both the polyamide and the polyolefin, at a process temperature higher than the highest melting temperature of any crystalline polymer present and higher than the highest glass transition temperature of any amorphous polymer present but such that significant degradation of any polymer present does not occur, all blend components being present within stated ranges, and the melt viscosity ratio of the polyamide to that of the polyolefin at the process temperature and a shear rate of about 100-200 sec-1 being about 0.1-1.2, especially 0.4-0.8. High stiffness, supertough polymer blends, where notched Izod impact strength exceeds 535 J/m, are obtained.
Description
wo 93/09l83 Pcr/US92/og34o 21~3080 TITLE
PROOE~SS FOR MAK~G POLYAMIDE/POLYOL~F1N BLENDS
BkCKGROUND OF THE INVENTION
s This invention relates to a process for preparing polyamide/polyolefin blends having superior toughness and stiffness compared with currently available blends of such polymers.
Polyamide resins (or polyamides) are well known in the art and have been used for many years, La, as engineering or molding resins, fiber-forming resins, and barrier resins in packaging materials. Crystalline polyamides, especially those made from sbort ch~in monomers, e.B., nylon 6 and nylon 66, are very stiff, which is desirable for molding resins, but tbey are sensitive to moisture. Addition of crystalline polyolefins, such as polyetbylene or polypropylene reduces moisture sensitivity but suffers from incompatibilitybetween tbese two polymers, so tbat acceptable end-use blends are not made. Further, although polyamides have good physical properties, such as tensile strength and flexural (or flex) modulus, thac make these resins suitable for fabricating a variety of articles, they are not conside~ed tough. Their notched Izod impact strength either is too low under ordinary test conditioDs or decreases significantlywith a modest change of temperature, thickness, orientadon, or notch radius. It, tberefore, is convendonal in the industry to toughen polyamide resins by blending them wi~ soft, rubbery polymers which can absorb mechanical shocks without significantly impainng the tensile properties of the polyamides with which 2s they are blended. However, because those soft polymers normally have very low s~ess (or flex moduli), addition of such polymers to thermoplastic resins normally results in blends that have lower flex moduli than the matrix resins alone, so tbat improvement of one property is accomplisbed at tbe sacrifice of ~e otber.
3 o ~ While there is abundant art describing such blends, the most pertinent patent in tbis area is U.S. 4,174,358, to Epstein, describing blends of polyamides witb ~r~ous types of tougber~ng polymers. Tbe Epstein invention invol~es a process for tbe preparation of multiph~se thermoplastic compositions comprising admLYing a defined polyamide matrix resin with at least one of a number of possible polymers having a much lower tensile SUBSrITUTE SHEET
WO g3/09183 Pcr/us92/os34o modulus and containing sites which are adherent to the matrix resin, and then shearing to disperse the polymer in the matrix resin to a particle size of 0.01 to 3 microns, so that the polymer adheres to the matr~x resin.
According to the patent specification and certain examples, tbe blend may be eitber binary or ternary. A ternary blend contains the matrix resin, a soft~
adherent polymer, and a third soft polymcr, which may or may not possess adberent sites; when it does not, it is a straight chain or brancbed polyethylene. Such blends can be made in one step, or the soft polymers can be preblended and tben re-extruded with the matrix resin. Additional compositions of this type are described in Japanese Patent Publications (Kokai) 59-78256 and 59-149940 (both 1984) of Mitsui Petrocbemical Industries, Ltd.
U.S. Patent 4,780,505 to Mashita et al. describes a process where polypropylene grafted with maleic anhydride is added to a 1~ polyamide/polypropylene blend to improve the compatibility of the blend.
This graftcd po~ymer can bc rcplaccd by or added together with another polymcr, such as a rubber grafted with maleic anhydridc or an ethylene copolymer containing a maleic anhydrido or glycidyl methacrylate comonomer.
A reccnt paper by Modic et al. in Plast~s Eng~neer~ng, luly 1991, pp. 37-39, describes blends of nylon 66with polypropylene and of nylon 6 with polypropylene, both witb a compatibilizer - styrenic block copolymer functionalized witb maldc anbydride - which bave high impact strength. The paper discusses mainly tbe situadon where polypropylene becomes tbe matrix and nylon the dispersed phase, although tbe possibility of phase illversion in tbe case of a large nylon/polypropylene rado is mendoned.
It thus is known that one can make ternary blends with desirable mechanical properties by properly selecting the component polymers A, B, and C in optimum ratios and blending them under suitable condidons. Ternary blends, when properly made, can pravide a more desirable balance of properties than binary blends; yet, in practice these terms 'properly", "optimum" and "suitable" are very broad and undefined.
Even for skilled plastics engineers and chemists, this is a rather occult art, 3s which requires a great deal of experimentadon before a satisfactory : ~ SUBSTITUTE SHEET
, ~ ~
W O 93/09183 ~ Z 1 ~ 3 0 8 0 PC~r/US92/09340 composition is obtained. Normally, the matrix polymer A is preselected according to the business need; the two otber components B and C are then varied, either with respect to their characteristics or amounts, or both, and one or more plots or tables reflecting the changes of desired properties with 5 changing compositions are made. Usually, those plots or tables show a trend of either increasing or decreasing property values as tbe compositions are varied. When the desired properties have been obtained, the operation is considered successful, and the blend is adopted for commercial purposes. In some cases, with a particular matrix resin, the experimenter may find that o the desired properties are difficult or impossible to obtain; the experimenterthen has the choice of making do with what he or she has or replacing the matrix resin with another matrix resin and repeating the series of experiments. By following the directives of the Epstein patent, one can in some cases obtain "supertough" nylon resiDs, which for the purpose of the 15 present invention means tbat tbeir notched Izod value is at least 10 ft.-lb/inch (about 534 J/m).
C~ystalline polyolefiDs such as, for example, polyethylene, pohJpropylene, and polyisobutylene are often considered suitable polymers for blending witb polyamides because they improve the polyamide toughness 20 while reducing the stiffness of polyamides to a lesser degree than do amorpbous and rubbery polyolefins. However, binary blends of polyamides with crystalline polyolefins do not show greatly improved toughness.
Addition of a tbird component, or compatibili~er, permits a more thorough blending, resulting in a better dispersion, so that the resulting blend has 25 considerably improved toughness. While tbis is known, the proper choice of the blend components as well as of the blending conditions still is to a large exten~ left to the experimenter who, after a number of trial runs, arrives at a satisfactory composition ~nd process.
Generally speaking, it is very difflcult to prepare a supertough polyamide with high stiffness or to even predict under what conditions or with what components such a composition could be made.
It is, therefore, highly desirable to be able to select in advance compatibilizer B for a given crystalline polyolefin C to be blended with matrix polyamide A under predetenTlined blending conditions in order to 3 5 obtain the maximum degree of improvement of notched Izod impact SUBSTITUTE SHEET
strength for a given flex modulus (which can be calculated in advance from the aex modhli of the components), and to obtain in fact such improvement with a minimum amount of experimentation.
SUM~L~RY OF THE INVENTION
Accord~g to the present invention, there is now provided a process for melt-blendLng at a shear rate of aboul 100-200 sec~1 at least one polyamide A havm~ a number average molecular weiahl, Mn Of abou~
5,000-35,000 with a crystalline polyolefin C incompatible with polyamide A, having a number average molecular weight, Mn~, of aboul 10,000-1,000,000 in the presence of a compatibilizing rubbery polymer B having a ,lass transition temperature, Tg, of at most -~0C and capable of chemically or physically associating with both polyamide A and crystalline polyolefin C~
~he ratio of melt viscosity of polyamide A. M~ o melt viscosi~v of polyolefin C, MVC, at the process temperature and at the same shear rate Wilhi~l the range o~ about 100-~00 sec~l being aboul 0.37-0.8~ and especially 0.4-0.8, to form a multiphase blend haviila a notched Izod impact stren~th of more than 535 J/m;
said process comprising melt-blendin~ polymers B and C with - polyamide A Ln their respecùve weight perceMages b%~ c%, and a% such that (1) a + b +c = 100;
) b = 3 to 15;
(3) b + c > 10;
(4) 1:1 < a/c <20:1; and ~: 25 (S) 1:5 < b/c < 3:1, at a process temperature which is higher than the hi~hest melting temperature of a~y crystallLne polymer present and higher than the highest glass transition temperature of anX amorphous polymer present but lower than the lowest temperature at which a~y poly~ner begins to si~nificantly 3 0 degrade, under residence time and mixing energy conditions such that polyamide A forms a conti~uous phase, while polymers B and C form a particulate phase dispersed in the continuous phase.
BRrEF DESCl~ION OF IHE DRAVV~iGS
Figs. 1 through 5 represent plots of notched Izod impacl 3 5 strength vs. melt viscosity ratio at a 104 sec~l shear rate for represerltative ,, Amended Page ,, ~
wo 93/09183 2 1 2 3 0 8 0 PCr/USg2/Og340 multiphase blends of polyamide/maleic group-containing compatibilizing rubbcry polymcr/polypropylene. In all these graphs, the ordinate represents notched Izod impact strengtb in J/rn, wbile the abscissa represents tbe melt viscosity ratio of polyamide A to crystalline polyolefin C.
DET~ILED DESCRIPIlON OF THE INVENTION
Definition: For the purpose of the present disclosurc and claims, tbe tenns "associating" and "association" include botb a chemical and a physical interaction, including, for cxample, a chemical reaction, cspecially grafting, hydrogen bonding, and ionic bonding; as well as electrostadc attracdon, and magnetic attraction. Associadon of two polymers is facilitated by, or necessarily requires, a low interfacial tension between them.
A compadbiLizing polymer normally would have an aliphatic chain, which would make it compatible with polyolefins, and at least one polar functional group, which would make it compatible with polyamides.
Typical such functional groups include, cg., carbonyl-containing groups such as carboxyl, ionic carbo~late, ester, and ketone; hydroxyl, thione, amine, and amide. ln order to determine whether a prospective compatibilizing polymer B is suitable for the proposed application, one only needs to pcrform two experiments, namely, prcparc under the proposed process conditions a blend of polymer B with polyan~ide A and a blcnd of polymer B
with crystalline polyolefin C in the desired ratios and determine the notched Izod strength of each such resulting blend. If the notched Izod ~alue of the first blend is higher than the notched Izod value of the corresponding 2s polyamide, and the notched Izod value of the second blend is higher than that of the polyolefin, then the selected polymer B is a suitable compatibili~ng agent.
