HK1064400B - Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby - Google Patents

Description

Method for preparing poly (arylene ether) -polyolefin composition and composition prepared thereby

RELATED APPLICATIONS

This application claims priority from U.S. application Ser. No. 09/682,929, 2001-11-01, filed from U.S. provisional application Ser. No. 60/258,894, 2000-12-28.

Background

[0001] Poly (arylene ether) -polyolefin compositions are well known. Many references mention the desirability of preparing such compositions by mixing all of the components in a single mixing step. See, for example, U.S. patent 4,764,559 to Yamauchi et al; U.S. patent 4,772,657 to Akiyama et al; U.S. patent 4,863,997 to Shibuya et al; U.S. patent 4,985,495 to Nishio et al; U.S. Pat. No. 4,990,558 to DeNicola, Jr. et al; U.S. patents 5,071,912, 5,075,376, 5,132,363, 5,159,004, 5,182,151 and 5,206,281 to Furuta et al; U.S. patent 5,418,287, to Tanaka et al, and European patent application No. 412,787A 2 to Furuta et al.

[0002] Alternatively, certain references disclose that it is desirable to add the components in order of high to low viscosity. See, for example, U.S. patent 4,764,559 to Yamauchi et al; 4,985,495 to Nishio et al; and 5,418,287 to Tanaka et al.

[0003] In other proposed blending methods, the polyphenylene ether and polypropylene-graft-polystyrene copolymer, with or without unmodified polypropylene, are premixed, then one or more rubbery materials are added and further mixed. See, for example, U.S. patents 5,071,912, 5,075,376, 5,132,363, 5,159,004, 5,182,151 and 5,206,281 to Furuta et al; european patent application No. 412,787A 2 to Furuta et al; and Shibuya et al, Japanese unexamined patent application No. 63[1988] -113049.

[0004] The above-described processes produce compositions that are inadequate for many commercial applications because they exhibit excessive variability in key properties, including stiffness and impact strength. There remains a need for a method of producing poly (arylene ether) -polyolefin compositions having improved balance of properties. In particular, there remains a need for a method of producing poly (arylene ether) -polyolefin compositions with less property variation and an improved balance between stiffness, impact strength, and heat resistance.

Summary of The Invention

[0005] The above-described and other drawbacks and disadvantages of the prior art are overcome by a method of making a thermoplastic composition, comprising: melt blending to form a first intimate blend comprising a poly (arylene ether), a poly (alkenyl aromatic) resin, a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend and the polyolefin.

Brief Description of Drawings

[0006] FIG. 1 is a schematic view of kneading blocks used for high and low intensity and upstream and downstream kneading.

Detailed description of the preferred embodiments

[0007] One embodiment is a method comprising the steps of: melt-blending to form a first intimate blend comprising a poly (arylene ether), a poly (alkenyl aromatic) resin, a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend and a polyolefin.

[0008] Extensive experimentation by the present inventors has resulted in the surprising discovery that the properties of compositions prepared according to this method are significantly and unexpectedly improved over compositions prepared according to known methods, particularly methods in which all components are blended simultaneously.

[0009] In a preferred embodiment, melt blending to form the first intimate blend comprises high energy mixing. The mixing energy can be expressed in various ways. One factor contributing to the mixing energy is the extruder feed point. For example, when the composition is compounded in an eleven barrel twin screw extruder, high energy mixing of the first intimate blend may be expressed as feeding the first intimate blend component into one of the first four barrels.

[0010] Another factor contributing to the mixing energy is the number of mixing sections, with a higher number of mixing sections corresponding to a higher mixing energy. Each mixing section may comprise at least one mixing element. Each of the first intimate blend and the second intimate blend is preferably formed using at least one mixing section. The mixing section and mixing elements are commonly referred to in the art as components of a twin screw extruder. Each mixing element is non-rotatably disposed on the screw shaft and is used to disperse and distribute the components of the thermoplastic composition throughout the blend. The mixing element may or may not advance the composition toward the extruder outlet. The inventors have found that the properties of the composition will be improved if the mixing process to form the first intimate blend and the second intimate blend each uses at least one mixing section. In a preferred embodiment, the mixing to form the first intimate blend and the second intimate blend each uses, on each screw shaft, at least two mixing elements.

[0011] There is no particular limitation on the pattern of the respective mixing elements. Suitable mixing elements include, for example, mixing elements on each of said shafts in radially wiping relation within the extruder barrel and shaped to wipe against each other and the barrel wall, as described in U.S. patent 4,752,135; mixing element disks with mixing fins, such as described in U.S. patent 3,195,868, to Loomans et al, and 5,593,227, to Scheuring et al; a mixing element having two opposing blades, one of which is tapered, as described in U.S. patent 6,116,770 to Kiani et al; there are also a variety of different mixing elements, including those specific to prior art mixing elements, described in U.S. Pat. No. 5,932,159 to Rauwendaal.

[0012] In one embodiment, the melt blending to form the first intimate blend and the melt blending to form the second intimate blend together comprise a mixing action having an energy input of at least about 0.20 kW-hr/kg. Preferably, an energy input of at least about 0.22kW-hr/kg, and more preferably, an energy input of at least about 0.24 kW-hr/kg. This quantitative mixing energy input can be determined by measuring the rotational speed of the extruder motor and the current draw (current draw) of the extruder motor. Since Direct Current (DC) motor speed is proportional to applied voltage, the measured motor speed, rpm, can be converted to voltage, V, using a proportionality constant previously measured. The energy input can then be calculated as the product of extruder motor current and voltage divided by the extruder throughput. For example, an extruder operating at 120V, 2A current, and 1kg/hr throughput will have an energy input

(120V)(2A)/(1kg/h)＝240W-hr/kg

Or 0.240 kW-hr/kg.

[0013] In one embodiment, a first intimate blend may be formed and pelletized in a first step and then mixed with a polyolefin in another step to form a second intimate blend.

[0014] Suitable temperatures for forming the composition are generally between about 80 ℃ and about 400 ℃. Within this range, it may be preferred that the first intimate blend is formed by exposing the first intimate blend components to a temperature of at least about 200 ℃, more preferably at least about 250 ℃, and even more preferably at least about 280 ℃. Also within the above ranges, it may be preferred that the first intimate blend is formed by exposing the first intimate blend components to a temperature of up to about 320 ℃, more preferably up to about 300 ℃, and even more preferably up to about 290 ℃. The same temperatures are also applicable to the formation of the second intimate blend.

[0015] The method is suitable for preparing poly (arylene ether) -polyolefin compositions on any scale, from grams to tons. For economical production of commercially significant quantities of the composition, it may be preferred that the mass throughput rate of the process be at least about 10kg/hr, more preferably at least about 5,000 kg/hr, based on the total weight of the composition. Material throughput rates of 100,000kg/h or more may be used.

[0016] Any known apparatus may be used to carry out the method. The method can be applied on a laboratory scale using a laboratory scale mixer, for example, Labo Plastomill supplied by Toyo Seiki, Hyogo, Japan. Preferred apparatus for carrying out the process on a larger scale include single screw and twin screw extruders, with twin screw extruders being more preferred. Extruders for melt blending thermoplastics are commercially available, for example, from Krupp Werner & Pfleiderer, Inc. (currently known as Coperion), Ramsey, N.J..

[0017] The first intimate blend may comprise any conventional poly (arylene ether). The term poly (arylene ether) includes polyphenylene ether (PPE) and poly (arylene ether) copolymers; a graft copolymer; a poly (arylene ether) ether ionomer; and block copolymers of alkenyl aromatic compounds, vinyl aromatic compounds, and poly (arylene ether) s, and the like; and combination systems comprising at least one of the foregoing; and so on. Poly (arylene ether) s are known polymers comprising a plurality of structural units of the general formula:

wherein in each structural unit, each Q¹Independently of one another halogen, primary or secondary C₁～C₈Alkyl, phenyl, C₁～C₈Haloalkyl, C₁～C₈Aminoalkyl radical, C₁～C₈Hydrocarbyloxy, or C₂～C₈A halohydrocarbyloxy group wherein at least two carbon atoms separate the halogen from the oxygen atom; and each Q²Independently of one another hydrogen, halogen, primary or secondary C₁～C₈Alkyl, phenyl, C₁～C₈Haloalkyl, C₁～C₈Aminoalkyl radical, C₁～C₈Hydrocarbyloxy, or C₂～C₈A halohydrocarbyloxy group wherein at least two carbon atoms separate the halogen from the oxygen atom. Preferably, each Q¹Is alkyl or phenyl, especially C_1-4Alkyl, and each Q²Independently hydrogen or methyl.

[0018] Both homopolymer and copolymer poly (arylene ether) s are included. Preferred homopolymers are those comprising 2, 6-dimethylphenylene ether units. Suitable copolymers include random copolymers containing, for example, such units in combination with 2,3, 6-trimethyl-1, 4-phenylene ether units or copolymers derived from copolymerization of 2, 6-dimethylphenol with 2,3, 6-trimethylphenol. Also included are poly (arylene ether) s containing moieties prepared by grafting of vinyl monomers or polymers such as polystyrene, as well as coupled poly (arylene ether) s in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly (arylene ether) chains to produce a higher molecular weight polymer. Poly (arylene ether) s of the present invention also include any combination of the above examples.

