WO2009128825A1

WO2009128825A1 - Polyether ether ketone / polyphenylene sulfide blend

Info

Publication number: WO2009128825A1
Application number: PCT/US2008/060613
Authority: WO
Inventors: Manoj Ajbani; Andrew Auerbach; Ke Feng
Original assignee: Ticona, Llc
Priority date: 2008-04-17
Filing date: 2008-04-17
Publication date: 2009-10-22

Abstract

This invention relates to a melt-processed polymeric composition having a combination of properties retained after extended heat aging at elevated temperatures. The present invention more specifically discloses a polymeric composition which is comprised of melt processed product of (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and an alkoxysilane. The product resulting therefrom contains a graft copolymer of the polyarylene sulfide resin and/or the polyaryl-ether-ketone resin. These polymeric compositions can be made by reacting an alkoxy silane with the polyarylene sulfide resin and the polyaryl-ether-ketone resin at elevated temperates, in the melt phase to produce the graft copolymer. It is normally preferred for the alkoxy silane to be an amino silane. The subject invention further reveals shaped articles, e.g., an insulated wire comprising (1) an electrical conductor and (2) a layer of polymeric composition surrounding the electrical conductor, wherein the polymeric composition is comprised of (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and (c)a graft copolymer of the polyarylene sulfide resin and the polyaryl-ether-ketone resin.

Description

POLYETHER ETHER KETONE / POLYPHENYLENE SULFIDE BLEND

Background of the Invention

Wires that are used in applications that involve exposure to high temperatures are typically coated with relatively expensive polymers, such as fluoropolymers or polyether ether ketone (PEEK). Less expensive polymers normally fail to provide the combination of physical properties, chemical resistance, and thermal resistance that are demanded in such applications. For instance, polyphenylene sulfide (PPS), a specific type of polyarylene sulfides, possesses many of the needed characteristics for utilization in coating wires, but has a maximum continuous use temperature (CUT) of only about 170°C. More specifically, PPS offers excellent solvent, chemical, and heat resistance. It also possesses high strength, stiffness and low elongation at yield and break. However, PPS cannot be used in coating wires that are utilized in applications involving exposure to high temperatures without compromising the maximum continuous use temperature of the wire.

United States Patent 6,608,136 discloses a polyphenylene sulfide alloy composition for wire and cables that comprises 40 to 90% by weight of PPS, about 1 to about 20 % of an ethylene based grafting agent with grafting groups selected from unsaturated epoxide, unsaturated isocyanate, silane, or an oxazoline, and another ethylene copolymer with carboxylic acid containing groups. However, such compositions do not provide adequate high temperature resistance for utilization in many wire coating applications.

United States Patent 4,421 ,588 discloses a plastics alloy for a bearing material comprising polyphenylene sulphide and polyether ether ketone. The alloy is formed by powder mixing, melt blending or solvent blending and applied to a metal backing either as a sheet, or in solution or in powder form. The alloy is heated and roll bonded to the backing.

United States Patent 4,684,699 discloses an alloy comprising from about 2 to about 98 weight percent of a poly(arylene sulfide) and from about 98 to about 2 weight percent of a crystalline poly(aryl ether ketone).

United States Patent 4,690,972 discloses compositions comprising a poly(arylene sulfide) which crystallizes to a fine-grained crystalline morphology. A method is also provided for treating compositions comprising a poly(arylene sulfide) by incorporation of a crystalline morphology altering additive, heating the resulting mixture above the melting point of the poly(arylene sulfide) and cooling the mixture at a rate of less than 50⁰C per minute.

United States Patent 5,095,078 discloses a heat-resistant film obtained by biaxially-stretching a composition which comprises (A) 50-90 parts by weight of a polyether ether ketone having predominant recurring units of the formula:

and (B) 50-10 parts by weight of a substantially linear poly(arylene sulfide) having melt viscosity of at least 1 ,000 poises. A production process of such a heat- resistant film is also disclosed, which comprises biaxially stretching the above composition in a temperature range at least equal to the crystallization temperature (Tc) of the poly(arylene sulfide) but not higher than the crystallization temperature (Tc) of the polyether ether ketone.

United States Patent 5,223,585 discloses a heat-resistant film obtained by biaxially-stretching a composition which comprises (A) 50-90 parts by weight of a polyether ether ketone having predominant recurring units of the formula:

and (B) 50-10 parts by weight of a substantially linear poly(arylene sulfide) having melt viscosity of at least 1 ,000 poises. United States Patent 5,286,814 discloses a heat-resistant stretched film that is obtained by stretching a resin composition comprising 100 parts by weight of a poly(arylene sulfide) of a substantially linear structure and 5 to less than 100 parts by weight of a melt-stable poly(arylene thioether-ketone).

United States Patent 5,079,290 describes a blend of polyarylene sulfide and polyetherether ketone at a low level up to 3 % by weight for increased nucleation. The patent does not suggest that the upper use temperature of polyarylene sulfide can be increased by this small addition of polyarylene ether ketone.

United States Patent 4,935,473 describes a composition comprising 100 parts of polyphenylene sulfide and a small amount of another thermoplastic polymer that includes a polyarylether ketone. The patent does not teach that the upper use temperature can be increased by higher PEEK additions and by using a PPS of higher sodium end group concentration. United States Patent 5,256,715 describes a polyarylene sulfide composition containing one azidosilane compound and an optional nucleating agent. Unfortunately, the levels required for nucleation are small and do not suggest the increase the continuous use temperature of the polyarylene sulfide.

United States Patent 5,300,552 describes a polyarylene sulfide composition with a polyether ether ketone included as a nucleating agent at levels of up to 2% by weight. At these low amounts of polyether ether ketone (PEEK), an increase in the upper use temperature of the polyarylene sulfide is not possible.

United States Patent 5,352768 describes a process for producing polyarylene sulfide polymer. Addition of PEEK at less than 1% is suggested for facilitating nucleation which is considered ineffective in increasing the upper use temperature of PPS and improving the tensile strength of the blend of polyarylene sulfide and polyether ether ketone.

There is currently a need for a less expensive polymer composition for coating wires that are used in applications that involve exposure to high temperatures for extended periods of time. Such a composition should possess good tensile properties, modulus, chemical resistance, and flexibility in addition to good thermal characteristics, as exemplified by a high continuous use temperature. It would be particularly desirable to utilize poly-aryl-ether-ketone in amounts that are high enough to improve the continuous use temperature, yet not high enough to increase the cost appreciably. It is also important for such a polymeric composition to be capable of being processed using standard wire coating procedures and equipment.

Summary of the Invention This invention relates to a melt-processed polymeric composition resulting in improved retention of properties rendering it well-suited for shaped articles exposed to high temperatures for extended periods of time in-service. These properties include good tensile strength, modulus, chemical resistance, and flexibility as well as good thermal characteristics.

The present invention more specifically discloses a melt-processed polymeric composition prepared by combining (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and certain organofunctional silanes wich undergoes a chemical reaction under heat and shear to form a graft copolymer of the polyarylene sulfide resin and/ or polyaryl-ether-ketone resin. The particular polyarylene sulfide resins suitable for obtaining surprising results will contain metal endgroup content of greater than about 270 ppm. For example, in one particular embodiment, the metal endgroup content can be from 270 ppm to 399 ppm. In addition to metal endgroup content, the polyarylene sulfide resin selected for use in the polymeric composition contains a total residual chlorine content from about 300 ppm to about 1200 ppm.