Proper blending conditions will depend on tbe particular needs. The components always are blended in the melt, either in one step or 3 o in two steps (by first preblending polymers B and C and then blending the resulting material with polyrner A), so long as blending in the presence of polymer A is conducted witb sufficient energy to produce uniform dispersion, preferably ha~ng dispersed particles of small size, for example, 3 micrometers or less. Preblending B ~nth A is generally not recommended 3s because these two polymers may react chemically or crosslink to the point of :
SUBSrITUTE SHEET
wo 93/09183 Pcr/uss2/os340 ~1~3q~0 6 becoming difficult or impossible to melt process, or tbeir viscosity may becomc so high that a uniform dispersion of B and C ~n A cannot be obtained. Blending in a twin-screw extruder has been found to produce consistently satisfactory and reproducible results but other blending 5 equipment may provide equally acceptable results. Sucb otber equipment includes, for example, Buss Kneader. Blending is carried out at a temperature at which all thc blend components are molten but not so high that any of them would begin to degrade. The blend polymers sbould not be suscepdble of crosslinking under the blending conditions but should remain 10 thermoplastic.
Typical matrix polyamides can be bighly or partly crystalline or amorphous, or can themselves be blends of crystalline and amorphous polymers. They can be made by condensation of substantially equimolar amounts of a saturated aliphadc, aromadc, or cycloaliphatic dicarboxylic 15 acid having 4-12 carbon atoms witb a primary or secondary aliphadc or ~ycloaliphadc diamine having 4-12 carbon atoms. Representadve dicarbodcylic acids include succinic, adipic, azelaic, sebacic, 1,12-dodecanoic,1,4g~clohexanedicarbadtylic, terephthalic, and isophthalic. Representative diamines indude tetramethylenediamine, pentamethylenediamine, 20 hexamethylenediamine, dodecamethylenediamine, and 1,4-cyclohexanediamine. Otber suitable polyam;ides can be made by homopolymerization, with ring opening, of lactams ha~nng from S to 13 ring atoms. Representative lactams include d-valerolactam, e-caprolactam, w-laurolactam, etc. Suitable polyamides also include polyamides made by 25 polycondensation of two or more components of the same type, such as, for exa~mple, two different dicarboxylic acids with one diamine, or two different diamines witb one dicarboxylic acid, or one diamine, one dicarboxylic acid, and one lactam, or a polyamide in wbicb a portion of the dicarboxylic acid is terephtbalic acid and another portion is isophthalic acid, etc. Preferably, the 3 o polya nides, if they are crystalline, should have a melting point in excess of 160 C. lt is further preferred that tbe polyamides have a relative viscosity, detenI~ined in 90% aqueous formic acid, of about 20-300. Especially preferred polyamides include, for example, poly(hexamethylene adipamide) or nylon 66, poly(e~aprolactam) or nylon 6, poly(bexamethylene 35 terephthalamide), nylon 12 and nylon 12,12~ Compatible blends of two or SUBSTITUTE SHEET
WO 93/09183 PCI/US92/Og340 2i2~080 7 ~r ~
more polyamides may be used, instead of a single polyamide, to form the matrix component of the blend. A satisfactory polyamide will have a notched Izod impact strength of more than 166 J/m and a ~ex modulus of more than 1380 MPa, but a more desirable polyamide will have a notched s Izod value of more than 330 J/m and a flex modulus of more than 1170 MPa The best polyarnides in this more desirable category will have a notched Izod value of more than about 555 J/m.
Typical crystalline polyolefins include both homopolymers and random or block copolymers, having a flexural modulus of more than about 10 345 MPa Suitable crystalline polyolefins indude, ~g., high density and low density, random and linear polyethylene; syndiotactic and isotactic polypropylene, poly(butene-1), poly(isobutene), poly(2-methylpentene-1), and poly(hexene-1). ~ystalline polyolefins incompatible with matrix polymer A do not have functional groups capable of reacting or associating 15 witb polymer A. For economic reasons, tbe most preferred crystalline polyolefin, having higb ae~mral modulus and high beat distortion temperature, is isotactic polypropylene, wbicb is readily available at a modest price, comparable to that of high density polyethylene.
Suitable compatibilizing polymers are normally known as soft 20 polymers; that is, they have a low aexural modulus. Usually, they have predorninant amorphous portions. Many of those polymers have been conventionally used in the prior art for tougbening polyamides. Suitable compatibilizing polymers include, for example, etbylene copolymers with alkyl acrylates and methacrylates sucb as ethylene/ethyl acrylate and 2s ethylene/me~yl methacrylate copolymers; ethylene terpalymers with aL~cyl acrylates or methacrylates and carbon mono~de such as ethylene/CO/n-butyl ac~ylate, ethylene/CO/methyl methacIylate, and ethylene/~)/ethyl acrylate terpolyrners; ethylene copolymers with an epoxy group-containing monomer and, optionally, a third monomer such as, ~g~, 3 o ethylene/vinyl acetate/glycidyl methacrylate and ethylene/n-butyl acrylate/glycidyl methacrylate terpolymers; styrene/ethylene-butylene/
styrene block copolymers containing either a carboxylic group or an e~oxy gro~lp; partially ionized copolymers of ethylene with an a,b-unsaturated carboxylic acid and optionally with a third comonomer, including 35 ethylene/acrylic acid, ethylene/mëtkac~ylic acid, ethylene/vinyl SUBSTITUTE SHEET
acetate/acrylic acid, ethylene/buryl acryla~e/methacrylic acid, and ethylene!vinyl acetate/monomethyl ester of maleic acid copolymers, each neutralized in part with zinc, magnesium, calcium, sodium, potassium, or lithiurn ions; anhydride group-containing polymers such as, for example, 5 EPDM elastomers having maleic anhydride or glycidyl me~hacrylate arafted thereon such as ethylene/propylene/1,4-hexadiene elaslomer or ethylene/propylenell,4-hexadiene/norbornene elastomer orafted with maleic anhydride, styrene/ethylene-butylene/slyrene block copolymers grafted with maleic anhydride or glycidyl methacrylale, and terpolymers of 10 ethylene with maleic anhydride and another monomer such as ethylene/vinyl acetate/maleic anhydride terpolymer. Preferred compatibilizing polymers are etnylene copolymers havina pendant anhydride or glycidyl groups or both. The most pret`erred compalibilizing polvmer B is an EPDM elastomer having at least one of maleic anhydride and ~lycidyl 15 methacrylate moie~ies grafted thereon, each in an arnoum of about 0.2-?%
; ~; of the total elastomer weight~ When polymer ~ is nylon 6 or nylon 66. andcrystalline polyolefin C is polypropylene, Ihe following relationship preferably should e~tist:
3 < b/c < 3:1 20 and the preferred amoun~ of this compalibilizing polymer is 5-1j% of the blend.
he preferred weight percentage of polvamide A is at least SO%, especially at least 60%. Within these ranges, supertough blends can be obtained within rather wide MV~A/MVc ratios, which ra~ios for the 2 5 purpose of ~he present disclosure will be sometimes represented below as A/C MVR. This is illustrated ~n Figs. 1 through S for blends of five compositions based on nylon 66 and nylon 6 (each as polyam~de A), polypropylene (polyolefin C), and a compatibilizing polymer, arl EPDM
mbber grafted with maleic anhydride (polymer B~. These figures~ based on 3 o experiments described in the examples below, represent plots of notched Izod impact strength (determ~ned according to AS~M standard O-256) vs.
A/C MVR. The respective weight percentages of A in those experiments were as follows:
. ~ ~
:
~ ~ ~ Amended Page :
S~ T
WO 93/09183 ~ 1 2 3 0 8 0 PCr/U~92/09~
A.~o B.% C.%
Fig. 1 85 10 5 Fig. 2 80 10 1 s Fig. 3 75 10 15 Fig. 4 70 10 20 Fig. 5 60 10 30 It can be seen from those graphs that for a constant axnount of 10 B component, while va~nng the amounts of A and C, the A/C MVR range ~,vithin which supertough blends can be obtained is wider for the compositions containing a larger ~nount of polyamide A. It is noted that the plot in Fig. 1 contains an irregularity in the A/C MVR region of about 035, which is believed to be fortuitous and not meaningful. However, a 15 rna~num usually is found, according to these plots, somewhere in the neighborhood of A/C MVR equal to abou~ 0.4. ~or different viscosi~
ratios, which would depend on a different selection of polyamide and polyolefîn, this ma~n num could be located elsewhere on the graph but could always bc determined with sufficient precision to be useful in evaluating 20 prospective resins. For practical purposes, one would ~ot have to make such determinations for more than one or two compositions per set of polymers because the location of the ma~num ~does not change significantly with the respecdve percentages of the compon~nts; it is the melt viscosity ratio that determines both the location of the maximum and the value of notched Izod 25 impact streng~h at that location. Accordingly, it is entirely feasible and prac tical to establish such plots in advance for future reference for a number of polyamides and polyolefins, using any desired compatibilizing polymer.
As will be shown below, this invention makes it possible to obtain, with small amounts of polyolefin in the blend, compositions that have 3 o highly improved toughness and bigh stiffness; while with larger amounts of polyolefin in the blend, compositions having toughness and stiffness properties comparable to those of toughened polyamides of the prior art can be ob~ained at a much lower cost.
Generally spealdng, the practice of this invention involves 35 both a material selection and a selection of process parameters. The SUBSTITUTE SHEET
wo 93/09183 PCr/USg2/Os340 2123~ lO
material selection involves the selection of polymers A, B, and C as well as of the molecular weight of each polymer. If the selection of all three polymers is imposed by cornmercial or other practical considerations, optimum toughness can be obtained for a specific weight ratio of those 5 polymers; but if the composition is not critical, then it is possible to also optimize the toughness, cg., by choosing a different polymer B or a different polymer C If the weight ratios are imposed in advance, for example, for reasons of cost or of certain properties, cg., the level of moisture absorption or shrinkage, then the optimum toughness can be obtained by selecting an 0 appropriate polymer combination for operation at a given temperature; for example, A1/C1 at one temperature and A2/C2 at another temperature.
Tbe process selection can involve, ~g., the selection of equipment, saew design, operating temperature, and shear. A twin-screw extruder preferably will be used in this process. However, it has been found 5 that whatever other process parameters are employed, the toughness of the final blcnd is primarily depcndent on the melt viscosity ratio of polymer A to polymer C The tempcrature is selected according to tbe melting temperature of the polyamide selected and the lowest temperature at which any one of the polymers decomposes. ln practice, the temperature range 20 will be about 180-300DC. In general, the larger the extruder the smaller is the shear. For a given machine, the higber is the speed of rotation of the screw (revolutions per rni~ute) tbe higber is the shear. Shear also is affected by tbe screw design, the milder the severity of tbe screw, the smaller tbe shear. It has been deterrnined experimentally, keeping in mind the above 25 three factors, that the average sbear experienced by polymers under a variety of conditions and equipment design is about 100 to 555 sec~l.
