WO2007115009A1

WO2007115009A1 - Poly(αrylene ether) composition and method of making the same

Info

Publication number: WO2007115009A1
Application number: PCT/US2007/064628
Authority: WO
Inventors: Steven Klei; John B. Yates
Original assignee: Sabic Innovative Plastics Ip B.V.
Priority date: 2006-03-30
Filing date: 2007-03-22
Publication date: 2007-10-11
Also published as: JP2009532526A; EP2004743A1

Abstract

A resin composition includes a poly(arylene ether) and a pH sensitive compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added to a basic or acidic solution.

Description

POLV(ΛRYLE]SE ETHER) COMPOSITION AND JVf ETHOD OF MAKING

THE SAME

BACKGROUND OF THE INVENTION

This disclosure relates to poly(arylene ether) compositions, and more specifically to polyCarylene ether) compositions capable of being authenticated.

Poly(arylene ether) resins, such as poiyphenyiene ether (PPE) resins, are an extremely useful class of high performance engineering thermoplastics by reason of their hydrolytic stability, high dimensional stability, toughness, heat resistance, and dielectric properties. This unique combination of properties renders polyførylene ether) based compositions suitable for a broad range of applications, which are well known in the art For example, polyCarylene ether) blends are being widely used in the fields of automobile parts, electric parts, office devices, and lhe like.

With the commercial success of poly (ary lea e ether) resins, the practice of misrepresenting well-established and branded polyCan lene ether) resins is becoming common. Since many counterfeit, knock-off or imitation resins are sub-standard in quality compared to authentic resins, damage can be caused to the reputation of the well-established and branded materials, as well as fo consumers that purchase these counterfeit materials. For example, as noted above. poiy(arylene ether) blends are employed in automobile parts, As such, use of a sub-standard material can possibly result in physical harm or loss of human life as a result of failure of those automobile parts.

Accordingly, there is a need for poiyCarylene ether) resins that can easily be authenticated.

BRIEF DESCRIPTION OF THE INVEN TION

The need discussed above has been satisfied by a resin composition comprising a poSvCarySene ether); and a pϊi sensitive compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added Io a basic or acidic solution. Also disclosed is a method of making a resin composition The method comprises melt mixing a poly(arylene ether) and a pH sensitive compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added Io a basic or acidic solution.

Further disclosed is a method of authenticating a resin composition or an article Hie method comprises at least partially extracting a pH serssuiv e compound from the resin composition or the article with a solvent, wherein the resin composition or the article comprises a poty(arv lene ether) and the pH sensitiv e compound, mixing the solv ent having the extracted pH sensitive compound with an acidic solution or a basic solution Io form an observ ation mixture; and observ ing the observation mixture to determine if a predetermined color change occurred in {he observation mixture.

DETAILED DESCRIPTION OF THE INVEN TION

In tliis specification and in the claims, which follow, reference will be made to a number of terms, which shall be defined to hav e the following meanings.

The singular forms "a,^" "an,^" and "the^" include plural referents unless the context clearly dictates otherwise.

"Optional" or "opϋonaliv ^" means that the subsequently described e^ent or circumstance mav or may not occur, and that the description includes instances Λvhere the e\ ent occurs and instances where it does not.

"^"Combination^" as used herein includes mixtures, copolymers, reaction products, blends, composites, and the like.

The terms ^"'neutral^", "basic^", and "acidic^" solutions are referred to throughout this disclosure. A neutral solution refers to a solution ha\ ing a pH of 6 to 8, with a pH of ? being completely neutral. A basic solution refers to a solution hav ing a pH greater than S An acidic solution refers to a solution having a pH less than 6.

Furthermore, the endpoints of all ranges reciting the same characteristic are iodepeodentK combinable and inclusiv e of the recited endpoint The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of lhe particular quantity).