The subject invention further reveals an insulated wire comprising (1) an electrical conductor, and (2) a layer of a polymeric composition surrounding the electrical conductor, wherein the polymeric composition is comprised of (a) polyarylene sulfide resin, (b) polyaryl-ether-ketone resin, and (c) a graft copolymer of the polyarylene sulfide resin and the polyaryl-ether-ketone resin.

The present invention also discloses a polymeric composition exhibiting a continuous phase and discontinuous phase. In some embodiments, the continuous phase is comprised of (a) a polyarylene sulfide resin, and in other embodiments, the continuous phase comprises (b) a polyaryl-ether-ketone resin. The resulting graft polymer of (a) and/or (b) is essential in the ability to form a homogenous mass and is believed to represent polyarylene sulfide chains having polyaryl-ether- ketone chains grafted thereto, and/or the reaction product of polyaryl-ether-ketone and an alkoxysilane.

The present invention further discloses a process for preparing a shaped article by molding, spinning, and extrusion methods which comprises subjecting the starting materials to heat and shear in the melt-phase to form a uniform reaction mixture. The reaction mixture is capable of injection molding, extrusion, spinning to form improved shaped articles. The polymeric composition resulting from melt-processing conditions comprises (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and (c) a graft copolymer of the polyarylene sulfide resin and/or the polyaryl-ether-ketone resin formed by reaction of an organosilane. The present invention further discloses a coated metal body comprising a metal base or a metal base having an undercoat of an inorganic and/or organic material and at least one coating layer formed on the metal base or the undercoat, wherein the coating layer has a thickness which is within the range of 5 μm to 1000 μm, and where in coating layer is comprised of a polymeric composition which is comprised of (a) polyarylene sulfide resin, (b) polyaryl-ether-ketone resin, and (c) a graft copolymer of the polyarylene sulfide resin and the polyaryl-ether-ketone resin.

The present invention further discloses a polymeric composition which is comprised of (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and a graft copolymer of (a) and (b) wherein said graft copolymer has a graftlinking group comprising a residue selected from (i), (ii) and (iii), wherein:

(i) has the structure:

R H R^1~?^~~~? ^0Ti(A>a^(B)b^(C) _c

R² H wherein R and R¹ can be the same or different and represent a monovalent alky!, alkenyl, alkynyl, aralkyl, aryl or alkaryl group of 1 to 20 carbon atoms, or an ether substituted derivative thereof, or a halogen, wherein R² represents a monovalent alkyl, alkenyl, alkynyl, aralkyl, aryl or alkaryl group of 1 to 20 carbon atoms, or an ether substituted derivative thereof, or an oxy derivative or an ether substituted oxy derivative thereof or a halogen, wherein A, B and C represent a monovalent aroxy group, a thioaroxy group, a diester phosphate group, a diester pyrophosphate group, a oxyalkylamino group, a sulfonyl group, or a carboxyl group, wherein a, b, and c represent integers, and wherein the sum of a, b, and c is 3; (ii) has the structure:

(R¹-O-)_y-X-(-O-R²-W)_z

wherein each R¹ represents an alkyl radicals having from 1 to 8 carbon atoms, wherein R² represents a divalent radical selected from the group consisting of alkylenes having 1 to 15 carbon atoms, arylene and alkyl substituted arylene groups having 6 to 10 carbon atoms, wherein W represents an epoxy group; wherein y represents an integer of from 1 to 3, wherein z represents an integer from 1 to 3, wherein the sum of y and z equals 4, and wherein X represents titanium or zirconium; and (iii) has the structure:

Z-AIk-S_n -AIk-Z (I) in which Z is selected from the group consisting of

R1 R1 R²

— Si-R¹ — Si-R ² , and — a— R²

R² R2 R2 where R¹ is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; wherein R² is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; and wherein AIk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8.

Brief Description of the Drawings Figure 1 is a graphical representation of the results obtained in Examples 4 through 8.

Detailed Description of the Invention The polyarylene sulfide resins that can be used in the present invention are comprised of repeating units represented by the formula: -(-Ar-S-)- wherein Ar is an arylene group. Such unfilled or unreinforced polyarylene sulfides are characterized by having excellent high temperature properties. The thermal resistance properties of polyarylene sulfide are improved by the practice of the invention, in particular increases in the thermal endurance of the polyarylene sulfide compositions are exhibited which is critical for expanding their performance envelope, without increasing the cost substantially. The polyarylene sulfide resins that are suitable in this invention should have a metal end group content of greater than about 270 ppm, such as from 270 ppm to 2,000 ppm or greater. In one particular embodiment, the metal endgroup content is from 270 ppm to 399 ppm. The metal end group content of the polyarylene sulfide resin is important in one aspect of the invention exhibiting extraordinary property improvements at relatively lower amounts of the polyaryl-ether-ketone resin, as explained below. For example, in certain embodiments, the polymer composition may contain the polyaryl-ether-ketone resin in amounts less than about 40% by weight of the total composition, while containing the polyarylene sulfide resin as the continuous phase in an amount present of greater than about 60% by weight. The polyarylene sulfide resin will typically have a metal endgroup wherein the metal is an alkali metal selected from the group consisting of sodium, lithium, and potassium. It is typically preferred for the metal end group to be a sodium end group. United States Patent 5,625,002 describes the process for providing desired levels of sodium end groups by means of different washing techniques. The teachings of United States Patent 5,625,002 are incorporated by reference herein in their entirety. For purposes of this invention , metal end group contents are measured by the Inductively Coupled Plasma-Optical Emission Spectroscopy technique used on samples of the polyarylene sulfide that have been digested in a mixture of nitric acid and sulfuric acid as known to persons skilled in the arts.

Examples of arylene groups that can be present in the polyarylene sulfide resin include p-phenylene, m-phenylene, o-phenylene and substituted phenylene groups (wherein the substituent is an alkyl group preferably having 1 to 5 carbon atoms or a phenyl group), p,p'-diphenylene sulfone, p,p'-biphenylene, p,p'- diphenylene ether, p,p'-diphenylenecarbonyl and naphthalene groups.

Although an arylene sulfide homopolymer constituted of the same repeating units among the arylene sulfide groups described above may be used in the present invention, the use of a copolymer constituted of a plurality of repeating units different from each other is preferable in some cases with respect to the processability of the resulting composition. In particular, a homopolymer composed of p-phenylene sulfide repeating units having a high degree of linearity is preferably used.

The copolymer to be used in the present invention may be any one constituted of two or more repeating units selected from among the arylene sulfide units mentioned above. In particular, a copolymer comprising p-phenylene sulfide units and m-phenylene sulfide units is preferably used. More particularly, it is suitable with respect to heat resistance, moldability, mechanical characteristics and so on to use a copolymer having a high degree of linearity which is comprising at least 60 mole percent, preferably at least 70 mole percent of p-phenylene sulfide units. Further, it is preferable that the copolymer contain 5 to 40 mole percent, still preferably 10 to 25 mole percent of m-phenylene sulfide units. The polyphenylene sulfide resin can be a block copolymer.