However, for practical purposes, it is sufficient to establish the process conditions for a fixed sbear rate, say, 100 1 sec.
This invention i~ now illustrated by representative examples of 3 o certain representative embodiments thereof, where all parts, proportions and percentages are by weigbt unless otherwise indicated. In all the examples, the melt viscosities were determined at a shear rate of 104 sec-l.
SUBSTITUTE SHEET
WO 93/0g183 2 1 2 3 0 8 0 Pcr/uss2/o934o POLYMERS
Po~amides (Po~merA) A~ - Nylon 66 witb an RV of about 50-55 A2 - Nylon 66witb an RV of about 40 13 A3 - Nylon 6 witb an RV of 58-62.
Al and A2 were commercial resins sold by E. I. du Pont de Nemours and Company under tbe trademark ZYTEL~ . Tbe nylon 6 resin 0 A3 is sold by NYLON de MEXICO, S.A. under tbe trademark Dl)RAM~A~ 6-Compa~bil~ing Rllbbery Po~mers (Po~merBJ
BI - Styrene/etbylcne-butylene/styrene copolymer grafted witb about 2% of maleic anbydride, sold by Sbell Company under tbe trademark KRATON~9 FG 1901X.
B2 - EPDM rubber containing about Q12% of copolymerized ~; norbornadiene, grafted with a monomer providing about 13~o of succinic anhydride groups (maldc anhydride, maleic acid, or fumaric acid).
B3 - EPDM rubber containing about 0.12% of copolymerized norbornadiene and grafted with a monomer providing about 2gb of succinic anhydride groups.
Both B2 and B3 were commercial products of E. I. du Pont de Nemours and Company but B3 had a slightly l~wer mole~ular weight than B2.
B4 was a commercial EPDM rubber of E. I. du Pont de Nemours and Company containing 0.12~o of norbornadiene but no succininc anhydride groups.
It is to be noted that, generally speaking, many compatibilizing rubbe~y polymers satisfying the requirements of Polymer B have been used in the past as toughening agents for a variety of engineering resins.
Crysta~line Po~ole~n (Po~rner CJ
C1 - C3 Homopolymers of propylene, with molecular weights increasing from C1 to C3, sold by HIMONT CO. under the trademark PROFAX~
with respective commercial designations 6231, 6323, and 6723.
SUBSTITUTE SHEET
wo 93/09183 PCr/USg2/09340 21230~ 12 C4 - Copolymer of propylene with ethylene, sold by HIMONT CO. under the trademark PROFAX~3) 6823. Tbe molecular weight of C4 was about tbe same as that ~f C3.
Additional compahbi~zingpo.~yma (Po~merD) s D1 - Homopolyrner of propylene grafted witb about 0.8% of maleic anbydride, witb a lecular wcight about tbe same as C2. Sold by DU PONT CANADA u~der the trademark FIJSABOND~ -Extruders MI - Werner & Pfleiderer (W&P), twin-screw, about 28 mm diameter.
10 Trilobal mixing screws with five heatinB zones and a vacuum port at the end.
M2 - W&P, twin-screw, about 30 mm diameter. Bilobal mixing screws with four heating zoncs and a vacuum port at the end.
M3 - Similar to M1, except tbat tbe screw configuration is about twice as severe.
15 M4 - twin-screw "ZSK" W~P, about 53 mm diameter. Trilobal rnixing screws ~nth nine heating zones and a vacuum port at tbe end.
All polymers were dry-mLl~ed as pellets before feeding to the extruder. The total amount of material in extruders M1 through M3 was 20 about 2-3 kg. Tbe amount in M4 was about 200 kg. Eacb composition was extruded as a strand, which was pelletized and then injection-molded into test samples. In all extruders, the temperatures in all zones were set at the same level, about 2~25 C lower than the melt processing temperature because additional beat was supplied by shearing.
25 Molding Condi~ions All the extruded pellets were dried overnight at 9~ C. They were injection molded in a nominal 6-ounce (177 ml) machine made by HMP Company running at a cycle ratio of 20/20 (seconds/seconds). The processing temperature for nylon 66 was set at 260 C and for nylon 6 at 30 240C for all four zones. The actual melting temperature of eacb type of nylon was about 20 C higher than the set temperature. The mold temperature was about 4~60~ C. The molding specimens were 03175 cm thick and were either flex bar ~pe (1.27x11.43 cm) or dog bone ~pe (1.27x21.6 cm).
- ~ 3 5 ':
SUBSTITUTE SHEET
WO 93/09183 2 1 2 3 0 8 0 Pcr~us92/o934o Testing Condihons (a) Melt viscosity was determined in a KAYNESS capillary rheometer according to ASTM D-3835-79 at a 104 sec~l shear rate.
(b) Flex modulus was determined according to ASTM D-790.
s (c) Notched Izod impact strength was determined according to ASTM D-256.
(d~ Tensile strengtb and elongation at break were determined according to ASTM D-638.
The above determinations (b) through (d) were made on samples dry as molded.
In Examples 1-36, polymer B always was B2.
E~ples 1-11 These examples show that for a given polymer B and a given weight ratio of polymers A, B, and C the optimum notched Izod value was obtained for a certain A/C MVR measured at the processing temperature.
For the particular polymer B and a given weight ratio (85/10/5), the flex modulus range was 1689 to 2068 MPa Table 1, below, summarizes the operating conditions and the test results. It can be seen that the optimum no~ched Izod value (larger than 535 J/m) was obtained within the A/C
MVR range of 0.17-1. A plot of impact strength vs. melt viscosity ratio is shown in Fig. 1, which is self-explanatory.
SUBSTITUTE SHEET
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o ~., _ ~ C~ ~ ;~~ ``I _ ~e e ~ ~ ~ V ~ ~", Amended Page Sa~ 3~ T, WO 93/09183 2 12 3 0 8 0 rCr/US92/Os340 E~ampl~s 12-19 These examples illustrate the same principle as shown above, except that the A/B/C rado was 80/10/10. Here, the optimum notched Izod value was obtained at an A/C MVR of 0.28-0.9. The flex modulus s range in this series of experiments was 1517-1793 MPa A plot of impact strength vs. melt viscosity ratio is shown in Fig. 2., while experimental data ~ are provided in Table 2, below.
:
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~ ,_ X ~ _ o ~ o 1--~ r ) ~ ~ C _ _ . ~ ~ ~`J :~ o ~.
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~mended Page S~5~3~' ;J . ~
WO g3/09183 PCr/US92/09340 17 ` i, ~xamples 20-25 In this series of experiments, tbe A/B/C ratio was 75/10/15.
The optimum notcbed Izod value was obtained within tbe A/C MVR range of 0.28-0.8, as sbown in Table 3, below, and in Fig. 3. Tbe flex modulus 5 values in tbese experiments were witbin the range of 1448-lS86 MPa.
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SUBSTITUTE SHEET
21~83080 ' `~
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Arnended Page wo 93/0~183 ~12 3~8~ Pcr/us92/os34o , .
E~mples 2~32 Tbc same principlc is here illustrated for blends in whicb tbe A/B/C ratio was 70/10/20. Tbe optimum notched Izod ~mpact streDgth was obtained for the A/C MVR range of 0.45-O.SQ. It is believed that 5 supertough compositions would be obtained within a range of about OAO-Q6Q, altbougb experiments supportiDg tbis full range bave not been run;
''l~be experimental results are presented in table 4, below and further illustrated in Fig. 4. '''Thc range of flex modulus values for these experimentswas 1413-1586 MPa t ~
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212~U80 1-'`, ~o _ ~ ~-- o o 8 ~
~ ~ o -_ .~ ~ ~ oo o .
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~mended Page Examples 33-36 Similar experiments were carried out with blends having an A/B/C ra~io of 60/10/30. Optimum notched Izod values were obtained for an A/C M~ range of 0.40-0.54, which can be further extrapolated to 0.~0-0.60. The fle.Y moduius values were within the range of 1?41-1379 MPa.
The experimemal results are presented in Table j, and a plot of notched kod unpacl slrength vs. A/C MVR is shown in Fig. S.
TABLE j Exam~le _ 33*_ 34 3~ 36 Polymer A A3 A3 A3 A3 Polymer C C3 C2 C~ C1 Extruder M1 M1 ~1 ~11 Exlr. temp. C 290 ~90 310 290 Melt visc.... Pa.sec of A 60 60 i0 60 of B 5j0 1~0 80 110 A/C MVR 0.11 0.40 0.~0 0.
Notched Izod, J/m 320 1067 101~ 961 ~`~ Fle~c mod.. MPa 1379 1310 1241 13~9 2 o *Comparative Examples ~7- ?~
These e:camples show that for a given AIB/C weight ratio, in this case, 80/10/10, and for given A and C, the value of notched Izod impac strength may depend on the Mn Of B. If A/C ~IVR is in the optimum range.
2 5 subslitution of B3 for B~ will affect that value or~ly slightly . bul when A/C
MVR is outside the optimum range, the change of the notched I~od value can be dramatic. Table 6 summanzes the operating conditions and the resul~s.
As can be seen. in each pair of e~cperiments, ~e sa~ne A and 3 o the same C were used, but B was either B3 or B2. In Examples 37 and 38, A/C MVR was 0.45, which is in the optimum range (see Fig. ~. Therefore~
the substitution of B2 for B3 did not significantly affect the notched Izod value, and both blends were supertough. In each one of Examples 39 and 40, run at different temperanlres, A/C MVR was outside the optimum 3 5 range, n~mely, 0.17 and 0~20~ ~he blends were not superlough in either caset although there was an improvement of the notched Izod value when B2 was substiluted for B3. Exarnples 40 and 41 also were run at differem Amended P2ge 53~ rT~
WO g3/09183 PCr/US92/09340 21~309 D 22 temperatures, so that A/C MVR was different in each case but in the optimum range. Substitudon of B2 for B3 had virtually no effect on the notched Izod value.
SUBSTITUTE SHEI~T
~t ~ ~ ~~ o X~ ~ ~ ~
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212~080 Examples 43-~6 These examples show the effect of the che~ical struclure and amount of Polymer B. Increasing the amount of B also increases the impact strength. but this also decreases the flex modulus. Further, replacing B2 s with B1 decreases the impact strenglh. ~hese results are summar~zed in Table 7, below.