[0019] The poly (arylene ether) typically has a number average molecular weight of about 3,000 to about 40,000 Atomic Mass Units (AMU) and a weight average molecular weight of about 20,000 to about 80,000AMU, as determined by gel permeation chromatography. The poly (arylene ether) may generally have an intrinsic viscosity of about 0.2 to about 0.6dL/g, as measured in chloroform at 25 ℃. Within this range, the intrinsic viscosity may preferably be up to about 0.5dL/g, more preferably up to about 0.47 dL/g. Also within this range, the intrinsic viscosity may preferably be at least about 0.3 dL/g. Combinations of high intrinsic viscosity poly (arylene ether) s with low intrinsic viscosity poly (arylene ether) s may also be employed. When two intrinsic viscosities are employed, the exact ratio will be determined depending upon the exact intrinsic viscosities of the poly (arylene ether) used and the ultimate physical properties desired.

[0020] Poly (arylene ether) s are typically prepared via the oxidative coupling of at least one monohydroxyaromatic hydrocarbon compound such as 2, 6-xylenol or 2,3, 6-trimethylphenol. Such coupling reactions typically require the use of a catalyst system; they usually contain at least one heavy metal compound such as a copper, manganese or cobalt compound, generally in combination with a wide variety of other materials.

[0021] Poly (arylene ether) s that are particularly useful for many purposes include those comprising molecules having at least one aminoalkyl-containing end group. The aminoalkyl radical is typically in the ortho position relative to the hydroxy group. Products containing such end groups may be obtained by incorporating, as one of the components of the oxidative coupling reaction mixture, an appropriate primary or secondary monoamine such as di-n-butylamine or dimethylamine. 4-hydroxybiphenyl end groups are also often present, which are typically obtained from reaction mixtures containing by-product diphenoquinones, particularly in copper-halide-secondary or primary amine systems. A substantial proportion of the polymer molecules, typically constituting about 90% by weight of the polymer, may comprise at least one of aminoalkyl-containing groups and 4-hydroxybiphenyl end groups.

[0022] The first intimate blend may comprise about 10 to about 70 weight percent, based on the total weight of the composition, of poly (arylene ether). Within this range, it may be preferred to use at least about 18 weight percent poly (arylene ether). Also within this range, it may be preferred to use up to about 50 weight percent, more preferably up to about 40 weight percent, of the poly (arylene ether).

[0023] The first intimate blend further comprises a poly (alkenyl aromatic) resin. The term "poly (alkenyl aromatic) resin" as used herein includes polymers prepared by methods known in the art, including bulk, suspension, and emulsion polymerization, which contain at least 25 weight percent structural units derived from alkenyl aromatic monomers of the formula

Wherein R is¹Is hydrogen, C₁～C₈Alkyl, halogen or the like; z is vinyl, halogen, C₁～C₈Alkyl or the like; preferred alkenyl aromatic monomers include styrene, chlorostyrenes such as p-chlorostyrene, vinyl toluenes such as p-vinyl toluene, and the like. The poly (alkenyl aromatic) resin comprises homopolymers of alkenyl aromatic monomers; random copolymers of alkenyl arene monomers such as random copolymers of styrene with one or more different monomers such as acrylonitrile, butadiene, alpha-methylstyrene, ethylvinylbenzene, divinylbenzene and maleic anhydride; and rubber-modified poly (alkenyl aromatic) resins comprising blends and/or grafts of a rubber modifier and an alkenyl aromatic monomer homopolymer (as described above), wherein the rubber modifier may be at least one C₄～C₁₀A polymerization product of a non-aromatic diene monomer such as butadiene or isoprene, and wherein the rubber-modified poly (alkenyl aromatic) resin comprises from about 98 to about 70 weight percent of a homopolymer of an alkenyl aromatic monomer and from about 2 to about 30 weight percent of a rubber modifier. Within this range, it is preferred to use at least 88 weight percent of alkenyl aromatic hydrocarbon monoAnd (3) a body. It is also preferred to use up to about 94 weight percent alkenyl aromatic monomer. It is also preferred to use at least 6 wt% of a rubber modifier. It is also preferred to use up to 12% by weight of rubber modifier.

[0024]The stereoregularity of the poly (alkenyl aromatic) resin may be atactic or syndiotactic. Highly preferred poly (alkenyl aromatic) resins include atactic and syndiotactic homopolystyrenes. Suitable atactic homopolystyrenes are commercially available, for example EB3300 from Chevron and P1800 from BASF. Suitable syndiotactic homopolystyrenes are commercially available, for example, from Dow chemical under the trade name QUESTRA^*(e.g., QUESTRA^*WA 550). Highly preferred poly (alkenyl aromatic) resins also include rubber-modified polystyrenes, also known as high impact polystyrenes or HIPS, comprising about 88 to about 94 weight percent polystyrene and about 6 to about 12 weight percent polybutadiene with an effective gel content of about 10 to about 35%. These rubber-modified polystyrenes are commercially available, for example, GEH 1897 by general electric plastics and BA 5350 by Chevron.

[0025] The first intimate blend may comprise about 1 to about 46 weight percent, preferably about 3 to about 46 weight percent, of the poly (alkenyl aromatic) resin, based on the total weight of the composition.

[0026] Alternatively, the poly (alkenyl aromatic) resin content may be expressed as the fraction of poly (arylene ether) and poly (alkenyl aromatic) resin based on the sum of the weight of the poly (arylene ether) and polyalkenyl aromatic trees. The first intimate blend may preferably comprise about 10 to about 80 weight percent of the poly (alkenyl aromatic) resin, based on the sum of the weight of the poly (arylene ether) and the weight of the poly (alkenyl aromatic) resin. Within this range, it may be preferred to use at least about 20 weight percent, more preferably at least about 40 weight percent, of the poly (alkenyl aromatic) resin, based on the sum of the poly (arylene ether) and poly (alkenyl aromatic) resin. Also within this range, it may be preferred to use up to about 70 weight percent, more preferably up to about 65 weight percent, of the poly (alkenyl aromatic) resin, based on the sum of the poly (arylene ether) and poly (alkenyl aromatic) resins. The glass transition temperature (Tg) of the single phase comprising the poly (alkenyl aromatic) resin and the poly (arylene ether) may be controlled by varying the ratio of the poly (alkenyl aromatic) resin to the poly (arylene ether), relative to the Tg of the poly (arylene ether) alone, or relative to the melting point (Tm) of the polyolefin alone. For example, the relative amounts of poly (alkenyl aromatic) resin and poly (arylene ether) may be selected such that the poly (arylene ether) and poly (alkenyl aromatic) resin form a single phase having a glass transition temperature that is at least about 20 ℃, preferably at least about 30 ℃ higher than the glass transition temperature of the poly (alkenyl aromatic) resin alone (which may be, for example, between about 100 ℃ and 110 ℃). Also, the relative amounts of poly (alkenyl aromatic) resin and poly (arylene ether) may be selected such that the poly (arylene ether) and poly (alkenyl aromatic) resin form a single phase having a glass transition temperature up to about 15 ℃, preferably up to about 10 ℃, more preferably up to about 1 ℃ higher than the Tm of the polyolefin alone. The relative amounts of poly (alkenyl aromatic) resin and poly (arylene ether) may be selected such that the poly (arylene ether) and poly (alkenyl aromatic) resin form a single phase having a glass transition temperature of between about 130 ℃ and about 180 ℃.

[0027] The first intimate blend further comprises a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene. The hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturated group content in the block (B) is reduced by hydrogenation. The arrangement of blocks (A) and (B) includes a linear structure and a so-called radial teleblock (teleblock) structure having a branched chain.

[0028] Preferred among these structures are linear structures including diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block) and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures, and linear structures containing 6 or more blocks in total of A and B. More preferred are diblock, triblock, and tetrablock structures, with A-B diblock and A-B-A triblock structures being particularly preferred.

[0029] The alkenyl aromatic compound providing the block (A) is represented by the following formula:

wherein R is²And R³Each independently represents a hydrogen atom, C₁～C₈Alkyl radical, C₂～C₈Alkenyl groups, and the like; r⁴And R⁸Each independently represents a hydrogen atom, C₁～C₈Alkyl groups, chlorine atoms, bromine atoms, etc.; and R is⁵～R⁷Each independently represents a hydrogen atom, C₁～C₈Alkyl radical, C₂～C₈Alkenyl radicals and the like, or R⁴And R⁵Taken together with the central aromatic ring to form a naphthyl radical, or R⁵And R⁶Taken together with the central aromatic ring to form a naphthyl group.

[0030] Specific examples of alkenyl arene compounds include styrene, p-methylstyrene, α -methylstyrene, vinylxylenes, vinyltoluenes, vinylnaphthalenes, divinylbenzenes, bromostyrenes, chlorostyrenes, and the like, as well as combinations comprising at least one of the foregoing alkenyl arene compounds. Of these, styrene, α -methylstyrene, p-methylstyrene, vinyltoluenes and vinylxylenes are preferred, with styrene being more preferred.