The polyarylene sulfide resin that can be used in practice of the present invention may be a polymer having improved molding processability by crosslinking a relatively low-molecular polymer oxidatively or thermally to increase its melt viscosity, or a polymer having a high degree of linearity prepared by the polycondensation of a monomer component mainly comprising a difunctional monomer. In many cases, the latter polymer is superior to the former with respect to the physical properties of the resulting molded article. According to the present invention, a resin composition may be used which is prepared by blending a crosslinked polyarylene sulfide resin prepared from a monomer having at least three functional groups as a part of the monomer component with the polymer having a high degree of linearity as described above. Polyphenylene sulfide resins are considered to have a high degree of linearity in cases where they exhibit a complex melt viscosity of less than 13,000 poise at 310°C and 0.1 rad/sec. It is preferred for polyphenylene sulfide resins having a high degree of linearity to exhibit a complex melt viscosity of less than 13,000 poise at 310⁰C and 0.1 rad/sec. For purposes of this invention the melt viscosity of the polyphenylene sulfide resin can be determined with an ARES® strain- controlled rheometer (from TA Instruments) operated in dynamic (oscillatory) shear mode using parallel plate geometery with 25 mm disks and a frequency of 0.1 rad/sec at 310⁰C. For a PPS having a high degree of linearity as defined above per the ARES® rheometer, the corresponding melt viscosity as measured in a capillary rheometer at 31 O⁰C, 1200 1/s shear rate will be preferably below 6500 poise.

The polyarylene sulfides that are useful in the practice of this invention include polyarylene thioethers containing repeat units of the formula:

-[(Ar¹)_n-X]_rn-[(Ar²),-Y]_r(Ar³)_k-Z]_l-[(Ar⁴)o-W]p-

wherein Ar¹, Ar², Ar³, and Ar⁴ are the same or different and are arylene units of 6 to 18 carbon atoms; W, X, Y, and Z are the same or different and are bivalent linking groups selected from -SO₂-, -S-, -SO-, -CO-, -O-, -COO- or alkylene or alkylidene groups of 1 to 6 carbon atoms and wherein at least one of the linking groups is -S-; and n, m, i, j, k, I, o, and p are independently zero or 1 , 2, 3, or 4, subject to the proviso that their sum total is not less than 2. The arylene units Ar¹, Ar², Ar³, and Ar⁴ may be selectively substituted or unsubstituted. Advantageous arylene systems are phenylene, biphenylene, naphthylene, anthracene and phenanthrene. The polyarylene sulfide typically includes at least 30 mole percent, particularly at least 50 mole percent and more particularly at least 70 mole percent arylene sulfide (-S-) units. Preferably the polyarylene sulfide polymer includes at least 85 mole percent sulfide linkages attached directly to two aromatic rings. Advantageously the polyarylene sulfide polymer is polyphenylene sulfide (PPS), defined herein as containing the phenylene sulfide structure -(CeH₄-S)_n- (wherein n is an integer of 1 or more) as a component thereof.

The polyarylene sulfide resin used in the practice of this invention will typically be polyphenylene sulfide. Synthesis techniques that can be used in making polyphenylene sulfide resins that are suitable for utilization in the practice of this invention are described in United States Patent 4,814,430, United States Patent 4,889,893, United States Patent 5,380,783, and United States Patent 5,840,830, the teachings of which are incorporated herein by reference in their entirety. The polyarylene sulfide resin can be washed with a liquid media. For instance, the polyarylene sulfide resin can optionally be washed with water, acetone, N-methyl-2-pyrrolidone (NMP), a salt solution, an acedic media, such as acetic acid or hydrochloric acid. The polyarylene sulfide resin will typically be washed in a sequential manner that is generally known to persons skilled in the prior art. Washing with an acidic solution or a salt solution may further reduce the sodium, lithium or calcium metal ion end group concentration from about 2000 ppm to about 100 ppm. United States Patent 5,625,002 describes several methods of washing PPS. The teachings of United States Patent 5,626,002 are incorporated herein by reference in their entirety. Typically, washing with acid or a salt solution will lower the sodium end group concentration. The PPS that is unwashed with acid or a salt solution is highly preferred.

The polyarylene sulfide thermoplastic resin that can also be used in this invention can be semi-linear, branched or slightly crosslinked. A process that can be used in making semi-linear polyarylene sulfide is described in United States Patent 3,354,129, United States Patent 3,919,177, United States Patent 4,371 ,671 , and United States Patent 4,368,321 the teachings of which are incorporated herein by reference in their entirety. The polyaryl-ether-ketones that are useful in the practice of this invention include polyetherketones (PEK), polyetheretherketones (PEEK), and polyetherketoneketone (PEKK). The preparation of such polymers is described in United States Patent 5,288,834, United States Patent 5,344,914, United States Patent 5,442,029, United States Patent 4,684,699, United States Patent 4,690,972, United States Patent 6,538,098, United States Patent 6,566,484,

United States Patent 6,881 ,816, United States Patent 7,034,187, and UK Patent Application 2,355,464. The teachings of these patents are incorporated herein by reference with respect to teaching techniques for synthesizing polyaryl-ether- ketone resins that can be utilized in the practice of this invention. The alkoxy silanes that are useful in this invention are described in United

States Patent 5,149,731 , the teachings of which are incorporated herein by reference in their entirety. The alkoxysilane compound is at least one silane compound selected from the group consisting of a vinlyalkoxysilanes, epoxyalkoxysilanes, aminoalkoxysilanes, and mercaptoalkoxysilanes. Examples of the vinylalkoxysilane that can be utilized include vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris(β-methoxyethoxy)silane. Examples of the epoxyalkoxysilanes that can be used include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. Examples of the mercaptoalkoxysilanes that can be employed include y- mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

Amino silanes are a preferred class of alkoxy silanes that can be used in the practice of this invention. The amino silane compounds that can be used in the compositions of this invention are typically of the formula: R¹-Si-(R²)3, wherein R¹ is selected from the group consisting of an amino group such as NH₂; an aminoalkyl of from about 1 to about 10 carbon atoms, preferably from about 2 to about 5 carbon atoms, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl, and the like; an alkene of from about 2 to about 10 carbon atoms, preferably from about 2 to about 5 carbon atoms, such as ethylene, propylene, butylene, and the like; and an alkyne of from about 2 to about 10 carbon atoms, preferably from about 2 to about 5 carbon atoms, such as ethyne, propyne, butyne and the like; and wherein R² is an alkoxy group of from about 1 to about 10 atoms, preferably from about 2 to about 5 carbon atoms, such as methoxy, ethoxy, propoxy, and the like. In a preferred embodiment, in the amino silane compound of the R¹-Si-(R²)₃, R¹ is selected from the group consisting of aminomethyl, aminoethyl, aminopropyl, ethylene, ethyne, propylene and propyne, and R² is selected from the group consisting of methoxy groups, ethoxy groups, and propoxy groups.