Eram~le 43 . 44_ 1 j 46*
Polymer A A3 A3 A3 A3 Polymer B B2 B2 B1 B1 Polymer C C~ C3 C3 C~
AmouMofPolymerB, % 10 15 1' 10 Amountof PolymerC~ % 10 10 10 10 E.~truder M? M? ~I? M~
Extr. temp., C ?60 260 160 ~60 Extr. revimin 110 110 110 1 0 ~lelt visc., Pa.sec of A 1?0 1?0 1'70 1?0 of C 600 600 600 ~?0 AIC MVR 0.~ 0.~ 0.~ 0.55 Notched Izod, Jim 534 106~ 694 182 Fle~cmod., MPa 1586 1379 1~48 165 Tens. str.~ MPa ~0 45 50 .~9 E~g, at br ~ % 90 180 170 85 2 5 *Comparative It is to be noled that an AJC MRV of 0.2 is rlot in the optimum range for a B2 level of 10% (Example 43, Fig. ~), while it is in the ~; ~ optimum range for a B~ level of 1 j ~ ~Example 44, Fig. 3). Substitution of B1 for B2 results in a significant lowering of the notched kod value. Ihis 3 0 sugges~s that B1 is a less effecdve toughening agent than B2, and that when it is used, the optimum A/C M~R range is narrower than whe~ B2 is used.
Essentially, what this means is that the absolute value of notched kod impact strength will depend on the chemical s~ucture of Polymer B, but the highest value will be obtained for each Polymer B when the value of A/C
3 5 MVR is in the optimum range, which can be determined independently.
Amended Page ~
WO 93/09183 212 3 0 8 o Pcr/usg2/o934o E~u72pl~s 47-S2 These cxamples are intendcd to show tbe relative unimportancc under tbe optimum conditions of tempcrature, sbear rate, or c~nruder scrcw scvcrity. Tbe expcrimcntal data and rcsults are presented in s Tablc 8, below. Tbe A/B/C ratio in all tbesc cxamplcs was 70/10/20. A
was A3; B was B2; and C was C2. It can be scen from Exunples 47-48 and S1-52 that when A/C MVR was maintaincd in tbe optimum rangc (see Fig.
PROOE~SS FOR MAK~G POLYAMIDE/POLYOL~F1N BLENDS
BkCKGROUND OF THE INVENTION
s This invention relates to a process for preparing polyamide/polyolefin blends having superior toughness and stiffness compared with currently available blends of such polymers.
Polyamide resins (or polyamides) are well known in the art and have been used for many years, La, as engineering or molding resins, fiber-forming resins, and barrier resins in packaging materials. Crystalline polyamides, especially those made from sbort ch~in monomers, e.B., nylon 6 and nylon 66, are very stiff, which is desirable for molding resins, but tbey are sensitive to moisture. Addition of crystalline polyolefins, such as polyetbylene or polypropylene reduces moisture sensitivity but suffers from incompatibilitybetween tbese two polymers, so tbat acceptable end-use blends are not made. Further, although polyamides have good physical properties, such as tensile strength and flexural (or flex) modulus, thac make these resins suitable for fabricating a variety of articles, they are not conside~ed tough. Their notched Izod impact strength either is too low under ordinary test conditioDs or decreases significantlywith a modest change of temperature, thickness, orientadon, or notch radius. It, tberefore, is convendonal in the industry to toughen polyamide resins by blending them wi~ soft, rubbery polymers which can absorb mechanical shocks without significantly impainng the tensile properties of the polyamides with which 2s they are blended. However, because those soft polymers normally have very low s~ess (or flex moduli), addition of such polymers to thermoplastic resins normally results in blends that have lower flex moduli than the matrix resins alone, so tbat improvement of one property is accomplisbed at tbe sacrifice of ~e otber.
3 o ~ While there is abundant art describing such blends, the most pertinent patent in tbis area is U.S. 4,174,358, to Epstein, describing blends of polyamides witb ~r~ous types of tougber~ng polymers. Tbe Epstein invention invol~es a process for tbe preparation of multiph~se thermoplastic compositions comprising admLYing a defined polyamide matrix resin with at least one of a number of possible polymers having a much lower tensile SUBSrITUTE SHEET
WO g3/09183 Pcr/us92/os34o modulus and containing sites which are adherent to the matrix resin, and then shearing to disperse the polymer in the matrix resin to a particle size of 0.01 to 3 microns, so that the polymer adheres to the matr~x resin.
According to the patent specification and certain examples, tbe blend may be eitber binary or ternary. A ternary blend contains the matrix resin, a soft~
adherent polymer, and a third soft polymcr, which may or may not possess adberent sites; when it does not, it is a straight chain or brancbed polyethylene. Such blends can be made in one step, or the soft polymers can be preblended and tben re-extruded with the matrix resin. Additional compositions of this type are described in Japanese Patent Publications (Kokai) 59-78256 and 59-149940 (both 1984) of Mitsui Petrocbemical Industries, Ltd.
U.S. Patent 4,780,505 to Mashita et al. describes a process where polypropylene grafted with maleic anhydride is added to a 1~ polyamide/polypropylene blend to improve the compatibility of the blend.
This graftcd po~ymer can bc rcplaccd by or added together with another polymcr, such as a rubber grafted with maleic anhydridc or an ethylene copolymer containing a maleic anhydrido or glycidyl methacrylate comonomer.
A reccnt paper by Modic et al. in Plast~s Eng~neer~ng, luly 1991, pp. 37-39, describes blends of nylon 66with polypropylene and of nylon 6 with polypropylene, both witb a compatibilizer - styrenic block copolymer functionalized witb maldc anbydride - which bave high impact strength. The paper discusses mainly tbe situadon where polypropylene becomes tbe matrix and nylon the dispersed phase, although tbe possibility of phase illversion in tbe case of a large nylon/polypropylene rado is mendoned.
It thus is known that one can make ternary blends with desirable mechanical properties by properly selecting the component polymers A, B, and C in optimum ratios and blending them under suitable condidons. Ternary blends, when properly made, can pravide a more desirable balance of properties than binary blends; yet, in practice these terms 'properly", "optimum" and "suitable" are very broad and undefined.
Even for skilled plastics engineers and chemists, this is a rather occult art, 3s which requires a great deal of experimentadon before a satisfactory : ~ SUBSTITUTE SHEET
, ~ ~
W O 93/09183 ~ Z 1 ~ 3 0 8 0 PC~r/US92/09340 composition is obtained. Normally, the matrix polymer A is preselected according to the business need; the two otber components B and C are then varied, either with respect to their characteristics or amounts, or both, and one or more plots or tables reflecting the changes of desired properties with 5 changing compositions are made. Usually, those plots or tables show a trend of either increasing or decreasing property values as tbe compositions are varied. When the desired properties have been obtained, the operation is considered successful, and the blend is adopted for commercial purposes. In some cases, with a particular matrix resin, the experimenter may find that o the desired properties are difficult or impossible to obtain; the experimenterthen has the choice of making do with what he or she has or replacing the matrix resin with another matrix resin and repeating the series of experiments. By following the directives of the Epstein patent, one can in some cases obtain "supertough" nylon resiDs, which for the purpose of the 15 present invention means tbat tbeir notched Izod value is at least 10 ft.-lb/inch (about 534 J/m).
C~ystalline polyolefiDs such as, for example, polyethylene, pohJpropylene, and polyisobutylene are often considered suitable polymers for blending witb polyamides because they improve the polyamide toughness 20 while reducing the stiffness of polyamides to a lesser degree than do amorpbous and rubbery polyolefins. However, binary blends of polyamides with crystalline polyolefins do not show greatly improved toughness.
Addition of a tbird component, or compatibili~er, permits a more thorough blending, resulting in a better dispersion, so that the resulting blend has 25 considerably improved toughness. While tbis is known, the proper choice of the blend components as well as of the blending conditions still is to a large exten~ left to the experimenter who, after a number of trial runs, arrives at a satisfactory composition ~nd process.
Generally speaking, it is very difflcult to prepare a supertough polyamide with high stiffness or to even predict under what conditions or with what components such a composition could be made.
It is, therefore, highly desirable to be able to select in advance compatibilizer B for a given crystalline polyolefin C to be blended with matrix polyamide A under predetenTlined blending conditions in order to 3 5 obtain the maximum degree of improvement of notched Izod impact SUBSTITUTE SHEET
strength for a given flex modulus (which can be calculated in advance from the aex modhli of the components), and to obtain in fact such improvement with a minimum amount of experimentation.
SUM~L~RY OF THE INVENTION
Accord~g to the present invention, there is now provided a process for melt-blendLng at a shear rate of aboul 100-200 sec~1 at least one polyamide A havm~ a number average molecular weiahl, Mn Of abou~
5,000-35,000 with a crystalline polyolefin C incompatible with polyamide A, having a number average molecular weight, Mn~, of aboul 10,000-1,000,000 in the presence of a compatibilizing rubbery polymer B having a ,lass transition temperature, Tg, of at most -~0C and capable of chemically or physically associating with both polyamide A and crystalline polyolefin C~
~he ratio of melt viscosity of polyamide A. M~ o melt viscosi~v of polyolefin C, MVC, at the process temperature and at the same shear rate Wilhi~l the range o~ about 100-~00 sec~l being aboul 0.37-0.8~ and especially 0.4-0.8, to form a multiphase blend haviila a notched Izod impact stren~th of more than 535 J/m;
said process comprising melt-blendin~ polymers B and C with - polyamide A Ln their respecùve weight perceMages b%~ c%, and a% such that (1) a + b +c = 100;
) b = 3 to 15;
(3) b + c > 10;
(4) 1:1 < a/c <20:1; and ~: 25 (S) 1:5 < b/c < 3:1, at a process temperature which is higher than the hi~hest melting temperature of a~y crystallLne polymer present and higher than the highest glass transition temperature of anX amorphous polymer present but lower than the lowest temperature at which a~y poly~ner begins to si~nificantly 3 0 degrade, under residence time and mixing energy conditions such that polyamide A forms a conti~uous phase, while polymers B and C form a particulate phase dispersed in the continuous phase.
BRrEF DESCl~ION OF IHE DRAVV~iGS
Figs. 1 through 5 represent plots of notched Izod impacl 3 5 strength vs. melt viscosity ratio at a 104 sec~l shear rate for represerltative ,, Amended Page ,, ~
wo 93/09183 2 1 2 3 0 8 0 PCr/USg2/Og340 multiphase blends of polyamide/maleic group-containing compatibilizing rubbcry polymcr/polypropylene. In all these graphs, the ordinate represents notched Izod impact strengtb in J/rn, wbile the abscissa represents tbe melt viscosity ratio of polyamide A to crystalline polyolefin C.