[0031] Specific examples of the conjugated diene include 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene and the like. Preferred among these are 1, 3-butadiene and 2-methyl-1, 3-butadiene, with 1, 3-butadiene being more preferred.

[0032] In addition to the conjugated diene, the hydrogenated block copolymer may contain a small amount of a lower olefin such as ethylene, propylene, 1-butene, dicyclopentadiene, a non-conjugated diene, or the like.

[0033] The content of the repeating unit derived from the alkenyl aromatic compound in the hydrogenated block copolymer is not particularly limited. Suitable alkenyl aromatic content may be about 10 to about 90 weight percent, based on the total weight of the hydrogenated block copolymer. Within this range, it may be preferred to have an alkenyl aromatic content of at least about 40 weight percent, more preferably at least about 50 weight percent, and even more preferably at least about 55 weight percent. Also within this range, it may be preferred to have an alkenyl aromatic content of up to about 85 weight percent, more preferably up to about 75 weight percent.

[0034] There is no particular limitation on the mode of incorporation of the conjugated diene in the hydrogenated block copolymer backbone. For example, when the conjugated diene is 1, 3-butadiene, it may be incorporated in about 1% to about 99% 1, 2-incorporation, with the remainder being 1, 4-incorporation.

[0035] The hydrogenated block copolymer is preferably hydrogenated to such an extent that less than 50%, more preferably less than 20%, and further preferably less than 10% of the unsaturated bonds in the aliphatic chain moiety derived from the conjugated diene remain unreduced. The aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated up to about 25%.

[0036] The hydrogenated block copolymer preferably has a number average molecular weight of about 5,000 to about 500,000AMU, as determined by Gel Permeation Chromatography (GPC) using polystyrene as a standard. Within this range, the number average molecular weight may preferably be at least about 10,000AMU, more preferably at least about 30,000AMU, and still more preferably at least about 45,000 AMU. Also within this range, the number average molecular weight may preferably be up to about 300,000AMU, more preferably up to about 200,000AMU, and even more preferably up to about 150,000 AMU.

[0037] The molecular weight distribution of the hydrogenated block copolymer, as measured by GPC, is not particularly limited. The copolymer can have any ratio between weight average molecular weight and number average molecular weight.

[0038] Some of these hydrogenated block copolymers may have hydrogenated conjugated diene polymer chains that contribute to crystallinity. The crystallinity of the hydrogenated block copolymer can be determined by using a Differential Scanning Calorimeter (DSC), for example, DSC-II manufactured by Perkin-Elmer Co. The heat of fusion can be determined from heating in an inert gas atmosphere such as nitrogen at a heating rate of, for example, 10 deg.C/min. For example, the sample may be heated to a temperature above the estimated melting point, cooled by lowering the temperature at a rate of 10 deg.C/min, held for about 1min, and then heated again at a rate of 10 deg.C/min.

[0039] The hydrogenated block copolymer can have any crystallinity. From the viewpoint of balance of mechanical strength of the obtained resin composition, it is preferred that the hydrogenated block copolymer has a melting point of about-40 ℃ to about 200 ℃ or has no definite melting point (i.e., has non-crystallinity), as measured according to the technique described above. More preferably, the hydrogenated block copolymer has a melting point of at least about 0 ℃, more preferably at least about 20 ℃, and even more preferably at least about 50 ℃.

[0040] The hydrogenated block copolymer can have any glass transition temperature (Tg) contributed by the hydrogenated conjugated diene polymer chain. It preferably has a Tg of at most about 0 deg.C, more preferably at most about-120 deg.C, from the viewpoint of low-temperature impact strength of the resulting resin composition. The glass transition temperature of the copolymer can be measured by the above-mentioned DSC method or can be observed from the viscoelastic behavior with temperature change by a mechanical spectrometer.

[0041] Particularly preferred hydrogenated block copolymers are styrene- (ethylene-butylene) diblock and styrene- (ethylene-butylene) -styrene triblock copolymers obtained by hydrogenation of styrene-butadiene and styrene-butadiene-styrene triblock copolymers, respectively.

[0042]Suitable hydrogenated block copolymers include those commercially available, for example, KRATON supplied by Kraton Polymers, a division of formerly Shell chemical company^*G1650, G1651, and G1652, and TUFTEC available from Asahi Chemicals^*H1041, H1043, H1052, H1062, H1141 and H1272. Preferred hydrogenated block copolymers include highly hydrogenated styrene- (ethylene-butylene) -styrene triblock copolymers such as TUFTEC available from Asahi chemical company^*H1043。

[0043] The first intimate blend may comprise about 1 to about 20 weight percent, preferably about 1 to about 18 weight percent, more preferably about 1 to about 15 weight percent, of the hydrogenated block copolymer, based on the total weight of the composition.

[0044] The first intimate blend further comprises an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene (hereinafter referred to as "unhydrogenated block copolymer"). The unhydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturated group in the block (B) has not been reduced by hydrogenation. The alkenyl aromatic compound (A) and the conjugated diene (B) have been specified in detail in the above paragraph describing the hydrogenated block copolymer. The arrangement of blocks (A) and (B) includes a linear structure and a so-called radial teleblock structure having a branched chain.

[0045] Preferred among these structures are linear structures including diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block) and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures, and linear structures containing 6 or more blocks in total of A and B. More preferred are diblock, triblock, and tetrablock structures, with an A-B-A triblock structure being particularly preferred.

[0046] The unhydrogenated block copolymer may comprise from about 10 to about 90 weight percent of the (A) block. Within this range, it may be preferred to use at least about 20 weight percent (A) of the block. Also within this range, it may be preferred to use up to about 80 weight percent (A) of the block.

[0047] Particularly preferred unhydrogenated block copolymers include styrene-butadiene-styrene triblock copolymers.

[0048]Suitable unhydrogenated block copolymers can be prepared in a known manner or are commercially available, for example, KRATON supplied by Kraton Polymers, a division of formerly Shell chemical company^*Polymers of the D series, including KRATON^*D1101 and D1102.

[0049] The unhydrogenated block copolymer may be used in an amount of about 1 to about 20 weight percent, preferably about 1 to about 15 weight percent, and more preferably about 1 to about 10 weight percent, based on the total weight of the composition.

[0050]The method comprises a first homogenizing stepThe blend is melt blended with a polyolefin to form a second intimate blend. The polyolefin may be a homopolymer or copolymer having at least about 80 weight percent of units derived from ethylene, propylene, butylene, or mixtures thereof. Examples of polyolefin homopolymers include polyethylene, polypropylene, and polybutylene. Examples of polyolefin copolymers include ethylene, propylene and butylene with each other and additionally up to 20% by weight of C₅～C₁₀Random, graft, and block copolymers of alpha-olefin (excluding aromatic alpha-polyolefin) derived units. Polyolefins also include blends of the above homopolymers and copolymers. Preferred polyolefins may have a flexural modulus at 23 ℃ of at least about 100,000 pounds per square inch (psi), as measured by ASTM D790. Suitable polyolefins may include, for example, linear low density polyethylene supplied by ExxonMobil as LL-6201, low density polyethylene supplied by ExxonMobil as LMA-027, high density polyethylene supplied by ExxonMobil as HD-6605, ultra high molecular weight polyethylene supplied by Montell polyolefins as Type 1900, and polybutylene supplied by Montell polyolefins as PB0110 (polybutene-1).

[0051]Presently preferred polyolefins include propylene polymers. The propylene polymer may be a homopolymer of propylene. Alternatively, the propylene polymer may be propylene with at least one member selected from ethylene and C₄～C₁₀Random, graft, or block copolymers of olefins of alpha-olefins (excluding aromatic alpha-olefins), provided that the copolymers contain at least about 80 weight percent, preferably at least about 90 weight percent, of repeating units derived from propylene. Blends of such propylene polymers with small amounts of another polymer such as polyethylene are also included within the scope of propylene polymers. The propylene polymer has a melt flow index of from about 0.1 to about 50g/10min, preferably from about 1 to about 30g/10min, as measured according to ASTM D1238 at 2.16kg and 200 ℃. The propylene polymers described above can be produced by a variety of known processes. Commercially available propylene polymers may also be used.

[0052] Preferred propylene polymers include homopolypropylenes. Highly preferred propylene polymers include homopolypropylenes having a crystalline content of at least about 20%, preferably at least about 30%. Suitable isotactic polypropylenes are commercially available, for example, as PD403 pellets supplied by Basell (formerly MontellPolyoleffs, North America).

[0053] The second intimate blend may comprise, based on the total weight of the composition, from about 10 to about 80 weight percent, preferably from about 10 to about 70 weight percent, and more preferably from about 10 to about 60 weight percent of a polyolefin.

[0054] Although the process includes melt blending the first intimate blend with a polyolefin to form a second intimate blend, a portion of the polyolefin may be added during the formation of the first intimate blend. Preferably, any polyolefin included in the first intimate blend is less than the amount of polyolefin blended with the first intimate blend during formation of the second intimate blend. It is preferred that at least half of the total polyolefin is added during the formation of the second intimate blend.