It is typically preferred for the amino silane compound to be of the formula: R³-Si-(R⁴)3 wherein R³ is an amino group such as NH₂ or an aminoalkyl of from about 1 to about 10 carbon atoms such as aminomethyl, aminoethyl, aminopropyl, aminobutyl, and the like, and wherein R⁴ is an alkoxy group of from about 1 to about 10 atoms, such as methoxy groups, ethoxy groups, propoxy groups, and the like. It is also preferred for the amino silane to be of the formula: R⁵-Si-(R⁶)₃ wherein R⁵ is selected from the group consisting of an alkene of from about 2 to about 10 carbon atoms such as ethylene, propylene, butylene, and the like, and an alkyne of from about 2 to about 10 carbon atoms such as ethyne, propyne, butyne and the like, and wherein R⁶ is an alkoxy group of from about 1 to about 10 atoms, such as methoxy group, ethoxy group, propoxy group, and the like. The amino silane can be a mixture of various compounds of the formula R¹-Si-(R²)3, R³-Si- (R⁴)₃, and R⁵-Si-(R⁶)₃.

Some representative examples of amino silane compounds that can be used include aminopropyl triethoxy silane, aminoethyl triethoxy silane, aminopropyl trimethoxy silane, aminoethyl trimethoxy silane, ethylene trimethoxy silane, ethylene triethoxy silane, ethyne trimethoxy silane, ethyne triethoxy silane, aminoethylaminopropyltrimethoxy silane, 3-aminopropyl triethoxy silane, 3- aminopropyl trimethoxy silane, 3-aminopropyl methyl dimethoxysilane or 3- aminopropyl methyl diethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, N-methyl-3-aminopropyl trimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, bis(3-aminopropyl) tetramethoxy silane, bis(3-aminopropyl) tetraethoxy disiloxane, and combinations thereof. The amino silane can also be an aminoalkoxysilane, such as γ-aminopropyltrimethoxysilane, y- aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, y- aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ- aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, y- diallylaminopropyltrimethoxysilaπe and y-diallylaminopropyltrimethoxysilane. A highly preferred amino silane is 3-aminopropyltriethoxysilane which is available from Degussa, Sigma Chemical Company, and Aldrich Chemical Company. The polymeric composition of this invention will typically be made by blending and reacting from 5 weight percent to 90 weight percent of the polyarylene sulfide, from 5 weight percent to 90 weight percent of the polyetherether ketone, and from 0.1 weight percent to 5 weight percent of a graftlinking agent, such as an alkoxy silane compound. It is normally preferred for the polymeric compositions of this invention to be made by blending 18 weight percent to 83 weight percent of the polyarylene sulfide, from 15 weight percent to 80 weight percent of the polyetherether ketone, and from 0.2 weight percent to 2 weight percent bf the alkoxy silane. It is generally more preferred for the polymeric blends of this invention be made by blending 24 weight percent to 74 weight percent of the polyarylene sulfide, from 25 weight percent to 75 weight percent of the polyetherether ketone, and from 0.3 weight percent to 1 weight percent of the alkoxy silane compound. The alkoxy silane will typically be amino silane. The polymer blends of this invention will typically contain at least 5 weight percent of the polyarylene sulfide to result in an appreciable cost savings. Lesser amounts of the polyarylene sulfide can be used with the significant disadvantage of the cost savings not being realized due to the correspondingly high level of the polyetherehter ketone that will be needed. On the other side of the coin the compositions of this invention will include at least 5 weight percent of the polyaryl- ether-ketone resin to effectuate an increase in continuous use temperature that is commercially useful. The polymeric blends of this invention will typically have a polyarylene sulfide phase glass transition temperature which is within the range of 1 19°C to 125°C, when measured by the Dynamic Analyzer technique.

In one embodiment, the polyarylene sulfide resin can be selected based upon metal endgroup content so as to minimize the amount of the polyaryl-ether- ketone resin. In fact, the present inventors unexpectedly discovered that by carefully controlling the metal endgroup content of the polyarylene sulfide resin, polymeric compositions can be made according to the present disclosure that not only have reduced amounts of polyaryl-ether-ketone resin but also exhibit excellent retention of strength properties when exposed to relatively high temperatures for prolonged lengths of time. For example, in one embodiment, the polymer composition may contain the polyaryl-ether-ketone resin in an amount from about 15% to about 40% by weight, such as in an amount from about 20% to about 35% by weight. In this embodiment, the polyarylene sulfide resin can be present in an amount from about 60% to about 85% by weight, such as from about 65% to about 80% by weight. The reactive compound, e.g., alkoxy silane, on the other hand, is generally present in an initial amount sufficient to form the graft reaction product and is less than about 2% by weight, such as from about 0.2% to about 2% by weight of initial ingredients combined, such as from about 0.3% to about 1 % by weight of the total starting ingredients.

As described above, polymer compositions made according to the present disclosure can exhibit excellent tensile strength, even after being subjected to high temperatures for prolonged periods of time. Of particular advantage, the present inventors discovered that controlling the metal endgroup content of the polyarylene sulfide resin as described above has surprising effects on the tensile retention properties of the resulting polymer composition even at low levels of polyaryl-ether- ketone resin. For example, in one embodiment, the polymer composition may exhibit at least 75% tensile strength retention after 500 hours of aging at 230^cC (based upon the original tensile strength of the polymer). In other embodiments, the polymer composition may exhibit greater than 85% tensile retention, such as greater than 90% tensile retention after 500 hours at 230⁰C.

The actual tensile strength of the polymer composition after 500 hours at 230⁰C, for instance, may be greater than about 55 MPa, such as greater than about 60 MPa, such as even greater than about 70 MPa in one particular application.

Per the preferred embodiments, the alkoxy silane reacts with the polyaryl- ether-ketone resin under melt-processing conditions of elevated temperature and mechanical shear to make a polymeric reaction product. In the absence of the reaction between the silane with the polyarylene sulfide and/or polyaryl-ether ketone under melt-processing conditions, a homogeneous mass is not obtainable, and loss of initial physical properties after heat aging increases. Accordingly, the melt-processed blends of this invention can contain the reaction product of the alkoxy silane with the polyaryl-ether-ketone resin. The melt-processed blends of this invention can also contain polyarylene sulfide chains having polyaryl-ether- ketone chains grafted thereto. For instance, the polymeric blends of this invention can contain (a) from 15 weight percent to 80 weight percent of a polyarylene sulfide resin, (b) from 10 weight percent to 75 weight percent of a polyaryl-ether- ketone resin, and (c) from 2 weight percent to 40 weight percent of polyarylene sulfide chains having polyaryl-ether-ketone chains grafted thereto. Such compositions will typically be comprised of (a) from 30 weight percent to 70 weight percent of a polyarylene sulfide resin, (b) from 15 weight percent to 65 weight percent of a polyaryl-ether-ketone resin, and (c) from 5 weight percent to 20 weight percent of polyarylene sulfide chains having polyaryl-ether-ketone chains grafted thereto Such compositions will more typically contain (a) from 35 weight percent to 60 weight percent of a polyarylene sulfide resin, (b) from 20 weight percent to 60 weight percent of a polyaryl-ether-ketone resin, and (c) from 5 weight percent to 10 weight percent of polyarylene sulfide chains having polyaryl-ether-ketone chains grafted thereto.