In one embodiment a resin composition comprises A) a poiy(arylene ether), and B) a pH sensitiv e compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and added to a basic or acidic solution, hi one embodiment, the pH sensitive compound is stable at temperatures up to about 220⁰C, more specifically up to about 280^'''C, even more specifically up to about 32O⁰C. The term '"stable" is used through this disclosure to refer to a compound that has not undergone significant chemical changes to substantially impair the desired properties of the compound. For example, lhe pH. sensitive compound remains capable of changing color when exposed to acidic or basic conditions even after being melt mixed with the polytarylene ether) and extracted from the composition. Stability can further be verified by various techniques that are well know in the art. which include, but are not limited to, differential scanning calonmetry (DSC) and thermogravimemc analysis (FGA).

In one embodiment, which is discussed in greater detail below, the composition further comprises a poly(aikeny) aromatic).

In other embodiments, the composition comprises a poivamide. Poly amides, also known as nylons, are characterized by the presence of recurring amide groups (- C(O)NH-). Polyamide resins are well known in the art, as are methods for their preparation. They are widely commercially available. Blends of poiy(aryiene ether)s and poly amides are described, for example, in U.S. Patent Nos. 4.732.938 to Grant el a)., 4,859,739 to Yafes et al , 4,873,276 to Fujii et aJL 4,874,81.0 Io Lee et aJL 4,923,924 to Grant et a!.. 4,960,825 to van der Meer, 4.963,620 to Grant et al., 5.134,196 to van der Meer, 5,248,728 to Lee, 5,260.374 to Gallucci. 5,977,240 Marie Lohmeijer et al., 6,166, 1 15 to Landa, 6.171,523 to Silvi et al., 6,469,093 and 6.486,255 to Koevoets et aJ., aid in U.S. Patent Application Publication Nos. US 2005/0038191 Al and US 2005/0038203 Al of Flkovitch et al. in yet other embodiments, the composition comprises a polyolefin. Suitable polyoiefins include, for example, horoopoiyrners and copolymers having at least aboul 80 weight percent of units derived from polymerization of ethylene, propylene. hutySene, or a mixture thereof. Examples of poly olefin homopolymers include polyethylene, polypropylene, and poiybutyiene. Examples of polyolefm copolymers include random, graft, and Mock copolymers of ethylene, propylene, and butyletie with each other, and further comprising up to 20 weight percent of units derived from Cj-C)_O alpha olefins (excluding aromatic alpha-olefins). Polyoiefins further include blends of the above homopolymers and copolymers. Blends of poly(arylene ether)s and polyoiefins are described, for example, in U.S. Patent Nos. 6,495,630. 6.545.080, 6,627.701, 6.660J94, 6,815,491. 6.855,767. and 6,86 K472 to Adβdeji et a!., and U.S. Patent Application Publication No. US 2005-0154130 Al to Adedeji et al.

In various other embodiments, the composition can further comprise reinforcing fillers and secondary additives as discussed below

As used herein, a "polyfarylene ether)" comprises a plurality of structural units of the formula (I):

wherein for each structural unit, each Q' is independently halogen, primary or secondary Ci-Cc alkyl, CVCn amsiioalkyL CrCY₁? hydroxy alkyl, aryl, CpC^ haloalkyl. Cj-Cu hydrocarbyioxv, or CpC₃₂ haSolrydroearbvloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and each Q" is independently hydrogen, halogen, primary or secondary Ci-C^' is alkyl, Ci-Cu aminoaikyl, Ci-Ci > hydroxy aJk> L aryl. Cj-C₁;? haloalkyl CrC₅.? hydrocarbyloxy, or C)-Cu halohvdrocarbvloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, in one embodiment each Q' is independently Cj-CY alkyl or phenyl, and each Q² is independently hydrogen or methyl. The ρo1y(ary1ene ether) can comprise molecules having aniinoalkyl-eontaining end group(s). typically located in an ortho position to the hydroxy group. Also frequently present are diphenoquinone end groups, typically obtained from reaction mixtures in which diphenoquinone byproduct is present.

^'The poiyCaryiene ether) can be in the form of a homopolymer, a copolymer, a graft copolymer, an ionomer, or a block copolymer, as w ell as combinations comprising at least one of the foregoing. For example, in one embodiment, the ρoly(arylene ether) comprises 2₅6-dimethyl-l ,4~phen.yIene ether units, optionally in combination with 2,3.6-1riniethyl~1 ,4-phenySene ether units.