[0055] The first intimate blend may optionally further comprise a polypropylene-polystyrene copolymer that is a graft copolymer, a diblock copolymer, a multiblock copolymer, a radial block copolymer, or a combination comprising at least one of the foregoing polypropylene-polystyrene copolymers. Alternatively, the polypropylene-polystyrene copolymer may be added as a component of the second intimate blend. In a third alternative, about 1% to about 99% of the total polypropylene-polystyrene copolymer may be added as a component of the first intimate blend, with the remainder added as a component of the second intimate blend.

[0056] In a preferred embodiment, the polypropylene-polystyrene copolymer is a graft copolymer. A polypropylene-polystyrene graft copolymer is defined herein as a graft copolymer having a propylene polymer backbone and one or more styrene polymer arms.

[0057]The propylene polymer material that constitutes the backbone or substrate of the polypropylene-polystyrene graft copolymer is (a) a propylene homopolymer; (b) propylene with a compound selected from ethylene and C₄～C₁₀Random copolymers of olefins, with the proviso that when the olefin is ethylene, the polymerized ethylene content is up to about 10% by weight, preferably up to about 4% by weight, and when the olefin is ethyleneIs C₄～C₁₀When an olefin is present, the C₄～C₁₀The polymerized content of olefin is up to about 20 wt%, preferably up to about 16 wt%; (c) propylene with at least two members selected from ethylene and C₄～C₁₀Random terpolymers of alpha-olefins, with the proviso that C is polymerized4～C 10An olefin content of up to about 20 wt%, preferably up to about 16 wt%, and, when ethylene is one of the olefins, a polymerized ethylene content of up to about 5 wt%, preferably up to about 4 wt%; or (d) a propylene homopolymer or random copolymer impact modified with an ethylene-propylene monomer rubber in the reactor and by physical compounding, wherein the ethylene-propylene monomer rubber content of the modified polymer is from about 5 to about 30 wt%, and the ethylene content of the rubber is from about 7 to about 70 wt%, preferably from about 10 to about 40 wt%. C₄～C₁₀The olefins comprising linear or branched C₄～C₁₀Alpha-olefins, for example, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 3, 4-dimethyl-1-butene, 1-heptene, 1-octene, 3-methyl-hexene, and the like. Propylene homopolymers and impact modified propylene homopolymers are preferred propylene polymer materials. Although not preferred, propylene homopolymers and random copolymers impact modified with ethylene-propylene-diene monomer rubbers having a diene content of about 2 to 8 wt.% may also be used as the propylene polymer material. Suitable dienes include dicyclopentadiene, 1, 6-hexadiene, ethylidene norbornene, and the like.

[0058]The term "styrene polymer" as used to refer to the graft polymer present on the backbone of the propylene polymer material in the polypropylene-polystyrene graft copolymer, refers to a copolymer of (a) styrene or having at least one C₁～C₄Alkyl polystyrenes substituted on the linear or branched alkyl ring, especially homopolymers of p-alkylstyrene; (b) (ii) (a) copolymers of monomers in any proportion to each other; and (c) a copolymer of at least one of (a) a monomer and an alpha-methyl derivative thereof, such as alpha-methylstyrene, wherein the alpha-methyl derivative comprises from about 1 to about 40 weight percent of the copolymer.

[0059] The polypropylene-polystyrene graft copolymer will typically comprise from about 10 to about 90 weight percent of a propylene polymer backbone and from about 90 to about 10 weight percent of styrene polymer arms. Within this range, the propylene polymer backbone may preferably comprise at least about 20 weight percent of the total graft copolymer; the propylene polymer backbone may preferably comprise at least about 40 wt% of the total graft copolymer. Also within this range, the styrenic polymer arms may preferably comprise at least about 50 weight percent, more preferably at least about 60 weight percent of the total graft copolymer.

[0060] The preparation of polypropylene-polystyrene graft copolymers is described, for example, in U.S. Pat. No. 4,990,558 to Denicola, Jr. Suitable polypropylene-polystyrene graft copolymers are also commercially available, for example, P1045H1 and P1085H1, supplied by Basell.

[0061] When present, the polypropylene-polystyrene graft copolymer may be used in an amount of about 0.5 to about 30 wt%, preferably about 0.5 to about 20 wt%, more preferably about 0.5 to about 10 wt%, based on the total weight of the composition.

[0062]The process may optionally further comprise adding an ethylene/alpha-olefin elastomeric copolymer. The alpha-olefin component of the copolymer may be at least one C₃～C₁₀An alpha-olefin. Preferred alpha-olefins include propylene, 1-butene and 1-octene. The elastomeric copolymer may be a random copolymer having from about 25 to about 75 weight percent, preferably from about 40 to about 60 weight percent ethylene and from about 75 to about 25 weight percent, preferably from about 60 to about 40 weight percent alpha-olefin. Within this range, it may be preferred to use at least about 40 weight percent ethylene; it may be preferred to use up to about 60 wt% ethylene. Also within this range, it may be preferred to use at least about 40 weight percent alpha olefin; it may be preferred to use up to about 60 wt% alpha-olefin. The ethylene-alpha-olefin elastomeric copolymer generally has a melt flow index of from about 0.1 to about 20g/10min, as measured at 2.16kg and 200 ℃, and a density of from about 0.8 to about 0.9 g/mL.

[0063] Particularly preferred ethylene/alpha-olefin elastomeric copolymer rubbers include ethylene-propylene rubbers, ethylene-butene rubbers, ethylene-octene rubbers, and mixtures thereof.

[0064]The ethylene/alpha-olefin elastomeric copolymers can be prepared according to known methods or are commercially available, for example as VISTALON from ExxonMobil chemical company^*878 pure ethylene propylene rubber and EXACT from ExxonMobil chemical company^*4033. Ethylene/alpha-olefin elastomeric copolymers are also commercially available as blends in polypropylene, such as ethylene-propylene rubber pre-dispersed in polypropylene sold by Basell under the product designations Profax 7624 and Profax 8023, and ethylene-butylene rubber pre-dispersed in polypropylene sold by Basell as catalloy k 021P.

[0065] In a first embodiment, the ethylene/a-olefin elastomeric copolymer may be added during formation of the first intimate blend. In a second embodiment, the ethylene/a-olefin elastomeric copolymer may be added during the formation of the second intimate blend. In a third embodiment, about 1 to about 99 percent of the ethylene/alpha-olefin elastomeric copolymer may be added during the formation of the first intimate blend, with the remainder being added during the formation of the second intimate blend. In a fourth embodiment, the ethylene/alpha-olefin elastomeric copolymer may be made into a heterophasic copolymer with the polyolefin, and the resulting heterophasic copolymer comprising the ethylene/alpha-olefin elastomeric copolymer and the polyolefin may be added during the formation of the first intimate blend, or preferably, during the formation of the second intimate blend.

[0066] When present, the ethylene/alpha-olefin elastomeric copolymer may be used in an amount of about 1 to about 20 weight percent, based on the total weight of the composition. Within this range, the ethylene/alpha-olefin elastomeric copolymer may preferably be used in an amount of at least about 3 weight percent. Also within this range, the ethylene/alpha-olefin elastomeric copolymer may preferably be used in an amount up to about 15 weight percent.

[0067] In one embodiment, the content of the ethylene/α -olefin elastomeric copolymer may be expressed as a fraction of the sum of the polyolefin and the ethylene/α -olefin elastomeric copolymer. Thus, when present, the ethylene/alpha-olefin elastomeric copolymer may be present in an amount of from about 1 to about 60 weight percent, preferably from about 10 to about 40 weight percent, based on the combined weight of the polyolefin and the ethylene/alpha-olefin elastomeric copolymer.

[0068] The method may optionally include the addition of one or more reinforcing fillers. Reinforcing fillers may include, for example, inorganic and organic materials, such as fibers, woven and non-woven fabrics of E-, NE-, S-, T-and D-type glasses and quartz; carbon fibers including poly (acrylonitrile) (PAN) fibers, vapor-formed carbon fibers, and particularly graphite vapor-formed carbon fibers having an average diameter of from about 3 to about 500nm (see, for example, U.S. Pat. Nos. 4,565,684 and 5,024,818 to Tibbetts et al; 4,572,813 to Arakawa; 4,663,230 and 5,165,909 to Tennent; 4,816,289 to Komatsu et al, 4,876,078 to Arakawa et al, 5,589,152 to Tennent et al, and 5,591,382 to Nahass et al); potassium titanate single crystal fibers, silicon carbide fibers, boron carbide fibers, gypsum fibers, alumina fibers, asbestos, iron fibers, nickel fibers, copper fibers, wollastonite fibers; and the like. The reinforcing filler may be glass roving cloth, glass cloth, chopped glass, hollow glass fiber, glass mat, glass veil mat and non-woven glass cloth, ceramic fiber cloth, and metal fiber cloth. In addition, synthetic organic reinforcing fibers may also be used, including organic polymers that can be formed into fibers. Illustrative examples of such reinforcing organic fibers are poly (ether ketone), polyimide benzoxazole, poly (phenylene sulfide), polyesters, aromatic polyamides, aromatic polyimides or polyetherimides, acrylic resins, and polyvinyl alcohol. Fluoropolymers such as polytetrafluoroethylene may be used. Also included are natural organic fibers known to those skilled in the art, including cotton, hemp and felt, carbon fiber cloth, and natural cellulosic cloth, such as Kraft paper, cotton paper, and glass fiber containing paper. Such reinforcing fillers may be in the form of monofilament or multifilament fibers, either alone or in combination with another type of fiber, such as by co-weaving or sheath-core, side-by-side, orange-peel or matrix-and-fibril constructions, or by other methods known to those skilled in the art of fiber manufacture. They may be used, for example, in the form of woven fibrous reinforcements, non-woven fibrous reinforcements or papers.