DET~ILED DESCRIPIlON OF THE INVENTION
Definition: For the purpose of the present disclosurc and claims, tbe tenns "associating" and "association" include botb a chemical and a physical interaction, including, for cxample, a chemical reaction, cspecially grafting, hydrogen bonding, and ionic bonding; as well as electrostadc attracdon, and magnetic attraction. Associadon of two polymers is facilitated by, or necessarily requires, a low interfacial tension between them.
A compadbiLizing polymer normally would have an aliphatic chain, which would make it compatible with polyolefins, and at least one polar functional group, which would make it compatible with polyamides.
Typical such functional groups include, cg., carbonyl-containing groups such as carboxyl, ionic carbo~late, ester, and ketone; hydroxyl, thione, amine, and amide. ln order to determine whether a prospective compatibilizing polymer B is suitable for the proposed application, one only needs to pcrform two experiments, namely, prcparc under the proposed process conditions a blend of polymer B with polyan~ide A and a blcnd of polymer B
with crystalline polyolefin C in the desired ratios and determine the notched Izod strength of each such resulting blend. If the notched Izod ~alue of the first blend is higher than the notched Izod value of the corresponding 2s polyamide, and the notched Izod value of the second blend is higher than that of the polyolefin, then the selected polymer B is a suitable compatibili~ng agent.
Proper blending conditions will depend on tbe particular needs. The components always are blended in the melt, either in one step or 3 o in two steps (by first preblending polymers B and C and then blending the resulting material with polyrner A), so long as blending in the presence of polymer A is conducted witb sufficient energy to produce uniform dispersion, preferably ha~ng dispersed particles of small size, for example, 3 micrometers or less. Preblending B ~nth A is generally not recommended 3s because these two polymers may react chemically or crosslink to the point of :
SUBSrITUTE SHEET
wo 93/09183 Pcr/uss2/os340 ~1~3q~0 6 becoming difficult or impossible to melt process, or tbeir viscosity may becomc so high that a uniform dispersion of B and C ~n A cannot be obtained. Blending in a twin-screw extruder has been found to produce consistently satisfactory and reproducible results but other blending 5 equipment may provide equally acceptable results. Sucb otber equipment includes, for example, Buss Kneader. Blending is carried out at a temperature at which all thc blend components are molten but not so high that any of them would begin to degrade. The blend polymers sbould not be suscepdble of crosslinking under the blending conditions but should remain 10 thermoplastic.
Typical matrix polyamides can be bighly or partly crystalline or amorphous, or can themselves be blends of crystalline and amorphous polymers. They can be made by condensation of substantially equimolar amounts of a saturated aliphadc, aromadc, or cycloaliphatic dicarboxylic 15 acid having 4-12 carbon atoms witb a primary or secondary aliphadc or ~ycloaliphadc diamine having 4-12 carbon atoms. Representadve dicarbodcylic acids include succinic, adipic, azelaic, sebacic, 1,12-dodecanoic,1,4g~clohexanedicarbadtylic, terephthalic, and isophthalic. Representative diamines indude tetramethylenediamine, pentamethylenediamine, 20 hexamethylenediamine, dodecamethylenediamine, and 1,4-cyclohexanediamine. Otber suitable polyam;ides can be made by homopolymerization, with ring opening, of lactams ha~nng from S to 13 ring atoms. Representative lactams include d-valerolactam, e-caprolactam, w-laurolactam, etc. Suitable polyamides also include polyamides made by 25 polycondensation of two or more components of the same type, such as, for exa~mple, two different dicarboxylic acids with one diamine, or two different diamines witb one dicarboxylic acid, or one diamine, one dicarboxylic acid, and one lactam, or a polyamide in wbicb a portion of the dicarboxylic acid is terephtbalic acid and another portion is isophthalic acid, etc. Preferably, the 3 o polya nides, if they are crystalline, should have a melting point in excess of 160 C. lt is further preferred that tbe polyamides have a relative viscosity, detenI~ined in 90% aqueous formic acid, of about 20-300. Especially preferred polyamides include, for example, poly(hexamethylene adipamide) or nylon 66, poly(e~aprolactam) or nylon 6, poly(bexamethylene 35 terephthalamide), nylon 12 and nylon 12,12~ Compatible blends of two or SUBSTITUTE SHEET
WO 93/09183 PCI/US92/Og340 2i2~080 7 ~r ~
more polyamides may be used, instead of a single polyamide, to form the matrix component of the blend. A satisfactory polyamide will have a notched Izod impact strength of more than 166 J/m and a ~ex modulus of more than 1380 MPa, but a more desirable polyamide will have a notched s Izod value of more than 330 J/m and a flex modulus of more than 1170 MPa The best polyarnides in this more desirable category will have a notched Izod value of more than about 555 J/m.
Typical crystalline polyolefins include both homopolymers and random or block copolymers, having a flexural modulus of more than about 10 345 MPa Suitable crystalline polyolefins indude, ~g., high density and low density, random and linear polyethylene; syndiotactic and isotactic polypropylene, poly(butene-1), poly(isobutene), poly(2-methylpentene-1), and poly(hexene-1). ~ystalline polyolefins incompatible with matrix polymer A do not have functional groups capable of reacting or associating 15 witb polymer A. For economic reasons, tbe most preferred crystalline polyolefin, having higb ae~mral modulus and high beat distortion temperature, is isotactic polypropylene, wbicb is readily available at a modest price, comparable to that of high density polyethylene.
Suitable compatibilizing polymers are normally known as soft 20 polymers; that is, they have a low aexural modulus. Usually, they have predorninant amorphous portions. Many of those polymers have been conventionally used in the prior art for tougbening polyamides. Suitable compatibilizing polymers include, for example, etbylene copolymers with alkyl acrylates and methacrylates sucb as ethylene/ethyl acrylate and 2s ethylene/me~yl methacrylate copolymers; ethylene terpalymers with aL~cyl acrylates or methacrylates and carbon mono~de such as ethylene/CO/n-butyl ac~ylate, ethylene/CO/methyl methacIylate, and ethylene/~)/ethyl acrylate terpolyrners; ethylene copolymers with an epoxy group-containing monomer and, optionally, a third monomer such as, ~g~, 3 o ethylene/vinyl acetate/glycidyl methacrylate and ethylene/n-butyl acrylate/glycidyl methacrylate terpolymers; styrene/ethylene-butylene/
styrene block copolymers containing either a carboxylic group or an e~oxy gro~lp; partially ionized copolymers of ethylene with an a,b-unsaturated carboxylic acid and optionally with a third comonomer, including 35 ethylene/acrylic acid, ethylene/mëtkac~ylic acid, ethylene/vinyl SUBSTITUTE SHEET
acetate/acrylic acid, ethylene/buryl acryla~e/methacrylic acid, and ethylene!vinyl acetate/monomethyl ester of maleic acid copolymers, each neutralized in part with zinc, magnesium, calcium, sodium, potassium, or lithiurn ions; anhydride group-containing polymers such as, for example, 5 EPDM elastomers having maleic anhydride or glycidyl me~hacrylate arafted thereon such as ethylene/propylene/1,4-hexadiene elaslomer or ethylene/propylenell,4-hexadiene/norbornene elastomer orafted with maleic anhydride, styrene/ethylene-butylene/slyrene block copolymers grafted with maleic anhydride or glycidyl methacrylale, and terpolymers of 10 ethylene with maleic anhydride and another monomer such as ethylene/vinyl acetate/maleic anhydride terpolymer. Preferred compatibilizing polymers are etnylene copolymers havina pendant anhydride or glycidyl groups or both. The most pret`erred compalibilizing polvmer B is an EPDM elastomer having at least one of maleic anhydride and ~lycidyl 15 methacrylate moie~ies grafted thereon, each in an arnoum of about 0.2-?%
; ~; of the total elastomer weight~ When polymer ~ is nylon 6 or nylon 66. andcrystalline polyolefin C is polypropylene, Ihe following relationship preferably should e~tist:
3 < b/c < 3:1 20 and the preferred amoun~ of this compalibilizing polymer is 5-1j% of the blend.
he preferred weight percentage of polvamide A is at least SO%, especially at least 60%. Within these ranges, supertough blends can be obtained within rather wide MV~A/MVc ratios, which ra~ios for the 2 5 purpose of ~he present disclosure will be sometimes represented below as A/C MVR. This is illustrated ~n Figs. 1 through S for blends of five compositions based on nylon 66 and nylon 6 (each as polyam~de A), polypropylene (polyolefin C), and a compatibilizing polymer, arl EPDM
mbber grafted with maleic anhydride (polymer B~. These figures~ based on 3 o experiments described in the examples below, represent plots of notched Izod impact strength (determ~ned according to AS~M standard O-256) vs.
A/C MVR. The respective weight percentages of A in those experiments were as follows:
. ~ ~
:
~ ~ ~ Amended Page :
S~ T
WO 93/09183 ~ 1 2 3 0 8 0 PCr/U~92/09~
A.~o B.% C.%
Fig. 1 85 10 5 Fig. 2 80 10 1 s Fig. 3 75 10 15 Fig. 4 70 10 20 Fig. 5 60 10 30 It can be seen from those graphs that for a constant axnount of 10 B component, while va~nng the amounts of A and C, the A/C MVR range ~,vithin which supertough blends can be obtained is wider for the compositions containing a larger ~nount of polyamide A. It is noted that the plot in Fig. 1 contains an irregularity in the A/C MVR region of about 035, which is believed to be fortuitous and not meaningful. However, a 15 rna~num usually is found, according to these plots, somewhere in the neighborhood of A/C MVR equal to abou~ 0.4. ~or different viscosi~
ratios, which would depend on a different selection of polyamide and polyolefîn, this ma~n num could be located elsewhere on the graph but could always bc determined with sufficient precision to be useful in evaluating 20 prospective resins. For practical purposes, one would ~ot have to make such determinations for more than one or two compositions per set of polymers because the location of the ma~num ~does not change significantly with the respecdve percentages of the compon~nts; it is the melt viscosity ratio that determines both the location of the maximum and the value of notched Izod 25 impact streng~h at that location. Accordingly, it is entirely feasible and prac tical to establish such plots in advance for future reference for a number of polyamides and polyolefins, using any desired compatibilizing polymer.
As will be shown below, this invention makes it possible to obtain, with small amounts of polyolefin in the blend, compositions that have 3 o highly improved toughness and bigh stiffness; while with larger amounts of polyolefin in the blend, compositions having toughness and stiffness properties comparable to those of toughened polyamides of the prior art can be ob~ained at a much lower cost.