The polymeric compositions of this invention are valuable in a wide variety of applications where high tensile strength, high modulus, good chemical resistance, flexibility and good thermal characteristics are desired. For instance, the polymeric compositions of this invention are particularly valuable in coating wires to make insulated wires for electrical applications. Insulated wires can be manufactured with the polymeric compositions of this invention using conventional equipment and standard extrusion coating techniques. Such techniques typically involve feeding a bare wire of a good electrical conductor, such as copper or aluminum, through a straightener and a preheater into a cross-head die. The heated wire is coated in the cross-head die and is then typically fed into a water bath to cool it prior to being collected on a spool.

Tubing type cross-head dies that can be used in the practice of this invention are described by United States Patent 4,588,546. The teachings of United States Patent 4,588,546 are incorporated herein by reference for the purpose of describing the kinds of tubing type cross-head dies and the general procedures that can be utilized in coating wires to make insulated wires in accordance with this invention. In such procedures the bare wire is normally preheated to a temperature which is above the melting point of the polymeric composition being used to coat the wire to insure that the polymer composition adheres to the wire. After being preheated the bare wire is fed into the back of the cross-head die where it is covered circumferentially with the molten polymeric composition. After exiting the cross-head die the coated wire can be exposed to an air or gas flame for surface annealing and is then rapidly cooled to below the melting point of the polymeric composition. This cooling step is normally carried out in a bath of cold water. The coated wire is subsequently collected on spools as a finished product.

The polymeric composition surrounding the conductor in such an embodiment is comprised of the melt-reaction product of a polyarylene sulfide, a polyaryl-ether-ketone, and an alkoxy silane. The composition may contain graft copolymer of polyarylene sulfide having polyaryl-ether-ketone chains grafted thereto and a reaction product of polyarylene sulfide and an alkoxysilane.

The melt-processed polymeric compositions disclosed can be used neat or with conventional additives, for example organic or inorganic fibers, particulate fillers, other polymers, pigments, nucleating agents and stabilizers. They can be shaped in conventional ways to produce for example fibers, films or granules or more complicated articles. When the polymers are incorporated with fibers of glass or carbon or alumina at a concentration of 5-40% by volume, the resulting composition is especially useful in making articles by injection molding. In such compositions the fibers are of length typically 0.5 to 5.0 mm.

Conventional shaping processes for forming articles out of the melt- processed compositions include, extrusion, injection molding, blow-molding, thermoforming, foaming, compression molding, hot-stamping, fiber spinning and the like which are known. Among the many shaped articles that can be formed, there are structural and non-structural shaped parts, well suited especially for appliance, electrical, electronic, fibrous webs, and automotive engineering thermoplastic assemblies. Exemplary automotive shaped plastic parts are suitable for under the hood applications, including fan shrouds, supporting members, wire and cable jacketing, covers, housings, battery pans, battery cases, ducting, electrical housings, fuse buss housings, blow-molded containers, nonwoven or woven geotextiles, baghouse filters, membranes, pond liners, to name a few. Other useful articles besides moldings, extrusion and fibers include wall panels, overhead storage lockers, serving trays, seat backs, cabin partitions, window covers, electronic packaging handling systems such as integrated circuit trays, to name a few.

Compositions of this invention are also useful to coat metal bodies. United States Patent 4,910,086 describes the process of preparing such coated articles. The teachings of United States Patent 4,910,086 are incorporated herein by reference in their entirety. The compositions may be further comprised of polyarylene thioether ketone.

United States Patent 4,873,283, United States Patent 4,895,892, United States Patent 4,895,912, United States Patent 4,910,086, United States Patent 4,975,479, and United States Patent 5,095,078 describe the process of making polyaryiene thioether ketone and are incorporated herein by reference. The morphology of the PPS and PEEK phases may be different depending on their relative compositional and melt viscosity ratios. At lower PEEK ratios, the PEEK may be the dispersed phase and at higher PEEK ratios, PEEK may be the continuous phase. At intermediate ratios, the PEEK and PPS phases may be co- continuous. It is desirable for the PEEK to be either the dispersed or the continuous phase. The average domain sizes of the dispersed phases will preferably be lower than 50 microns, more preferably below 10 micron, and most preferably below 3 micron.

The polymeric blends of this invention can be utilized in manufacturing microfibers, long-fibers, long-fiber reinforced plastic structures and multi- component fibers. The blends of this invention can be utilized in manufacturing microfibers utilizing the general technique described by United States Patent 5,695,869, the teachings of which are incorporated herein by reference in their entirety with respect to techniques for manufacturing microfibers. The technique described by United States Patent 6,949,288 can be utilized manufacturing multi- component fibers with the blends of this invention wherein a polymeric blend of this invention is used in conjunction with an isotropic semi-crystalline polyester or a polyolefin resin. The teachings of United States Patent 6,949,288 are incorporated herein by reference for the purpose of teaching techniques for manufacturing multi- component fibers. United States Patent 6,794,032 discloses a technique for manufacturing long-fiber reinforced polyolefin plastic structures wherein the long- fibers utilized have a length of ≥ 3 mm. The teachings of United States Patent 6,794,032 are incorporated herein by reference for the purpose of teaching techniques for making such long-fiber reinforced plastic structures. United States Patent 7,060,326 describes a process for making aluminum conductor composite core reinforced cable. The teachings of United States Patent 7,060,326 are incorporated herein by reference for the purpose of disclosing a method of making such composite cores. Coated metal bodies can be made by substituting the polymeric composition of this invention for the resin coating material used in United States Patent 4,910,086 for making such coated metal bodies. More specifically, such coated metal bodies are comprised of a metal base or a metal base having an undercoat of an inorganic and/or organic material and at least one coating layer formed on the metal base or the undercoat, wherein the coating layer has a thickness of 5 μm to 1000 μm, and wherein the coating layer is comprised of the polymeric composition of this invention. The teaching of United States Patent 4,910,086 are incorporated herein by reference for the purpose of illustrating such coated metal bodies and techniques for making such coated metal bodies. In another embodiment of this invention an organotitanium compound, an organozirconium compound, or an organosilicon compound is utilized in place of the alkoxy silane compound as a graftlinking agent. The graftlinking agent acts in a manner whereby polymeric chains of the polyarylether ketone resin are grafted onto polymeric chains of the polyarylene sulfide resin. Accordingly, this graftlinking reaction results in the formation of a graft copolymer comprising the residue of the polyarylether ketone resin, the polyarylene sulfide resin, and the graftlinking agent (the organotitanium compound, the organozirconium compound, or the organosilicon compound).

The neoalkoxy organotitanates that can be employed in the practice of this invention are of the structural formula:

R H R¹— C— C OTi(A)_a(B)_b(C)_c

R² H wherein R and R¹ can be the same or different and represent a monovalent alkyl, alkenyl, alkynyl, aralkyl, aryl or alkaryl group of 1 to 20 carbon atoms, or an ether substituted derivative thereof, or a halogen, wherein R² represents a monovalent alkyl, alkenyl, alkynyl, aralkyl, aryl or alkaryl group of 1 to 20 carbon atoms, or an ether substituted derivative thereof, or an oxy derivative or an ether substituted oxy derivative thereof or a halogen, wherein A, B and C represent a monovalent aroxy group, a thioaroxy group, a diester phosphate group, a diester pyrophosphate group, a oxyalkylamino group, a sulfonyl group, or a carboxyl group, wherein a, b, and c represent integers, and wherein the sum of a, b, and c is 3. The various R, R¹ and R² may each contain up to three ether oxygen or halogen substituents, provided the total number of carbon atoms for each such R group does not exceed 20, inclusive of the carbon atoms contained in substituent portions. A, B and C may be an aroxy (ArO-), thioaroxy (ArS-), diester phosphate ((R³O)(R⁴O)P(O)O-), diester pyrophosphate ((R³O)(R⁴O)P(O)OP(O)), oxyalkylamino (R⁵R⁶NR⁷O-), sulfonyl (ArS(O)₂ 0-) or carboxyl (RC(O)O-). Each group may contain up to 30 carbon atoms.