[0069] Preferred reinforcing fillers include glass fibers. Preferred glass fibers may have a diameter of about 2 to about 25 μm, more preferably about 10 to about 20 μm, and still more preferably about 13 to about 18 μm. The glass fibers may have a length of about 0.1 to about 20mm, more preferably about 1 to about 10mm, and still more preferably about 2 to about 8 mm. Glass fibers comprising a size that enhances their compatibility with polyolefins are particularly preferred. Suitable compounds are described, for example, in U.S. Pat. No. 5,998,029 to Adzima et al. Suitable glass fibers are commercially available, for example, under product numbers 147A-14P (14 μm diameter) and 147A-17P (17 μm diameter) from Owens Corning.

[0070]Preferred reinforcing fillers also include talc. There is no particular limitation on the physical properties of the talc powder. Preferred talc powders may have an average particle size of about 0.5 to about 25 μm. Within this range, it may be preferred to use talc having an average particle size of up to about 10 μm, more preferably up to about 5 μm. For use of certain compositions, it may be preferred to use f.d.a. compliant talc (i.e., compliant with U.S. food and drug administration regulations). Suitable talc includes, for example, CIMPACT by Luzenac^*610(C) sold F.D.A. standard talc having an average particle size of about 3.2 μm.

[0071]The compatibility between the reinforcing filler and the polyolefin can be improved not only by surface sizing of the reinforcing filler, but also by adding to the composition a graft copolymer comprising a polyolefin backbone and polar arms formed from one or more cyclic anhydrides. Such materials include polyolefins and C₄～C₁₂Graft copolymers of cyclic anhydrides, e.g. EXXELOR by ExxonMobil^*And Dupont under the trade name FUSABOND^*Those supplied. Examples of suitable polyolefin-graft-cyclic anhydride copolymers are polypropylene-graft-poly (maleic anhydride) materials from ExxonMobil as EXXELOR^*PO1020 and DuPont under FUSABOND^*M613-05. Suitable amounts of such materials can be readily determined and are generally from about 0.1 to about 10 weight percent, based on the total weight of the composition. Within this range, it may be preferred to use at least about 0.5 weight percent polyolefin-graft-cyclicAn acid anhydride copolymer. Also within this range, it may be preferred to use up to about 5 weight percent of the polyolefin-graft-cyclic anhydride copolymer.

[0072] The one or more reinforcing fillers may be blended with the first intimate blend and the polyolefin during formation of the second intimate blend. Alternatively, the method may comprise an additional blending step wherein the one or more reinforcing fillers are blended with the second intimate blend. In another alternative, it may be advantageous to add reinforcing fillers, particularly particulate fillers (i.e., those having an aspect ratio less than about 3), during the formation of the first intimate blend.

[0073] The method may optionally include adding an additive to the composition. Such additives may include, for example, stabilizers, mold release agents, processing aids, flame retardants, drip retardants, nucleating agents, ultraviolet blocking agents, dyes, pigments, particulate fillers (i.e., those having an aspect ratio less than about 3), antioxidants, antistatic agents, blowing agents, and the like. Such additives are well known in the art and suitable amounts thereof can be readily determined. There is no particular limitation as to how and when the additives are added. For example, the additives may be added during the formation of the first intimate blend. Alternatively, the additives may be added during the formation of the second intimate blend. In another alternative, the additives may be added in a separate step after the second intimate blend is formed.

[0074] Where a composition is defined as comprising multiple components, it will be understood that each component has chemically distinct characteristics, particularly where one chemical compound can satisfy the definition of more than one component.

[0075] In a preferred embodiment, a method of making a thermoplastic composition comprises: melt-blending to form a first intimate blend comprising about 10 to about 59 weight percent of a poly (arylene ether), about 1 to about 46 weight percent of a poly (alkenyl aromatic) resin, about 1 to about 20 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and about 1 to about 20 weight percent of an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend and from about 10 to about 60 weight percent of a polyolefin; wherein all weight percents are based on the total weight of the composition.

[0076] In another preferred embodiment, a method of making a thermoplastic composition comprises: melt-blending to form a first intimate blend comprising about 10 to about 59 weight percent of a poly (arylene ether), about 1 to about 46 weight percent of a poly (alkenyl aromatic) resin, about 1 to about 20 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and about 1 to about 20 weight percent of an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend, about 10 to about 60 weight percent of a polyolefin, and about 1 to about 20 weight percent of an ethylene/alpha-olefin elastomeric copolymer; wherein all weight percents are based on the total weight of the composition.

[0077] In another preferred embodiment, a method of making a thermoplastic composition comprises: melt-blending to form a first intimate blend comprising about 10 to about 59 weight percent of a poly (arylene ether), about 1 to about 46 weight percent of a poly (alkenyl aromatic) resin, about 1 to about 20 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, about 1 to about 20 weight percent of an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and about 0.5 to about 30 weight percent of a polypropylene-polystyrene graft copolymer; and melt blending to form a second intimate blend comprising the first intimate blend and about 10 to about 60 weight percent of a polyolefin; wherein all weight percents are based on the total weight of the composition.

[0078] In another preferred embodiment, the method of making a thermoplastic composition comprises: melt-blending to form a first intimate blend comprising about 10 to about 59 weight percent of a poly (arylene ether), about 1 to about 46 weight percent of a poly (alkenyl aromatic) resin, about 1 to about 20 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and about 1 to about 20 weight percent of an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend, about 10 to about 60 weight percent of a polyolefin, and about 1 to 50 weight percent of a reinforcing filler; wherein all weight percents are based on the total weight of the composition.

[0079] In another preferred embodiment, the method of making a thermoplastic composition comprises: melt-blending to form a first intimate blend comprising about 10 to about 59 weight percent of a poly (arylene ether), about 1 to about 46 weight percent of a poly (alkenyl aromatic) resin, about 1 to about 20 weight percent of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and about 1 to about 20 weight percent of an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and melt blending to form a second intimate blend comprising the first intimate blend and from about 10 to about 60 weight percent of a polyolefin; and melt blending to form a third intimate blend comprising the second intimate blend and about 1 to about 50 weight percent of a reinforcing filler; wherein all weight percents are based on the total weight of the composition.

[0080] Another embodiment is a thermoplastic composition made according to any of the methods described above.

[0081] While the method has been described in terms of poly (arylene ether) -polyolefin blends, it is generally applicable to a wide variety of thermoplastic blends made from a relatively stiff (e.g., higher flexural modulus) polymer dispersed in a less stiff (e.g., lower flexural modulus) polymer matrix, with the intent of producing blends with consistently reproducible properties.

[0082] The method is particularly useful for thermoplastic blends comprising at least three components, wherein a first component is intended to constitute the matrix phase of the final blend, a second component is intended to be the dispersed phase, and a third component is intended to be at least partially distributed at the interface of the matrix phase and the dispersed phase. Thus, the method may comprise: melt blending to form a first intimate blend comprising a dispersed phase component and an interfacial component; and melt blending to form a second intimate blend comprising the first intimate blend and the matrix component.

[0083] The invention will now be further illustrated by way of non-limiting examples.

Examples 1 to 3, comparative examples 1 and 2

[0084] The separately formulated materials were compounded in a twin screw extruder using a variety of different methods. The components and amounts of the formulation are summarized in table 1.

TABLE 1

Materials abbreviations	Description of the invention	wt％
			PP	Polypropylene, available as PH280 from Montell Polyolefin	57.2
EPR	Ethylene propylene rubber available from ExxonMobil chemical company as VISTALON*878 to get	7.3
			PP-g-PS	Polypropylene-polystyrene graft copolymer available from MontelPolyolefin as Interloy PH 1045H1	13.3
SEBS G1652	Styrene- (ethylene-butadiene) -styrene copolymers from Kraton polymers as KRATON*1652 available from G1652	2.7
			PPE	Poly (2, 6-dimethylphenylene ether), IV 0.40dl/g, available from general electric company	6.7
SBS	Styrene-butadiene-styrene block copolymers from Kraton polymers by KRATON*D1101 is purchased from	5.1
			xPS	Homopolystyrene, also known as crystalline polystyrene, was obtained as PP-738 from Huntsman chemical company at an MFI of 10.5g/10min, 200 ℃ and 5kg	7.7

[0085] General blending/mixing procedure: PP-g-PS, PPE, xPS, HIPS, SEBS and SBS were mixed by hand in bags in the amounts specified in Table 1. The resulting mixture was then mixed stepwise with a mechanical blender to achieve homogeneity. The homogeneous mixture is then fed to a feeder and into the extruder from the initial feed point of the extruder. When the amount of poly (alkenyl aromatic) resin is equal to or greater than 10 weight percent of the total blend, the poly (alkenyl aromatic) resin may be fed through a separate upstream feeder. The components PP and EPR were fed upstream or downstream in the amounts specified in Table 1. The downstream addition corresponds to the barrel section 6 addition in a ten barrel extruder.