Generally spealdng, the practice of this invention involves 35 both a material selection and a selection of process parameters. The SUBSTITUTE SHEET
wo 93/09183 PCr/USg2/Os340 2123~ lO
material selection involves the selection of polymers A, B, and C as well as of the molecular weight of each polymer. If the selection of all three polymers is imposed by cornmercial or other practical considerations, optimum toughness can be obtained for a specific weight ratio of those 5 polymers; but if the composition is not critical, then it is possible to also optimize the toughness, cg., by choosing a different polymer B or a different polymer C If the weight ratios are imposed in advance, for example, for reasons of cost or of certain properties, cg., the level of moisture absorption or shrinkage, then the optimum toughness can be obtained by selecting an 0 appropriate polymer combination for operation at a given temperature; for example, A1/C1 at one temperature and A2/C2 at another temperature.
Tbe process selection can involve, ~g., the selection of equipment, saew design, operating temperature, and shear. A twin-screw extruder preferably will be used in this process. However, it has been found 5 that whatever other process parameters are employed, the toughness of the final blcnd is primarily depcndent on the melt viscosity ratio of polymer A to polymer C The tempcrature is selected according to tbe melting temperature of the polyamide selected and the lowest temperature at which any one of the polymers decomposes. ln practice, the temperature range 20 will be about 180-300DC. In general, the larger the extruder the smaller is the shear. For a given machine, the higber is the speed of rotation of the screw (revolutions per rni~ute) tbe higber is the shear. Shear also is affected by tbe screw design, the milder the severity of tbe screw, the smaller tbe shear. It has been deterrnined experimentally, keeping in mind the above 25 three factors, that the average sbear experienced by polymers under a variety of conditions and equipment design is about 100 to 555 sec~l.
However, for practical purposes, it is sufficient to establish the process conditions for a fixed sbear rate, say, 100 1 sec.
This invention i~ now illustrated by representative examples of 3 o certain representative embodiments thereof, where all parts, proportions and percentages are by weigbt unless otherwise indicated. In all the examples, the melt viscosities were determined at a shear rate of 104 sec-l.
SUBSTITUTE SHEET
WO 93/0g183 2 1 2 3 0 8 0 Pcr/uss2/o934o POLYMERS
Po~amides (Po~merA) A~ - Nylon 66 witb an RV of about 50-55 A2 - Nylon 66witb an RV of about 40 13 A3 - Nylon 6 witb an RV of 58-62.
Al and A2 were commercial resins sold by E. I. du Pont de Nemours and Company under tbe trademark ZYTEL~ . Tbe nylon 6 resin 0 A3 is sold by NYLON de MEXICO, S.A. under tbe trademark Dl)RAM~A~ 6-Compa~bil~ing Rllbbery Po~mers (Po~merBJ
BI - Styrene/etbylcne-butylene/styrene copolymer grafted witb about 2% of maleic anbydride, sold by Sbell Company under tbe trademark KRATON~9 FG 1901X.
B2 - EPDM rubber containing about Q12% of copolymerized ~; norbornadiene, grafted with a monomer providing about 13~o of succinic anhydride groups (maldc anhydride, maleic acid, or fumaric acid).
B3 - EPDM rubber containing about 0.12% of copolymerized norbornadiene and grafted with a monomer providing about 2gb of succinic anhydride groups.
Both B2 and B3 were commercial products of E. I. du Pont de Nemours and Company but B3 had a slightly l~wer mole~ular weight than B2.
B4 was a commercial EPDM rubber of E. I. du Pont de Nemours and Company containing 0.12~o of norbornadiene but no succininc anhydride groups.
It is to be noted that, generally speaking, many compatibilizing rubbe~y polymers satisfying the requirements of Polymer B have been used in the past as toughening agents for a variety of engineering resins.
Crysta~line Po~ole~n (Po~rner CJ
C1 - C3 Homopolymers of propylene, with molecular weights increasing from C1 to C3, sold by HIMONT CO. under the trademark PROFAX~
with respective commercial designations 6231, 6323, and 6723.
SUBSTITUTE SHEET
wo 93/09183 PCr/USg2/09340 21230~ 12 C4 - Copolymer of propylene with ethylene, sold by HIMONT CO. under the trademark PROFAX~3) 6823. Tbe molecular weight of C4 was about tbe same as that ~f C3.
Additional compahbi~zingpo.~yma (Po~merD) s D1 - Homopolyrner of propylene grafted witb about 0.8% of maleic anbydride, witb a lecular wcight about tbe same as C2. Sold by DU PONT CANADA u~der the trademark FIJSABOND~ -Extruders MI - Werner & Pfleiderer (W&P), twin-screw, about 28 mm diameter.
10 Trilobal mixing screws with five heatinB zones and a vacuum port at the end.
M2 - W&P, twin-screw, about 30 mm diameter. Bilobal mixing screws with four heating zoncs and a vacuum port at the end.
M3 - Similar to M1, except tbat tbe screw configuration is about twice as severe.
15 M4 - twin-screw "ZSK" W~P, about 53 mm diameter. Trilobal rnixing screws ~nth nine heating zones and a vacuum port at tbe end.
All polymers were dry-mLl~ed as pellets before feeding to the extruder. The total amount of material in extruders M1 through M3 was 20 about 2-3 kg. Tbe amount in M4 was about 200 kg. Eacb composition was extruded as a strand, which was pelletized and then injection-molded into test samples. In all extruders, the temperatures in all zones were set at the same level, about 2~25 C lower than the melt processing temperature because additional beat was supplied by shearing.
25 Molding Condi~ions All the extruded pellets were dried overnight at 9~ C. They were injection molded in a nominal 6-ounce (177 ml) machine made by HMP Company running at a cycle ratio of 20/20 (seconds/seconds). The processing temperature for nylon 66 was set at 260 C and for nylon 6 at 30 240C for all four zones. The actual melting temperature of eacb type of nylon was about 20 C higher than the set temperature. The mold temperature was about 4~60~ C. The molding specimens were 03175 cm thick and were either flex bar ~pe (1.27x11.43 cm) or dog bone ~pe (1.27x21.6 cm).
- ~ 3 5 ':
SUBSTITUTE SHEET
WO 93/09183 2 1 2 3 0 8 0 Pcr~us92/o934o Testing Condihons (a) Melt viscosity was determined in a KAYNESS capillary rheometer according to ASTM D-3835-79 at a 104 sec~l shear rate.
(b) Flex modulus was determined according to ASTM D-790.
s (c) Notched Izod impact strength was determined according to ASTM D-256.
(d~ Tensile strengtb and elongation at break were determined according to ASTM D-638.
The above determinations (b) through (d) were made on samples dry as molded.
In Examples 1-36, polymer B always was B2.
E~ples 1-11 These examples show that for a given polymer B and a given weight ratio of polymers A, B, and C the optimum notched Izod value was obtained for a certain A/C MVR measured at the processing temperature.
For the particular polymer B and a given weight ratio (85/10/5), the flex modulus range was 1689 to 2068 MPa Table 1, below, summarizes the operating conditions and the test results. It can be seen that the optimum no~ched Izod value (larger than 535 J/m) was obtained within the A/C
MVR range of 0.17-1. A plot of impact strength vs. melt viscosity ratio is shown in Fig. 1, which is self-explanatory.
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o ~., _ ~ C~ ~ ;~~ ``I _ ~e e ~ ~ ~ V ~ ~", Amended Page Sa~ 3~ T, WO 93/09183 2 12 3 0 8 0 rCr/US92/Os340 E~ampl~s 12-19 These examples illustrate the same principle as shown above, except that the A/B/C rado was 80/10/10. Here, the optimum notched Izod value was obtained at an A/C MVR of 0.28-0.9. The flex modulus s range in this series of experiments was 1517-1793 MPa A plot of impact strength vs. melt viscosity ratio is shown in Fig. 2., while experimental data ~ are provided in Table 2, below.
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WO g3/09183 PCr/US92/09340 17 ` i, ~xamples 20-25 In this series of experiments, tbe A/B/C ratio was 75/10/15.
The optimum notcbed Izod value was obtained within tbe A/C MVR range of 0.28-0.8, as sbown in Table 3, below, and in Fig. 3. Tbe flex modulus 5 values in tbese experiments were witbin the range of 1448-lS86 MPa.
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E~mples 2~32 Tbc same principlc is here illustrated for blends in whicb tbe A/B/C ratio was 70/10/20. Tbe optimum notched Izod ~mpact streDgth was obtained for the A/C MVR range of 0.45-O.SQ. It is believed that 5 supertough compositions would be obtained within a range of about OAO-Q6Q, altbougb experiments supportiDg tbis full range bave not been run;
''l~be experimental results are presented in table 4, below and further illustrated in Fig. 4. '''Thc range of flex modulus values for these experimentswas 1413-1586 MPa t ~
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~mended Page Examples 33-36 Similar experiments were carried out with blends having an A/B/C ra~io of 60/10/30. Optimum notched Izod values were obtained for an A/C M~ range of 0.40-0.54, which can be further extrapolated to 0.~0-0.60. The fle.Y moduius values were within the range of 1?41-1379 MPa.
The experimemal results are presented in Table j, and a plot of notched kod unpacl slrength vs. A/C MVR is shown in Fig. S.
TABLE j Exam~le _ 33*_ 34 3~ 36 Polymer A A3 A3 A3 A3 Polymer C C3 C2 C~ C1 Extruder M1 M1 ~1 ~11 Exlr. temp. C 290 ~90 310 290 Melt visc.... Pa.sec of A 60 60 i0 60 of B 5j0 1~0 80 110 A/C MVR 0.11 0.40 0.~0 0.
Notched Izod, J/m 320 1067 101~ 961 ~`~ Fle~c mod.. MPa 1379 1310 1241 13~9 2 o *Comparative Examples ~7- ?~
These e:camples show that for a given AIB/C weight ratio, in this case, 80/10/10, and for given A and C, the value of notched Izod impac strength may depend on the Mn Of B. If A/C ~IVR is in the optimum range.
2 5 subslitution of B3 for B~ will affect that value or~ly slightly . bul when A/C
MVR is outside the optimum range, the change of the notched I~od value can be dramatic. Table 6 summanzes the operating conditions and the resul~s.
As can be seen. in each pair of e~cperiments, ~e sa~ne A and 3 o the same C were used, but B was either B3 or B2. In Examples 37 and 38, A/C MVR was 0.45, which is in the optimum range (see Fig. ~. Therefore~
the substitution of B2 for B3 did not significantly affect the notched Izod value, and both blends were supertough. In each one of Examples 39 and 40, run at different temperanlres, A/C MVR was outside the optimum 3 5 range, n~mely, 0.17 and 0~20~ ~he blends were not superlough in either caset although there was an improvement of the notched Izod value when B2 was substiluted for B3. Exarnples 40 and 41 also were run at differem Amended P2ge 53~ rT~
WO g3/09183 PCr/US92/09340 21~309 D 22 temperatures, so that A/C MVR was different in each case but in the optimum range. Substitudon of B2 for B3 had virtually no effect on the notched Izod value.