Ar, in the above formulas, may be a monovalent aryl or alkaryl group having from 6 to about 20 carbon atoms, optionally containing up to 3 ether oxygen substituents, and substituted derivatives thereof wherein the substitutions are up to a total of three halogens or amino groups having the formula NR⁸R⁹ wherein R⁸ and R⁹ are each hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, a cycloalkyl group having from 3 to 12 carbon atoms, and an aryl group having from 6 to 12 carbon atoms; and R³ and R⁴ may each be the same group as R, R¹ and Ar, R⁵ and R⁶ may be hydrogen, an alkyl or aminoalkyl group having from 1 to 15 carbon atoms and R⁷ may be an alkylene group having from 1 to 6 carbon atoms or an arylene group having from 6 to 10 carbon atoms or a combination thereof; and a+b+c is equal to 3.

Particularly preferred examples of the R, R¹ and R² groups are alkyl having 1 to 8 carbon atoms; aralkyl having 6 to 10 carbon atoms such as benzyl; the aryl and alkaryl groups having from 6 to 10 carbon atoms including phenyl, naphthyl, tolyl, xylyl; and the halogen-substituted bromophenyl; and the allyloxy-substituted alkyl having from 4 to 20 carbon atoms and the allyloxy-substituted aryl having from 9 to 20 carbon atoms. Where R² is an oxy derivative, the most preferred compounds are the alkoxy derivatives having from 1 to 3 carbon atoms and the phenoxy group.

Preferred R³ and R⁴ groups are alkyl groups having 1 to 12 carbon atoms, aryl and alkaryl groups having from 6 to 12 carbon atoms and ether-substituted alkyl having from 3 to 12 carbon atoms.

Examples of specific, R, R¹, R², R³ and R⁴ groups are: methyl, propyl, cyclohexyl, 2,4-dimethoxybenzyl, 1-methyl-4-acenaphthyl-2--ethyl-2-furyl and methallyl. R², in addition, may be methoxy, phenoxy, naphthenoxy, cyclohexene-3- oxy, 4-isobutyl-3-methoxy, 1-phenanthroxy and 2,4,6-trimethylphenoxy.

Examples of A, B and C ligands useful in the practice of this invention are likewise numerous. These include aryl and thioaryl ligands such as phenoxy, 2,4- dimethyl-1-naphthoxy, 3-octyl-1-phenanthroxy and 3,5-diethyl-2-thioanthryl and 2- methyl-3-methoxy thiophenyl as well as diester phosphates such as dibutyl, methylphenyl, cyclohexyl, lauryl and bismethoxyethoxyethyl phosphate and their pyrophosphate analogs as well as aryl sulfonyl groups such as phenylsulfonyl, 2,4- dibutyl-1 -naphthalene sulfonyl and 2-methyl-3-ethyl-4-phenanthryl sulfonyl.

Particularly effective are carboxyl groups such as acetyl, methacryl, stearyl, 4-phenoxy and 4-phenoxy butyl. Some representative examples of the neoalkoxy organotitanates that can be employed in the practice of this invention include: (CHa)₃CCH₂ OTi[OC(O)Ci₇H₃₅I₃, (CHa)₂(C₆H₅)CCH₂OTi(OC₆ Hs)₂[OC(O)C₆ H₅],

(CH3 =C(CH₃)CH₂O)₂(C₂H₅)CCH₂OTi[2SC₆H₄-N-3C₂H₅]₂(OC₆H₄C(CH₃)₂C₆H₅3, (C₆ H₁₁O)(iso-C₁2H₂₅)₂CCH₂OTi[OS(O)₂C₆H₄C₁₂H₂₅]3, (CH₂=CHCH₂O)(C₃H₇)(C₂ H₅)CCH₂OTi[OP(O)(OC4H9)OP(O)(OH)OC₄H9)]3,

(CH₃)(HC=CCH₂O)(C₆H₅)CCH₂ OTi[OP(O)(OC₂H₄OCH₃)(OCH₃)I₂[OC₆H₄-P-C₂H₅], (C₆HiI)(IsO-C₃H₇)(C₄H₉O)CCH₂ OTi[S(O)₂C₆H₄-O-CH₃][SC₆Hs]₂, (CH₃)(C₆HSCH₂O)(C₂H₅)CCH₂OTi[OP(O)(OC₆H₄-P-CH₃)(OC₂ H₄OCH₃)], [OP(O)(OH)OP(O)(OC₃H₇)₂]_2, (C₂H5)(C₃H₇)(CH₂=CHO)CCH₂OTi[OC(O)neo-C₉H₁₇]₃,

[C(CH₃)₂=C(C₆H₅)OCH₂]₂(iso-C₃H₇)CCH₂OTi[OCioH₇][OC(0)CH₂CH₃]_2, (C₂H₅OCH₂)(CH₃)(C₆H₅)CCH₂ OTi[OC₂H₄NHCHa]₃, (CH₃)₂(C₄H9)CCH₂OTi[OC₃H₆N(C₆H5)C₄H_aCioH₇]₂[OC(0)CH₃]. Specific neoalkoxy organotitanates that can be employed in the practice of this invention and methods for the synthesis thereof are disclosed in United States Patent 4,600,789. The teachings of United States Patent 4,600,789 are incorporated by reference herein. The titanium and zirconium compounds that can be utilized in the practice of this invention are of the structural formula:

(R¹-O-)_y-X-(-O-R²-W)_z

wherein each R¹ represents an alkyl radicals having from 1 to 8 carbon atoms, wherein R² represents a divalent radical selected from the group consisting of alkylenes having 1 to 15 carbon atoms, arylene and alkyl substituted arylene groups having 6 to 10 carbon atoms, wherein W represents an epoxy group; wherein y represents an integer of from 1 to 3, wherein z represents an integer from 1 to 3, wherein the sum of y and z equals 4, and wherein X represents titanium or zirconium. Preferably, each R1 is an alkoxy radical having from 1 to 3 carbon atoms, R2 is a divalent radical selected from the group consisting of alkylenes having from 1 to 5 carbon atoms, y is 3, and z is 1 , and X represents titanium. Specific titanium and zirconium compounds that can be employed in the practice of this invention and methods for the synthesis thereof are disclosed in

United States Patent 6,870,064. The teachings of United States Patent 6,870,064 are incorporated by reference herein.

The organosilicon compounds that can be employed in the practice of this invention are of the structural formula:

Z-AIk-S_n -AIk-Z (I)

in which Z is selected from the group consisting of

where R¹ is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; wherein R² is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; and wherein AIk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8.