[0086] General extrusion procedure: a30 mm co-rotating twin screw extruder was used. The blend is melt extruded at 520 ° F, 450 to 500rpm, and an extrusion rate of 30 to 50 pounds per hour. The melt is forced from the extruder through a three-hole die to produce a melt strand. These strands were rapidly cooled by passing through a cold water bath. The cooled strands were cut into chips. And drying the slices in an oven at 200 ℃ for 2-4 h.

[0087] General molding: ASTM parts are molded on 120 ton molding machines (manufactured by Van Dorn) at barrel temperatures of 450 to 550 DEG F and mold temperatures of 100 to 120 DEG F.

[0088] The parts were tested according to ASTM methods. Izod notched impact strength, measured according to ASTM D256 at 23 ℃ and-30 ℃. Dynatup (Dart) Total energy and failure energy were measured at 23 ℃ and-30 ℃ at 5 and 7.5mph according to ASTM D3763. Heat Distortion Temperature (HDT) was measured according to ASTM D648 on 1/8 inch samples at 66psi and 264 psi. Flexural modulus and flexural strength were measured according to ASTM D790 on 1/8 inch samples at 23 ℃. Tensile strength and elongation at break, measured at 23 ℃ according to ASTM D638. When given, the standard deviation reflects the measurements for 5 samples.

[0089] Process variations included extruder barrel temperature, screw speed ("RPM"), extrusion capacity, split between the polyolefin addition upstream (i.e., during formation of the first intimate blend) and the addition downstream (i.e., during formation of the second intimate blend), and split between the SEBS and PP-g-PS additions upstream and downstream. For all formulations, the first intimate blend was formed using high intensity mixing, abbreviated as "+ 1" and corresponding to the use of 6 mixing elements on each screw shaft, while the second intimate blend was formed using low intensity mixing, abbreviated as "-1" and corresponding to the use of 5 mixing elements on each screw shaft. Also, for all examples and comparative examples, PPE, xPS and SBS were added upstream and EPR was added downstream. The examples differ from the comparative examples in that the examples employ downstream addition of all PP, whereas the comparative examples employ upstream addition of 75% PP and downstream addition of 25% PP. The process variations and resulting properties are summarized in table 2. The standard deviation reflects the measurements for 5 samples. The best overall performance balance is reflected in example 1, which employs downstream addition of PP, and upstream addition of PP-g-PS and SEBS.

TABLE 2

	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Process variations
Upstream mixing	+1	+1	+1	+1	+1
						Downstream mixing	+1	+1	+1	+1	+1
RPM	450	450	450	250	250
						Extrusion volume (lb/h)	55	25	55	55	25
Barrel temperature (. degree. C.)	240	240	290	290	240
						Upstream addition fraction of PP (%)	0	0	0	75	75
PP-g-PS and SEBS upstream addition fraction (%)	100	0	0	0	0
						Performance of
Notched Izod, 23 ℃ (ft-lb/in)	7.219	2.742	2.961	3.309	4.400
						Standard deviation (ft-lb/in)	0.391	0.091	0.195	0.103	0.186
Relative standard deviation (%)	5.4	3.3	6.6	3.1	4.2
						Notched Izod, -30 ℃ (ft-lb/in)	1.385	0.723	0.851	1.183	1.257
Standard deviation (ft-lb/in)	0.053	0.071	0.144	0.172	0.109
						Relative standard deviation (%)	3.8	9.8	16.9	14.5	8.7
Dart total energy, 5mph, 23 deg.C (ft-lb)	26.23	16.98	22.03	24.77	22.27
						Standard deviation (ft-lb)	0.34	5.06	3.12	1.54	4.55
Relative standard deviation (%)	1.3	29.8	14.2	6.2	20.4
						Dart total energy, 5mph, -30 ℃ (ft-lb)	13.51	0.9	3.66	12.11	3.19
Standard deviation (ft-lb)	2.09	0.47	2.38	1.53	0.81
						Relative standard deviation (%)	15.5	52.2	65.0	12.6	25.4
Flexural modulus, 23 ℃, 1/8in (psi)	186,300	202,700	200,600	207,400	199,100
						Standard deviation (ft-lb)	4848	2743	2823	2832	4825
Relative standard deviation (%)	2.6	1.4	1.4	1.4	2.4

Examples 4 to 10

[0090] Samples were prepared by mixing using the same formulation as above, varying the process including upstream and downstream mixing intensity, extruder barrel temperature, screw speed ("RPM") and throughput. For all samples, PPE, xPS, SBS, SEBS and PP-g-PS were added upstream; while PP and EPR are added downstream. The results are shown in Table 3.

TABLE 3

	Example 4	Example 5	Example 6	Example 7	Example 8	Example 9	Example 10
								Process variations
Upstream mixing	-1	-1	-1	+1	+1	+1	+1
								Downstream mixing	-1	+1	+1	-1	+1	+1	+1
RPM	450	350	350	450	450	450	450
								Extrusion volume (kg/h)	40	55	55	55	55	25	25
Barrel temperature (. degree. C.)	290	240	240	240	290	290	240
								Performance of
HDT，66psi，1/8in(°F)	221.7	211.1	207.9	206.4	219.8	216.0	215.8
								HDT，264psi，1/8in(°F)	143.6	144.0	141.1	139.1	144.1	141.5	142.3
Notched Izod, 23 ℃ (ft-lb/in)	2.373	3.804	4.444	7.219	2.273	1.567	2.667
								Standard deviation (ft-lb/in)	0.104	0.200	0.079	0.391	0.077	0.081	0.101
Relative standard deviation (%)	4.4	5.3	1.8	5.4	3.4	5.2	3.8
								Notched Izod, -30 ℃ (ft-lb/in)	0.896	1.273	1.037	1.385	0.827	0.638	0.933
Standard deviation (ft-lb/in)	0.088	0.077	0.026	0.053	0.194	0.030	0.055
								Relative standard deviation (%)	9.8	6.0	2.5	3.8	23.5	4.7	5.9
Dart total energy, 7.5mph, 23 deg.C (ft-lb)	10.34	15.10	16.66	27.84	19.79	13.65	24.88
								Standard deviation (ft-lb)	2.63	1.07	1.13	0.39	6.16	4.81	0.98
Relative standard deviation (%)	25.4	7.1	6.8	1.4	31.1	35.2	3.9
								Dart total energy, 5mph, 23 deg.C (ft-lb)	12.32	14.22	16.93	26.23	14.57	8.56	18.67
Standard deviation (ft-lb)	5.59	2.54	0.62	0.34	6.26	3.62	5.14
								Relative standard deviation (%)	45.4	17.9	3.7	1.3	43.0	42.3	27.5
Dart total energy, 5mph, -30 ℃ (ft-lb)	1.38	1.67	1.09	13.51	2.28	1.31	6.27
								Standard deviation (ft-lb)	0.67	0.40	0.23	2.09	2.01	0.36	1.98
Relative standard deviation (%)	48.6	24.0	21.1	15.5	88.2	27.5	31.6
								Flexural modulus, 23 ℃, 1/8in (psi)	202,400	192,400	185,700	186,300	198,800	193,500	198,200
Standard deviation (psi)	5235	2846	4341	4848	853	1767	1085
								Relative standard deviation (%)	2.6	1.5	2.3	2.6	0.4	0.9	0.5
Elongation at break, 23 ℃ (%)	56.2	69.0	61.1	100.6	66.5	61.9	55.8

Example 11

[0091]A composition was compounded using the formulation detailed in Table 4. SEBS H1043 is a hydrogenated styrene-butadiene-styrene triblock copolymer with 66 wt% polystyrene, TUFTEC by Asahi Chemicals^*Obtained in the form of pellets. The amounts of all components are expressed in parts by weight. Upstream mixing used 6 mixing elements per screw shaft; downstream mixing employed 3 mixing elements per screw shaft. These two were added downstream, except for EPR and 75% PP, with all other components added upstream of the extruder. The extruder barrel temperature was 288F and the screw speed was 450 RPM. The properties were measured as described above and the results are shown in Table 4.

TABLE 4

	Example 11
		Composition of
PP	33.90
		EPR	6.20
PP-g-PS	5.90
		SBS	11.40
SEBS H1043	6.30
		xPS	20.20
PPE	16.20
		Performance of
Flexural modulus, 23 ℃, 1/8 "(psi)	221,000
		Flexural Strength at yield (psi)	7300
HDT，66psi，1/8″(°F)	229
		HDT，264psi，1/8″(°F)	170
Notched Izod, 23 ℃, (ft-lb/in)	8.9
		Notched Izod, -30 ℃, (ft-lb/in)	2.5
Unnotched Izod, 23 ℃, (ft-lb/in)	--
		Destruction energy, 23 ℃, 7.5mph (ft-lb)	19.2
Total energy, 23 ℃, 7.5mph (ft-lb)	32.4
		Destruction energy-30 ℃ C., 7.5mph (ft-lb)	14.7
Total energy-30 ℃, 7.5mph (ft-lb)	17
		Destruction energy-30 ℃ 5mph (ft-lb)	--
Total energy-30 ℃, 5mph (ft-lb)	--
		Tensile Strength at yield (psi)	5,060
Tensile stress at Break (psi)	5,079
		Elongation at Break (%)	273

Examples 12 to 47

[0092] These examples collectively demonstrate the effect of mixing energy inputs on the performance of a single composition.