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212~080 Examples 43-~6 These examples show the effect of the che~ical struclure and amount of Polymer B. Increasing the amount of B also increases the impact strength. but this also decreases the flex modulus. Further, replacing B2 s with B1 decreases the impact strenglh. ~hese results are summar~zed in Table 7, below.
Eram~le 43 . 44_ 1 j 46*
Polymer A A3 A3 A3 A3 Polymer B B2 B2 B1 B1 Polymer C C~ C3 C3 C~
AmouMofPolymerB, % 10 15 1' 10 Amountof PolymerC~ % 10 10 10 10 E.~truder M? M? ~I? M~
Extr. temp., C ?60 260 160 ~60 Extr. revimin 110 110 110 1 0 ~lelt visc., Pa.sec of A 1?0 1?0 1'70 1?0 of C 600 600 600 ~?0 AIC MVR 0.~ 0.~ 0.~ 0.55 Notched Izod, Jim 534 106~ 694 182 Fle~cmod., MPa 1586 1379 1~48 165 Tens. str.~ MPa ~0 45 50 .~9 E~g, at br ~ % 90 180 170 85 2 5 *Comparative It is to be noled that an AJC MRV of 0.2 is rlot in the optimum range for a B2 level of 10% (Example 43, Fig. ~), while it is in the ~; ~ optimum range for a B~ level of 1 j ~ ~Example 44, Fig. 3). Substitution of B1 for B2 results in a significant lowering of the notched kod value. Ihis 3 0 sugges~s that B1 is a less effecdve toughening agent than B2, and that when it is used, the optimum A/C M~R range is narrower than whe~ B2 is used.
Essentially, what this means is that the absolute value of notched kod impact strength will depend on the chemical s~ucture of Polymer B, but the highest value will be obtained for each Polymer B when the value of A/C
3 5 MVR is in the optimum range, which can be determined independently.
Amended Page ~
WO 93/09183 212 3 0 8 o Pcr/usg2/o934o E~u72pl~s 47-S2 These cxamples are intendcd to show tbe relative unimportancc under tbe optimum conditions of tempcrature, sbear rate, or c~nruder scrcw scvcrity. Tbe expcrimcntal data and rcsults are presented in s Tablc 8, below. Tbe A/B/C ratio in all tbesc cxamplcs was 70/10/20. A
was A3; B was B2; and C was C2. It can be scen from Exunples 47-48 and S1-52 that when A/C MVR was maintaincd in tbe optimum rangc (see Fig.
4), a lSC increasc of temperature did not affcct the Izod valuc either for an extludcr with a scrcw of mild sevcrity or for one with a s~ew of higb 0 severity. Examples 4849 show tbat the Izod value also was unaffected by an incrcasc of revolutions pcr minute from 150 to 2S0. And, finally, Examples 49-51 show tbat this was true also for a change of screw design from mild to severe. In all these Examples, thc blends werc supertough.
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WO 93/Og183 ' 2 1 2 3 0 8 o Pcr/USg2/09340 E~lples 53-60 These examples demonstrate that production of supertough blends in an iDdustrial size macbine at industrial production rates can be readily achieved so long as A/C MVR is maintained witbin tbe optimum 5 range. In the normal course of development work, scale up of processes run in laboratory cquipment to industrial size equipment produces inconsistent or unreliable results; sometimes, the theory derived from laboratory work is proven wrong by large scale experiments. In the present case, howe~er, the laboratory scale results have been corroborated by large scale experiments.
o The experimental conditions and results are presented in Table 9, below.
Ex~mples 53 and 56 are control experiments. All experiments were run in a 53 mm extruder (M4) at a production rate of 9~140 kg/hr. When Polyrner B4 of Example 53 was replaced witb Polymer C3 in Example 54, tbe blend remained supertough at 25C. When the arnount of Polymer B2 was 5 inGreased from lO~o to 15% in Example 55, the blends remained supertougb both at 25C and at 0C F~ampbs 56 and 57 provide a comparison for a differcnt polyamide, and examples 58-60 provide data for selected blends of polyamides, each one with the same crystalline po~olefin C2 and the same oompa~bili~ng Polymer B2.
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`` 29 212 Examples 61-64 lhese examples show the importance of using a crystalline polyolef~ C that is incompatible with polyamide A. As long as this condition is satisfied, and as long as A/C MVR is ~n ~he optimum range, S supertough blends are obtained in the presence of compatibilizing Polymer B2. Howeveri when crystalline polyolefin C has fimctional groups such that it can react or associate with the polyamide, supertough blends are not obtained. It is known in the art that when maleic anhydride-grafted - polypropylene is blended with a polyamide, only modest improvemeM of notched Izod impact strength is obtained, from. say, initial 30 le maybe 110 J/m, irrespective of dle amount of such polypropylene. On the other hand~ a grafted elastomer of the type used in dlis inveMion as comp~tibilizing polymer B can improve ~he impact strenglh considerably, as also is known.
The present inventor believes that when un~rafted crystalline polyoletln C is 15 used, C and compadbilizing polymer B can folm a coreJshell strucn~re~ with C being the core and B the shell. The lar~,e core/shell particle interacts wilh nylon to improve the impact streng~h to a ~reater extent than the sum of ~he : ~ ~ small improvement possible with grafted polypropylene acting independeMly of B and the incremental improvemeM obtained with the smaller particle of 2 0 B. These results, although perhaps unexpected at first blush, are shown in Table 10, below. Here, C3 is ungrafted polypropylene, while Dl is polypropylene graRed with maleic anhydride, as explained above.
2 s E:;cample _ 61 62~ 63 64*
Polymer A1, % 80 80 85 85 PolymerB2, % 10 10 10 10 PolymerC3, ~ 10 0 5 0 Polymer D1 0 10 0 Extr. temp., C 280 280 280 280 Extr. rev/miD 140 110 140 110 Melt visc., Pa.sec of A 250 250 ~50 250 of C 560 -- j60 --3s of D1 --~ 5 - - 1~5 A/C MVR 0.45 ---- 0.45 ----Notched Iz~d, J/m 854 294 854 278 mended Page ~_~
S~
Fle,~c mod., MPa 1827 1620 2103 1793 Tens. scr., MPa 55 59 58 58 Elong. a~ br~ak. % 150 85 80 70 *Comparative nded ~age ~'
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WO 93/Og183 ' 2 1 2 3 0 8 o Pcr/USg2/09340 E~lples 53-60 These examples demonstrate that production of supertough blends in an iDdustrial size macbine at industrial production rates can be readily achieved so long as A/C MVR is maintained witbin tbe optimum 5 range. In the normal course of development work, scale up of processes run in laboratory cquipment to industrial size equipment produces inconsistent or unreliable results; sometimes, the theory derived from laboratory work is proven wrong by large scale experiments. In the present case, howe~er, the laboratory scale results have been corroborated by large scale experiments.
o The experimental conditions and results are presented in Table 9, below.
Ex~mples 53 and 56 are control experiments. All experiments were run in a 53 mm extruder (M4) at a production rate of 9~140 kg/hr. When Polyrner B4 of Example 53 was replaced witb Polymer C3 in Example 54, tbe blend remained supertough at 25C. When the arnount of Polymer B2 was 5 inGreased from lO~o to 15% in Example 55, the blends remained supertougb both at 25C and at 0C F~ampbs 56 and 57 provide a comparison for a differcnt polyamide, and examples 58-60 provide data for selected blends of polyamides, each one with the same crystalline po~olefin C2 and the same oompa~bili~ng Polymer B2.
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SUBSTITUTE SHEET
`` 29 212 Examples 61-64 lhese examples show the importance of using a crystalline polyolef~ C that is incompatible with polyamide A. As long as this condition is satisfied, and as long as A/C MVR is ~n ~he optimum range, S supertough blends are obtained in the presence of compatibilizing Polymer B2. Howeveri when crystalline polyolefin C has fimctional groups such that it can react or associate with the polyamide, supertough blends are not obtained. It is known in the art that when maleic anhydride-grafted - polypropylene is blended with a polyamide, only modest improvemeM of notched Izod impact strength is obtained, from. say, initial 30 le maybe 110 J/m, irrespective of dle amount of such polypropylene. On the other hand~ a grafted elastomer of the type used in dlis inveMion as comp~tibilizing polymer B can improve ~he impact strenglh considerably, as also is known.
The present inventor believes that when un~rafted crystalline polyoletln C is 15 used, C and compadbilizing polymer B can folm a coreJshell strucn~re~ with C being the core and B the shell. The lar~,e core/shell particle interacts wilh nylon to improve the impact streng~h to a ~reater extent than the sum of ~he : ~ ~ small improvement possible with grafted polypropylene acting independeMly of B and the incremental improvemeM obtained with the smaller particle of 2 0 B. These results, although perhaps unexpected at first blush, are shown in Table 10, below. Here, C3 is ungrafted polypropylene, while Dl is polypropylene graRed with maleic anhydride, as explained above.