Specific examples of sulfur containing organosilicon compounds which may be used in accordance with the present invention include: 3,3'- bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(triethoxysilylpropyl) tetrasulfide, 3,3'- bis(triethoxysilylpropyl) octasulfide, 3,3'-bis(trimethoxysilylpropyl) tetrasulfide, 2,2'- bis(triethoxysilylethyl) tetrasulfide, 3,3'-bis(trimethoxysilylpropyl) trisulfide, 3,3'- bis(triethoxysilylpropyl) trisulfide, 3,3'-bis(tributoxysilylpropyl) disulfide, 3,3'- bis(trimethoxysilylpropyl) hexasulfide, 3,3'-bis(trimethoxysilylpropyl) octasulfide, 3,3'-bis(trioctoxysilylpropyl) tetrasulfide, 3,3'-bis(trihexoxysilylpropyl) disulfide, 3,3'- bis (tri-2"-ethylhexoxysilylpropyl) trisulfide, 3,3'-bis(triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis(tri-t-butoxysilylpropyl) disulfide, 2,2'- bis(methoxydiethoxysilylethyl) tetrasulfide, 2,2'-bis(tripropoxysilylethyl) pentasulfide, 3,3'-bis(tricyclonexoxysilylpropyl) tetrasulfide, 3,3'- bis(tricyclopentoxysilylpropyl) trisulfide, 2,2'-bis(tri-2"-methylcyclohexoxysilylethyl) tetrasulfide, bis(trimethoxysilylmethyl) tetrasulfide, 3-methoxy ethoxy propoxysilyl 3'-diethoxybutoxysilylpropyltetrasulfide, 2,2'-bis(dimethyl methoxysilylethyl) disulfide, 2,2'-bis(dimethyl sec.butoyxysilylethyl) trisulfide, 3,3'-bis(methyl butylethoxysilylpropyl) tetrasulfide, 3,3'-bis(di t-butylmethoxysilylpropyl) tetrasulfide, 2,2'-bis(phenyl methyl methoxysilylethyl) trisulfide, 3,3'-bis(diphenyl isopropoxysilylpropyl) tetrasulfide, 3,3'-bis(diphenyl cyclohexoxysilylpropyl) disulfide, 3,3'-bis(dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2,2'-bis(methyl dimethoxysilylethyl) trisulfide, 2,2'-bis(methyl ethoxypropoxysilylethyl) tetrasulfide, 3,3'-bis(diethyl methoxysilylpropyl) tetrasulfide, 3,3'-bis(ethyl di-sec. butoxysilylpropyl) disulfide, 3,3'-bis(propyl diethoxysilylpropyl) disulfide, 3,3'- bis(butyl dimethoxysilylpropyl) trisulfide, 3,3'-bis(phenyl dimethoxysilylpropyl) tetrasulfide, 3-phenyl ethoxybutoxysilyl 3'-trimethoxysilylpropyl tetrasulfide, 4,4'- bis(trimethoxysilylbutyl) tetrasulfide, 6,6'-bis(triethoxysilylhexyl) tetrasulfide, 12,12'- bis(triisopropoxysilyl dodecyl) disulfide, 18,18'-bis(trimethoxysilyloctadecyl) tetrasulfide, 18,18'-bis(tripropoxysilyloctadecenyl) tetrasulfide, 4,4'- bis(trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4'-bis(trimethoxysilylcyclohexylene) tetrasulfide, 5,5'.-bis(dimethoxymethylsilylpentyl) trisulfide, 3,3'-bis(trimethoxysilyl- 2-methylpropyl) tetrasulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide.

The preferred sulfur containing organosilicon compounds are the 3,3'- bis(trimethoxy or triethoxy silylpropyl) sulfides. The most preferred compound is 3,3'-bis(triethoxysilylpropyl) tetrasulfide. Therefore as to formula I₁ preferably Z is

where R² is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; AIk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer of from 3 to 5 with 4 being particularly preferred.

This invention is illustrated by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.

Examples 1-3

Table 1. Compositions and Properties

Example 1 2 3

(Control)

Ingredients

Fortron® 0214B1¹ 60 39.5 100

Victrex® 381 G ² 39.5 60 0

Amino Silane 0.5 0.5 0

Glass Transition (Tg) 1 19.4 122.0 116.7 of PPS phase Distortion Temp°C 136.2 142.9 107.6

(HDT @ 1.8 MPa)

Tensile strength MPa 42.5 89.1 82.2 Tensile strength after 42.7 84.0 58.6 1000 Hr aging @ 200⁰C % Retention 100 94 71

Tensile Elongation % 1.16 3.79 2.81 Tensile Elongation after 11..0099 2.57 1.55 1000 Hr aging at 200°C Notes

1 ) Polyphenylene sulfide having a high degree of linearity and having a measured melt viscosity of 1400 poise (310⁰C, 1200 1/s) and a measured sodium end group concentration of 81 7 parts per million (ppm) The Fortron® 0214B1

PPS utilized in this experiment was manufactured by Fortron Industries and marketed by Ticona Polymers LLC The sodium concentration was measured by Inductively Coupled Plasma-Optical Emission Spectrometry technique by digesting the polymer in a Nitric and Sulfuric acid mixture 2) Medium viscosity polyether ether ketone manufactured by Victrex It has a

MFR of 4 5 g/1 Omin under the condition of 400°C/2 16 kg 3) Dynasylan® AMEO-Pure Silane (3-Amιnopropyltrιethoxysιlane) manufactured by Degussa

The data in Table 1 shows that Examples 1 and 2 have a glass transition temperature that is higher than the Control Example 3 that has 100% PPS, indicating some increased miscibility of the blends to make an alloy The alloys also have a higher heat distortion temperature (HDT) than the Example 3 that contained all PPS The alloys of this invention (Examples 1 and 2) that contain relatively high PEEK amounts and amino silane can be used at higher continuous use temperatures than the control with 100% PPS Such alloys would have industrial utilities as cost-effective alternate materials to a 100% PEEK containing thermoplastic composition Such alloys could also be used to draw fibers, such as mono-filaments and multi-filaments, for preparing woven and non-woven fabrics with increased thermal stability The fibers and filaments could be bicontinuous with the alloy forming the sheath or the core and the other thermoplastic material, such as high temperature nylon, polyester, or liquid crystalline polyester or liquid crystalline polyester-amide, as the core of the sheath material

Examples 4-8

The following test results illustrate the effect of metal endgroup content of the polyarylene sulfide resin on the retention of strength properties of the melt- processed polymer composition The below tests also demonstrate surprising retention of properties for the melt-processed polymer compositions containing relatively low wt % amounts of the polyaryl-ether-ketone resin

The examples provided below in the following tables were prepared by melt mixing in a continuous mixing extruder (Haake® or twin-screw extruder) by feeding the ingredients in the feed throat. Temperatures above the melting point of PEEK, namely, 340 ⁰C, were used to conduct the melt mixing. The extrudates were pelletized and injection molded for obtaining tensile/ impact specimens for physical testing. The acid washed products are produced by the following procedure. A pre- weight amount of FORTRON^® 0320B0 flakes was first mixed with ethanol. The flakes were then filtered and washed with distilled water twice. A preset amount of glacial acetic acid was then added into the flake/distilled water slurry. The slurry was stirred and the reaction times range 40 minutes to 2 hours. After that, the flakes were washed again with distilled water twice before finally deionized water wash. All flakes were dry in an oven at 180 ⁰F for at least 24 hours.