[0093] The compositions are summarized in Table 5; all amounts are in weight percent based on the total composition. The components are specified in Table 1 except that EPR is obtained from MontellPolyolefins as PROFAX 7624, which is a heterogeneous/predispersed blend of about 20 weight percent EPR in polypropylene; polypropylene (PP) is a mixture of PD403, obtained from Montell Polyolefin, and PROFAX 7624 with a polypropylene content of 80 wt%.

TABLE 5

PPE	16.14
		SBS	11.36
xPS	20.13
		SEBS H1043	6.28
PP-g-PS	5.88
		PP	33.76
EPR	6.20
		Heat stabilizer	0.25

[0094] The composition was extruded using an upstream addition of all components except EPR and PP, both of which were added downstream. Barrel temperature was 500 ° F for all samples. The mixing energy input was varied by varying the number of downstream mixing elements in the extruder and varying the extruder screw speed and the total feed rate of all components. The energy input for each sample was calculated as follows

E＝V*A/T

Where E is the energy input (kW-hr/kg), V is the applied voltage (V, volts) of the DC extruder motor, A is the current drawn by the extruder motor (A, amps), and T is the material throughput (g).

[0095] ASTM parts were molded as described above, at-30 ℃ and 5mph until energy to failure value, as determined by ASTM D3763. The results are set forth in Table 6, which shows that there is a clear correlation between higher downstream energy input and higher destruction energy values.

TABLE 6

Example No.	Energy input (kW-hr/kg)	Destruction energy-30 ℃ 5mph (ft-lb)
			12	0.228	11.83
13	0.241	15.23
			14	0.218	11.61
15	0.234	11.32
			16	0.229	5.87
17	0.224	10.32
			18	0.211	8.99
19	0.227	10.52
			20	0.215	12.41
21	0.247	19.36
			22	0.233	6.74
23	0.216	10.72
			24	0.227	13.46
25	0.251	14.80
			26	0.224	11.03
27	0.226	10.10
			28	0.225	5.80
29	0.243	18.11
			30	0.246	13.30
31	0.230	11.10
			32	0.241	16.94
33	0.223	6.74
			34	0.233	9.54
35	0.222	3.79
			36	0.224	7.74
37	0.267	21.74
			38	0.255	21.16
39	0.245	20.29
			40	0.240	20.06
41	0.267	14.88
			42	0.245	13.29
43	0.245	23.24
			44	0.245	21.71
45	0.245	21.41
			46	0.245	23.47
47	0.245	22.28

Examples 48 to 59

[0096] These examples further demonstrate the effect on performance of upstream and downstream partitioning of polyolefin addition, upstream kneading strength, and downstream kneading strength.

[0097] The composition is detailed in table 5 above. The process variations were upstream addition partitioning of PP and EPR, upstream mixing of high (+1) and low (-1) intensity, and downstream kneading of high (+1) and low (-1) intensity. High intensity upstream and downstream kneading corresponds to an assembly employing multiple right-hand, left-hand, and neutral kneading elements, kneading 1(+1) and kneading 2(+1) as shown in FIG. 1, respectively. Also, the low-intensity upstream-downstream kneading corresponds to the use of an assembly of kneading 1(-1) and kneading 2(-1) as shown in FIG. 1, respectively.

[0098] The process variations and performance values are shown in Table 7. Comparison between examples 52 and 53 and 54 and 55 shows the effect of upstream and downstream addition partitioning of polyolefin with high intensity upstream mixing and low intensity downstream mixing, respectively. It is noted that examples 54 and 55, with downstream addition of polyolefin, show superior 23 ℃ notched Izod impact strength, -30 ℃ failure energy, -total energy at 30 ℃, yield flexural strength and yield tensile strength compared to examples 52 and 53 with upstream addition of polyolefin.

[0099] Comparison between examples 54 and 55 and 56 and 57 shows the effect of low intensity downstream kneading and high intensity downstream kneading with downstream addition of PP and EPR and high intensity upstream mixing, respectively. It is noted that examples 54 and 55, using low-strength downstream kneading, exhibited superior 23 ℃ and-30 ℃ notched Izod impact strengths than examples 56 and 57 of high-strength downstream kneading.

TABLE 7

	Example 48	Example 49	Example 50	Example 51	Example 52	Example 53
							Process variations
Percentage of (PP + EPR) downstream addition	0	0	100	100	0	0
							Upstream mixing	-1	-1	-1	-1	+1	+1
Downstream mixing	-1	-1	-1	-1	-1	-1
							Performance of
HDT，66psi，1/8in(°F)	223.7	225.1	227.9	228.3	--	230.4
							Standard deviation (F degree)	9.1	5.7	0.6	2.3	--	1.9
HDT，264psi，1/8in(°F)	163.2	166.6	164.4	164.6	165.6	166.7
							Standard deviation (F degree)	0.9	2.4	0.6	2.4	1.3	1.4
Notched Izod, 23 ℃ (ft-lb/in)	8.1	8.2	7.8	8.8	7.8	7.6
							Standard deviation (ft-lb/in)	0.1	0.3	0.3	0.4	0.3	0.2
Notched Izod, -30 ℃ (ft-lb/in)	2.3	2.9	2.6	2.6	2.4	3.0
							Standard deviation (ft-lb/in)	0.4	0.8	0.5	0.3	0.3	0.7
Dart destruction energy, 7.5mph, 23 deg.C (ft-lb)	17.55	17.61	17.61	17.74	17.90	17.98
							Standard deviation (ft-lb)	0.46	0.24	0.59	0.54	0.23	0.51
Dart total energy, 7.5mph, 23 deg.C (ft-lb)	28.57	26.69	25.38	27.02	29.16	30.39
							Standard deviation (ft-lb)	1.78	2.97	3.19	2.64	2.44	1.03
Dart destruction energy, 7.5mph, -30 ℃ (ft-lb)	11.13	7.83	6.41	8.22	10.03	10.73
							Standard deviation (ft-lb)	4.17	3.42	2.30	4.42	5.26	5.40
Total Dart energy, 7.5mph, -30 ℃ (ft-lb)	12.51	8.32	7.08	8.64	10.52	11.22
							Standard deviation (ft-lb)	5.67	3.43	2.68	4.54	5.42	5.55
Dart destruction energy, 5mph, -30 ℃ (ft-lb)	15.04	15.11	9.82	10.14	17.87	17.93
							Standard deviation (ft-lb)	4.11	5.46	3.97	4.63	3.08	4.35
Dart total energy, 5mph, -30 ℃ (ft-lb)	15.50	15.54	10.16	10.49	19.06	19.69
							Standard deviation (ft-lb)	4.23	5.58	4.04	4.74	4.13	6.52
Flexural modulus, 23 ℃, 1/8in (psi)	203,900	210,300	209,800	214,000	213,100	212,200
							Standard deviation (psi)	980	755	3936	2612	3368	1532
Flexural Strength at yield, 23 ℃, 1/8in (psi)	6,704	6,830	6,878	6,994	6,888	6,875
							Standard deviation (psi)	21	17	32	32	22	23
Tensile Strength at yield, 23 ℃, 1/8in (psi)	4,693	4,721	4,809	4,818	4,703	4,693
							Standard deviation (psi)	27.4	5.8	19.4	10.8	6.0	27.3
Tensile Strength at Break, 23 ℃, 1/8in (psi)	4,216	4,454	4,358	4,508	4,588	4,216
							Standard deviation (psi)	182.6	105.3	89.8	108.8	32.4	182.6
Elongation at break, 23 ℃ (%)	137.42	203.69	171.06	205.44	248.66	137.6
							Standard deviation (%)	64.02	30.87	19.52	32.55	10.74	64.07

Table 7 (continuation)