2 s E:;cample _ 61 62~ 63 64*
Polymer A1, % 80 80 85 85 PolymerB2, % 10 10 10 10 PolymerC3, ~ 10 0 5 0 Polymer D1 0 10 0 Extr. temp., C 280 280 280 280 Extr. rev/miD 140 110 140 110 Melt visc., Pa.sec of A 250 250 ~50 250 of C 560 -- j60 --3s of D1 --~ 5 - - 1~5 A/C MVR 0.45 ---- 0.45 ----Notched Iz~d, J/m 854 294 854 278 mended Page ~_~
S~
Fle,~c mod., MPa 1827 1620 2103 1793 Tens. scr., MPa 55 59 58 58 Elong. a~ br~ak. % 150 85 80 70 *Comparative nded ~age ~'
Claims (8)
1. Process for melt-blending at a shear rate of about 100-200 sec-1 at least one polyamide A having a number average molecular weight, Mn, of about 5,000-35,000 with a crystalline polyolefin C lacking functional groups capable of reacting or associating with polyamide A and thus incompatible therewith, having a number average molecular weight, Mn', of 10,000-1,000,000 and a flexural modulus in excess of 345 MPa. in the presence of a rubbery polymer B having a glass transition temperature, Tg, of at most -20°C and capable of chemically or physically associating with both polyamide A and crystalline polyolefin C, the ratio of melt viscosity of polyamide A, MVA, to melt viscosity of polyolefin C, MVC, at the process temperature and at the same shear rate within the range of 100-200 sec-1, determined in a Kayness capillary rheometer according to ASTM D-3835-79, being about 0.37 to 0.8, to form a multiphase blend:
said process comprising melt-blending polymers B and C with polyamide A in their respective weight percentages b%, c%, and a% such that (1) a + b +c = 100:
(2) b = 3 to 15;
(3) b + c > 10;
(4) 1:1 < a/c <20:1; and (5) 1:5 < b/c < 3:1, at a process temperature which is higher than the highest melting temperature of any crystalline polymer present and higher than the highest glass transition temperature of any amorphous polymer present but lower than the lowest temperature at which any polymer begins to significantly degrade, the resulting blend comprising a continuous phase of polyamide A
and a particulate phase of polymers B and C dispersed in the continuous phase, said blend having a notched Izod impact strength of more than 535 J/m.
said process comprising melt-blending polymers B and C with polyamide A in their respective weight percentages b%, c%, and a% such that (1) a + b +c = 100:
(2) b = 3 to 15;
(3) b + c > 10;
(4) 1:1 < a/c <20:1; and (5) 1:5 < b/c < 3:1, at a process temperature which is higher than the highest melting temperature of any crystalline polymer present and higher than the highest glass transition temperature of any amorphous polymer present but lower than the lowest temperature at which any polymer begins to significantly degrade, the resulting blend comprising a continuous phase of polyamide A
and a particulate phase of polymers B and C dispersed in the continuous phase, said blend having a notched Izod impact strength of more than 535 J/m.
2. The process of Claim 1 wherein polyamide A is selected from the group consisting of nylon 6, nylon 66, nylon 12, nylon 12,12, and poly(hexamethylene terephthalamide). .
3. The process of Claim 1 wherein the crystalline polyolefin C
is selected from the group consisting of polyethylene, polypropylene, poly(butene-1), and poly(2-methylpentene-1).
is selected from the group consisting of polyethylene, polypropylene, poly(butene-1), and poly(2-methylpentene-1).
4. The process of Claim 1 wherein polymer B is an ethylene copolymer with at least one other ethylenically unsaturated comonomer and has pendant anhydride or glycidyl groups.
5. A process of Claim 1 carried out in a twin-screw extruder.
6. The process of Claim 8 wherein the weight proportion of polyamide A in the blend is at least 60%.
7. A polymer blend obtained by the process of any one of Claims 1-6.
8. A blend of Claim 7 wherein polyamide A is nylon 6 or nylon 66 present in an amount of 60 to less than 90%; polymer B is an EPDM elastomer grafted with at least one of maleic anhydride and glycidyl methacrylate, each being present in an amount of 0.2-2% of polymer B;
polyolefin C is polypropylene; and the amounts of B and C are such that 1:3 < b/c < 3:1.
polyolefin C is polypropylene; and the amounts of B and C are such that 1:3 < b/c < 3:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/789,685 US5234993A (en) | 1991-11-08 | 1991-11-08 | Process for making polyamide/polyolefin blends having superior improved toughness and stiffness |
| US07/789,685 | 1991-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2123080A1 true CA2123080A1 (en) | 1993-05-13 |
Family
ID=25148387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002123080A Abandoned CA2123080A1 (en) | 1991-11-08 | 1992-11-09 | Process for making polyamide/polyolefin blends having superior improved toughness and stiffness |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5234993A (en) |
| EP (1) | EP0611385A1 (en) |
| JP (1) | JPH07500860A (en) |
| CA (1) | CA2123080A1 (en) |
| WO (1) | WO1993009183A1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4131908C2 (en) * | 1991-09-25 | 1999-05-12 | Du Pont | Polyamide / polyolefin mixtures and their use |
| US5550192A (en) * | 1992-12-07 | 1996-08-27 | Lyondell Petrochemical Company | Dyeable polyolefin compositions and dyeing polyolefin compositions |
| US5468259A (en) * | 1992-12-07 | 1995-11-21 | Sheth; Paresh J. | Dyeable polyolefin compositions and dyeing polyolefin compositions |
| US5683818A (en) * | 1993-05-04 | 1997-11-04 | Kawasaki Chemical Holding Co., Inc. | Method for improving the friction and wear properties of a polyamide and polyproyplene blend |
| DE69511615T2 (en) * | 1994-05-20 | 1999-12-09 | Ube Industries | Polyamide matrix with resin composite material containing dispersed polyolefin grains |
| JP2766875B2 (en) * | 1995-04-10 | 1998-06-18 | 日本ピラー工業株式会社 | Shaft sealing system device |
| US5574105A (en) * | 1995-05-12 | 1996-11-12 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved high temperature performance |
| US5626939A (en) * | 1995-09-05 | 1997-05-06 | Georgia Tech | Synthetic wood from waste fibrous waste products |
| EP0803539A1 (en) * | 1996-04-22 | 1997-10-29 | Elf Atochem S.A. | Container comprising an external rigid envelope and an internal flexible pocket |
| US6646052B2 (en) | 1996-11-01 | 2003-11-11 | General Electric Company | Solid polymer dispersions and method for their preparation |
| JPH10182845A (en) * | 1996-11-01 | 1998-07-07 | General Electric Co <Ge> | Solid polymer dispersion and its production |
| US5936039A (en) * | 1997-11-10 | 1999-08-10 | Wang; Kang-Bo | Processes for producing thermoplastic elastomers having improved engineering performance |
| US6124406A (en) | 1998-03-31 | 2000-09-26 | The B. F. Goodrich Company | Blocky chlorinated polyolefins, process for making and use as impact modifier compatibilizer for PVC or CPVC |
| WO2000036011A1 (en) | 1998-12-17 | 2000-06-22 | Montell Technology Company B.V. | Polyolefin graft copolymer/polyamide blend |
| US6277915B1 (en) | 1999-09-29 | 2001-08-21 | Pmd Holdings Corporation | Block chlorinated polyolefins for use as impact modifier enhancers for PVC or CPVC |
| CZ291312B6 (en) * | 2001-02-09 | 2003-01-15 | Ústav Makromolekulární Chemie Av Čr | Composition based on a polyamide/polyisobutylene mixture and process for preparing thereof |
| US6685871B2 (en) * | 2001-05-15 | 2004-02-03 | Honeywell International Inc. | Toughened biaxially oriented film |
| US6670421B1 (en) | 2001-08-03 | 2003-12-30 | Aci Technologies, Llc | Olefin-polyamide thermoplastic alloy and process for making the same |
| FR2831239B1 (en) * | 2001-10-23 | 2004-01-23 | Alphacan Sa | MULTI-LAYERED PLASTIC TUBE FOR TRANSPORTING DRINKING WATER AND MANUFACTURING METHOD THEREOF |
| US20060280889A1 (en) * | 2005-06-10 | 2006-12-14 | Powell Steven M | Tubular nylon alloy members for tubing and hose constructions |
| JP4983135B2 (en) * | 2005-08-08 | 2012-07-25 | 三菱瓦斯化学株式会社 | Thermoplastic resin composition molded article with excellent barrier properties |
| EP1752492B1 (en) * | 2005-08-08 | 2009-09-02 | Mitsubishi Gas Chemical Company, Inc. | Fuel-barrier thermoplastic resin compositions and articles |
| CN100347242C (en) * | 2005-12-20 | 2007-11-07 | 吴觅修 | Highly fire-retardant polymer PA/PP alloy |
| KR101063227B1 (en) * | 2009-10-12 | 2011-09-07 | 현대자동차주식회사 | Nylon-4 Composite Composition |
| KR101741934B1 (en) | 2012-12-20 | 2017-05-30 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Process for preparing dynamically vulcanized alloys |
| US20180177254A1 (en) * | 2016-12-22 | 2018-06-28 | Russell Neuman | Method of extruding a thermoplastic polymer to produce random coloration and a product using same |
| US11332615B2 (en) * | 2017-05-26 | 2022-05-17 | Basf Se | Core/shell ternary blend and preparation thereof |
| CN112430391A (en) * | 2020-11-23 | 2021-03-02 | 山东星达新材料有限公司 | Super-tough super-low temperature-resistant super-wear-resistant flexible nylon alloy material and preparation method thereof |
| CN112646364A (en) * | 2020-12-18 | 2021-04-13 | 意得凯(深圳)科技有限责任公司 | High-elasticity transparent mirror frame material |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174358A (en) * | 1975-05-23 | 1979-11-13 | E. I. Du Pont De Nemours And Company | Tough thermoplastic nylon compositions |
| US4338413A (en) * | 1980-10-16 | 1982-07-06 | Monsanto Company | Polymer blends |
| JPS5978256A (en) * | 1982-10-27 | 1984-05-07 | Mitsui Petrochem Ind Ltd | Polyamide composition and production thereof |
| JPS59122546A (en) * | 1982-12-28 | 1984-07-16 | Mitsui Petrochem Ind Ltd | Polyamide composition |
| JPS59126462A (en) * | 1983-01-11 | 1984-07-21 | Mitsui Petrochem Ind Ltd | Polyamide composition |
| JPS59131648A (en) * | 1983-01-19 | 1984-07-28 | Mitsui Petrochem Ind Ltd | Polyamide composition |
| JPS59149940A (en) * | 1983-02-16 | 1984-08-28 | Mitsui Petrochem Ind Ltd | Propylene polymer composition |
| JPH0618953B2 (en) * | 1984-09-05 | 1994-03-16 | 住友化学工業株式会社 | Thermoplastic resin composition |
| US5006601A (en) * | 1986-09-25 | 1991-04-09 | Shell Oil Company | Impact resistant blends of thermoplastic polyamides, polyolefins and elastomers |
| JPS6487652A (en) * | 1987-09-29 | 1989-03-31 | Toyota Motor Corp | Impact-resistant polypropylene resin composition |
-
1991
- 1991-11-08 US US07/789,685 patent/US5234993A/en not_active Expired - Lifetime
-
1992
- 1992-11-09 CA CA002123080A patent/CA2123080A1/en not_active Abandoned
- 1992-11-09 JP JP5508628A patent/JPH07500860A/en active Pending
- 1992-11-09 EP EP92923532A patent/EP0611385A1/en not_active Withdrawn
- 1992-11-09 WO PCT/US1992/009340 patent/WO1993009183A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US5234993A (en) | 1993-08-10 |
| EP0611385A1 (en) | 1994-08-24 |
| JPH07500860A (en) | 1995-01-26 |
| WO1993009183A1 (en) | 1993-05-13 |
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