All tensile properties were tested under ISO 527 method. The Sodium contents of PPS and other experimental materials given below are obtained using inductively coupled plasma/optical emission spectrometry (ICP-OES, Vista MPX made by VARIAN). Polymer samples are first digested with concentrated sulfuric acid (94- 98%) and nitric acid (70%) in a closed vessel microwave digester (MARS made by CEM Corporation). The digested sample is diluted with purified water prior to the ICP-OES analysis. The dilution factor is 480. The standard deviation of Na content measurement for this set of experiments is calculated to be 17 ppm.

Table 2. Compositions & Properties: Effect of Na content on property retention

Example 4 5 6 7 8

Control Control

Ingredients

Fortron^® 0214B1¹ 77

Fortron^® 0320B0² 77

Acid washed product 1 77

Acid washed product 2 77

Acid washed product 3 77 Victrex^® 150G ³ 22.5 22.5 22.5 22.5 22.5 Amino Silane ⁴ 0.5 0.5 0.5 0.5 0.5

Sodium (ppm) 40 399 303 282 263 Chlorine (ppm) 600 410 570 560 490

Tensile strength (MPa) Without heat aging 72.5 68.3 71.2 75.1 72.5 Standard Deviation 0.3 0.5 0.4 0.6 0.8

After 500 hours @ 230 ⁰C 52.9 70.8 73.4 68.2 48.6 Standard Deviation 13.9 8.1 2.4 6.4 17.3 % Tensile Retention 75% 103% 103% 90% 67%

Notes

1 ) Polyphenylene sulfide having a high degree of linearity and having a measured melt viscosity of 1400 poise (310⁰C₁ 1200 1/s). The Fortron® 0214B1 PPS utilized in this experiment was manufactured by Fortron Industries and marketed by Ticona Polymers LLC.

2) Fortron® 0320 is an extrusion grade polyphenylene sulfide having a high degree of linearity. This PPS is manufactured by Fortron Industries and marketed by Ticona Polymers LLC and it has typical melt viscosity of 2400 poise (@310°C, 1200 1/s).

3) Poiyether ether ketone manufactured by Victrex. It has a melt flow rate (MFR) of 44g/10min under the condition of 400°C/2.16 kg.

4) Dynasylan® AMEO-Pure Silane (3-Aminopropyltriethoxysilane) manufactured by Degussa. 5) The sodium endgroup content and the chlorine endgroup content are for the initial polyphenylene sulfide resin prior to being combined with the poiyether ether ketone.

As shown above, in this embodiment, better results were obtained when the metal endgroup content was above about 270 ppm. The tensile strength data from the above table is also illustrated in Fig. 1. As shown above in the table and on Fig. 1 , when the metal endgroup content was above 270 ppm for the polyphenylene sulfide resin, the resulting composition exhibited dramatically improved tensile retention properties. Of particular advantage, the surprising effect on tensile retention properties was exhibited for compositions containing polyether ether ketone in relatively low amounts, such as in amounts less than 25% by weight. While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.

Claims

WHAT IS CLAIMED IS:

1. A melt-processed, polymeric composition which formed by combining (a) a polyarylene sulfide resin having a metal endgroup content of from about 270 ppm to about 399 ppm, (b) a polyaryl-ether-ketone resin, and, wherein (c) a graft copolymer of (a) and/or (b) is formed rendering the composition homogeneous.

2. A polymeric composition as specified in claim 1 , wherein the polyarylene sulfide resin has a total residual chlorine content of from 300 ppm to 1200 ppm.

3. A polymeric composition as specified in claim 1 or 2, wherein the composition has a tensile strength retention after 500 hours at 230⁰C of from about 75% - 103%.

4. A polymeric composition as specified in claim 1 or 2, wherein the polyaryl-ether-ketone is combined in an amount of from about 18 to 83 percent by weight.

5. A polymeric composition as specified in claim 1, 2, 3 or 4, wherein the polyaryl-ether-ketone resin is polyetheretherketone resin.

6. A polymeric composition as specified in claim 1, 2, 3, 4 or 5, wherein said graft copolymer is a reaction product resulting from melt-processing comprises the reaction product of (a) the polyarylene sulfide resin, (b) the polyaryl-ether-ketone resin, and (c) a reactive compound selected from the group consisting of organotitanium compound, an organozirconium compound, and an organosilicon compound.

7. A polymeric composition as specified in claim 6, wherein the polyaryl- ether-ketone resin is present in the composition in an amount from about 15% to about 40%, the polyarylene sulfide resin is present in the composition in an amount from about 60% to about 85% by weight, and the reactive compound is an alkoxy silane present in the composition in an initial amount from about 0.2% to about 2% by weight.

8. A polymeric composition as specified in claim 1-6 or 7, wherein the polyarylene sulfide resin is of the formula:

-[(Ar¹)_n-X]_m-[(Ar²)_l-Y]_J-(Ar³)_k-Z]_l-[(Ar⁴)₀-W]_p- wherein Ar¹, Ar², Ar³, and Ar⁴ are the same or different and are arylene units of 6 to 18 carbon atoms; W, X, Y, and Z are the same or different and are bivalent linking groups selected from -SO₂-, -S-, -SO-, -CO-, -0-, -COO- or alkylene or alkylidene groups of 1 to 6 carbon atoms and wherein at least one of the linking groups is -S-; and n, m, i, j, k, I, o, and p are independently zero or 1 , 2, 3, or 4, subject to the proviso that their sum total is not less than 2.

9. A polymeric composition as specified in claim 6, wherein the alkoxy silane is an amino silane.

10. A polymeric composition as specified in claim 9, wherein the alkoxy silane is 3-aminopropyltriethoxysilane.

11. A polymeric composition as specified in claims 1-9 or 10, wherein the graft copolymer comprises polyarylene sulfide chains having polyaryl-ether-ketone chains grafted thereto, and wherein the polymeric composition has a continuous phase and discontinuous phase.

12. A polymeric composition as specified in claim 11 , wherein said continuous phase is the polyarylene sulfide resin, and said polyaryl-ether-ketone is present in an amount of from about 15 to 40 weight %. .

13. A polymeric composition as specified in claim 10 wherein said continuous phase is the polyaryl-ether-ketone resin.

14. A polymeric composition as specified in claim 1-12 or 13, wherein the metal in the metal endgroup is an alkali metal selected from the group of sodium, lithium and potassium.

15. The polymeric composition as specified in claim 1-13 or 14, further comprising a reinforcing filler selected from the group consisting of carbon fibers and glass fibers.

16. A coated metal body comprising a metal base or a metal base having an undercoat of an inorganic and/or organic material and at least one coating layer formed on the metal base or the undercoat, wherein the coating layer has a thickness which is within the range of 5 μm to 1000 μm, and where in coating layer is comprised of the polymeric composition specified in claim 1-14 or 15.

17. A process for extruding an article which comprises extruding a melt- processed polymeric composition comprised of (a) a polyarylene sulfide resin, (b) a polyaryl-ether-ketone resin, and (c) a graft copolymer of (a) and/or (b).