	Example 54	Example 55	Example 56	Example 57	Example 58	Example 59
							Process variations
Percentage of (PP + EPR) downstream addition	100	100	100	100	0	0
							Upstream mixing	+1	+1	+1	+1	+1	+1
Downstream mixing	-1	-1	+1	+1	+1	+1
							Performance of
HDT，66psi，1/8in(°F)	225.5	230.4	238.1	233.6	235.4	234.6
							Standard deviation (F degree)	8.1	0.9	0.8	1.9	2.3	3.0
HDT，264psi，1/8in(°F)	165.5	168.7	171.4	170.3	169.7	169.0
							Standard deviation (F degree)	1.7	0.9	2.3	0.8	0.8	2.6
Notched Izod, 23 ℃ (ft-l)b/in)	8.4	8.5	7.5	7.8	7.2	7.5
							Standard deviation (ft-lb/in)	0.4	0.2	0.3	0.4	0.2	0.3
Notched Izod, -30 ℃ (ft-lb/in)	2.7	2.7	2.2	2.1	2.1	2.1
							Standard deviation (ft-lb/in)	0.3	0.3	0.2	0.1	0.2	0.2
Dart destruction energy, 7.5mph, 23 deg.C (ft-lb)	17.77	17.75	17.52	17.5	16.83	17.52
							Standard deviation (ft-lb)	0.40	0.17	0.5	0.52	0.28	0.13
Dart total energy, 7.5mph, 23 deg.C (ft-lb)	28.84	29.89	28.07	27.07	25.59	28.47
							Standard deviation (ft-lb)	3.20	1.57	1.13	3.22	2.56	1.41
Dart destruction energy, 7.5mph, -30 ℃ (ft-lb)	15.62	15.83	17.18	16.61	13.39	16.56
							Standard deviation (ft-lb)	5.38	6.89	6.80	6.12	7.66	5.44
Total Dart energy, 7.5mph, -30 ℃ (ft-lb)	17.88	20.65	18.26	19.21	14.45	18.05
							Standard deviation (ft-lb)	7.80	12.27	7.37	8.76	8.49	6.66
Dart destruction energy, 5mph, -30 ℃ (ft-lb)	17.09	20.81	15.17	18.22	12.13	16.05
							Standard deviation (ft-lb)	6.56	3.49	6.13	3.80	6.45	6.95
Dart total energy, 5mph, -30 ℃ (ft-lb)	20.63	27.63	17.73	19.85	13.33	18.84
							Standard deviation (ft-lb)	9.48	8.10	9.08	5.06	8.09	9.37
Flexural modulus, 23 ℃, 1/8in (psi)	215,700	218,400	225,100	220,400	220,900	220,600
							Standard deviation (psi)	997	2,298	2,172	1,398	1,373	728
Flexural Strength at yield, 23 ℃, 1/8in (psi)	7,052	7,098	7,307	7,195	7,075	7,099
							Standard deviation (psi)	23	35	35	44	29	50
Tensile Strength at yield, 23 ℃, 1/8in (psi)	4,826	4,867	4,936	4,910	4,824	4,814
							Standard deviation (psi)	13.0	11.4	25.8	19.4	19.7	32.5
Tensile Strength at Break, 23 ℃, 1/8in (psi)	4,541	4,472	4,601	4,665	4,607	4,575
							Standard deviation (psi)	67.4	105.8	88.7	62.0	60.2	153.4
Elongation at break, 23 ℃ (%)	215.86	212.81	196.47	232.73	216.67	206.02
							Standard deviation (%)	26.76	33.25	33.81	9.92	18.80	80.46

[0100] While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

[0101] All patents, patent applications, and other references cited herein are incorporated by reference in their entirety.

Claims (31)

1. A method of making a thermoplastic composition comprising:

melt-blending to form a first intimate blend comprising,

a poly (arylene ether);

poly (alkenyl aromatic) resins;

a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and

an unhydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene; and

melt-blending to form a second intimate blend comprising,

a first intimate blend; and

a polyolefin.

2. The method of claim 1, wherein the melt blending to form the first intimate blend comprises heating to a temperature of from 80 ℃ to 400 ℃.

3. The method of claim 1, wherein the melt blending to form the first intimate blend comprises mixing with at least two mixing elements.

4. The method of claim 1, wherein melt blending to form the first intimate blend and melt blending to form the second intimate blend together comprise mixing with a mixing energy input of at least 0.20 kW-hr/kg.

5. The method of claim 1 having a throughput of at least 10 kg/hr.

6. The process of claim 1, wherein the first intimate blend further comprises a polyolefin in an amount not exceeding the amount of polyolefin added during formation of the second intimate blend.

7. The method of claim 1, wherein the first intimate blend comprises 10 to 59 weight percent, based on the total weight of the composition, of the poly (arylene ether).

8. The method of claim 1, wherein the poly (alkenyl aromatic) resin comprises at least 25 weight percent structural units derived from an alkenyl aromatic monomer of the formula:

wherein R is¹Is hydrogen, C₁～C₈Alkyl or halogen; z is vinyl, halogen, or C₁～C₈An alkyl group; and p is 0 to 5.

9. The method of claim 1, wherein the poly (alkenyl aromatic) resin comprises at least one poly (alkenyl aromatic) resin selected from the group consisting of atactic homopolystyrenes, syndiotactic homopolystyrenes, rubber-modified polystyrenes, and mixtures comprising at least one of the foregoing poly (alkenyl aromatic) resins.

10. The method of claim 1, wherein the first intimate blend comprises 1 to 46 weight percent of a poly (alkenyl aromatic) resin, based on the total weight of the composition.

11. The process of claim 1, wherein the hydrogenated block copolymer comprises:

(A) at least one block derived from an alkenyl aromatic compound of the formula,

wherein R is²And R³Each independently represents a hydrogen atom, C₁～C₈Alkyl radical, C₂～C₈An alkenyl group; r⁴And R⁸Each represents a hydrogen atom, C₁～C₈An alkyl group, a chlorine atom or a bromine atom; and R is⁵～R⁷Each independently represents a hydrogen atom, C₁～C₈Alkyl radicals or C₂～C₈Alkenyl radical, or R⁴And R⁵Taken together with the central aromatic ring to form a naphthyl radical, or R⁵And R⁶Taken together with the central aromatic ring to form a naphthyl group; and

(B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturation content in block (B) is reduced by hydrogenation.

12. The process of claim 1, wherein the hydrogenated block copolymer has an alkenyl aromatic content of 40 to 90 weight percent.

13. The thermoplastic composition of claim 1, wherein the hydrogenated block copolymer comprises a styrene- (ethylene-butylene) -styrene triblock copolymer.

14. The process of claim 1, wherein the first intimate blend comprises from 1 to 20 weight percent hydrogenated block copolymer, based on the total weight of the composition.

15. The method of claim 1, wherein the unhydrogenated block copolymer comprises a styrene-butadiene diblock copolymer or a styrene-butadiene-styrene triblock copolymer.

16. The process of claim 1, wherein the first intimate blend comprises from 1 to 20 weight percent unhydrogenated block copolymer, based on the total weight of the composition.

17. The process of claim 1 wherein the polyolefin comprises a homopolymer or copolymer having at least 80 weight percent of units derived from polymerization of ethylene, propylene, butene, or mixtures thereof.

18. The method of claim 1, wherein the polyolefin comprises homopolypropylene.

19. The process of claim 1 wherein the second intimate blend comprises 10 to 60 weight percent polyolefin, based on the total weight of the composition.

20. The method of claim 1, wherein the first intimate blend and/or the second intimate blend further comprises a polypropylene-polystyrene copolymer selected from the group consisting of graft copolymers, diblock copolymers, multiblock copolymers, star block copolymers, and combinations comprising at least one of the foregoing polypropylene-polystyrene copolymers.

21. The method of claim 20, wherein the polypropylene-polystyrene copolymer is present in an amount of 0.5 to 30 weight percent, based on the total weight of the composition.

22. The process of claim 1, wherein the first intimate blend and/or the second intimate blend further comprises an ethylene/alpha-olefin elastomeric copolymer.

23. The process of claim 22 wherein the ethylene/alpha-olefin elastomeric copolymer is ethylene-butene rubber, ethylene-propylene rubber, or mixtures thereof.

24. The process of claim 22 wherein the ethylene/α -olefin elastomeric copolymer is present in an amount of from 1 to 20 weight percent, based on the total weight of the composition.

25. The method of claim 1, wherein the second intimate blend further comprises at least one reinforcing filler.

26. The method of claim 25, wherein the second intimate blend further comprises a graft copolymer comprising a polyolefin backbone and polar arms formed from one or more cyclic anhydrides.

27. The method of claim 1, further comprising blending the second intimate blend with at least one reinforcing filler.

28. The method of claim 1, further comprising blending the second intimate blend with at least one reinforcing filler and a graft copolymer comprising a polyolefin backbone and polar arms formed from one or more cyclic anhydrides.

29. The method of claim 25 or 27, wherein the reinforcing filler is selected from the group consisting of glass fibers, talc, quartz fibers, carbon fibers, potassium titanate fibers, silicon carbide fibers, boron carbide fibers, gypsum fibers, alumina fibers, iron fibers, nickel fibers, copper fibers, wollastonite fibers, poly (ether ketone) fibers, polyimide benzoxazole fibers, poly (phenylene sulfide) fibers, polyester fibers, aromatic polyamide fibers, aromatic polyimide fibers, aromatic polyetherimide fibers, acrylic fibers, polyvinyl alcohol fibers, polytetrafluoroethylene fibers, and combinations comprising at least one of the foregoing reinforcing fillers.

30. The method of claim 25 or 27, wherein the reinforcing filler is glass fiber.

31. The method of claim 1, wherein the first intimate blend and/or the second intimate blend further comprises an additive selected from the group consisting of: stabilizers, mold release agents, processing aids, flame retardants, drip retardants, nucleating agents, ultraviolet blocking agents, dyes, pigments, antioxidants, antistatic agents, and combinations comprising at least one of the foregoing additives.