The poMaryiene ether) can be prepared by the oxidative coupling of monohydroxy aromatic compound(s) such as 2,6-xylenol and 2.3.6-triniethylphenol. Catalyst systems are generally employed for such coupling; they can contain heavy metal ion such as a copper, manganese, iron, or cobalt ions, usually in combination with v arious other materials such as secondary amines, tertiary amines. NJ^T -dialkylalkyienediamines, halides, or combinations of two or more of the foregoing.

The polyCaryiene ether) can be functionalized with a polyfunctions! compound such as a poh'carboxylic acid or those compounds having in the molecule both (a) a carbon-carbon double bond or a carbon-carbon triple bond and (b) at least one carboxyiic acid, anhydride, amide, ester, imide. amino, epoxy, orthoester, or hydroxy group. Examples of such polyfunctional compounds include maleic acid, rnaieic anhydride, fυmaric acid, aid citric acid.

Jn one embodiment, the poly(ary1ene ether) comprises a capped po5y(arylene ether). The terminal hydroxy groups may be capped with a capping agent via an acylation reaction, for example. The capping agent chosen is desirably one that results in a less reactive po!y(ary!ene ether) thereby reducing or preventing crosslinking of the polymer chains and the formation of gels or black specks during processing at elev ated temperatures. Suitable capping agents include, for example, esters of salicylic acid, antbranilic acid, or a substituted derivative thereof, and the like: esters of salicylic acid, and especially salicylic carbonate and linear polysalicylates, are preferred As used herein, the term "ester of salicylic acid" includes compounds in which the carboxy group, the hydroxy group, or both have been eslerified. Suitable salicylates include, for example, aryS salicylates such as phenyl salicylate, acetylsalieylic acid, salicylic carbonate, and polysalicylates. including both linear poIysalicySates and cyclic compounds such as disahcylide and trisalicylide. The preferred capping agents are salicylic carbonate and the poly salicylates, especially linear

When capped, the poly(arylene ether) may be capped to any desirable extent up to 80 percent, more specifically up to about 90 percent, and even more specifically up to 1.00 percent of the hydroxy groups are capped. Suitable capped poiy(arylene ether) and their preparation are described in United States Patent N os 4.760.1 1 8 to White et al. and 6,306,978 to Braat et al.

Capping polyl^'arylene ether) with poly sal icy I ate is also believed to reduce the amount of aminoalkyi terminated groups present in the poMarylene ether) chain. The aminoalkyi groups are the result of oxidative coupling reactions that employ amines in the process to produce the poly{arylene ether). The aminoalkyl group, orlho to the terminal hydroxy group of the polvCarylene ether), can be susceptible to decomposition at high temperatures. The decomposition is believed to result in the regeneration of primary or secondary amine and the production of a qiύnone methide end group, which may m turn generate a 2,6-dialkyl-l-hydroxyρhenyl end group. Capping of polyCaryiεne ether) containing aminoalkyi groups with poiysaiicylate is believed to remove such amino groups to result in a capped terminal hydroxy group of the polymer chain and the formation of 2-hydroxy-N.N~alkylben7.arnine (salicylamide). The removal of the amino group and the capping provides a poiy(arylene ether) that is more stable to high temperatures, thereby resulting in fewer degradative products, such as geis or black specks, during processing of the poiy(aryiene ether).

The po.ty(aryle.ne ether) can have a number average molecular weight of about 3,000 grams per mole (g/mol) to about 40,000 g/mol and a weight average molecular weight of about 5,000 g/moi to about 80,000 g/moi. as determined by gei permeation chromatography using monodisperse polystyrene standards, a styrene divinvl benzene gel at 40⁰C and samples having a concentration of 1 milligram per milliliter of chloroform The poly(arylene ether) or combination of poly (aiylene ether)s may have

(S an initial intrinsic MSCOSJK of about 0 OS deciliter per gram <dl»'g1 to about 0 50 deciliter per gram, as measured in chloroform at 25⁰C Within this sange. the initial intrinsic uscossts nia> be at least about 0 W decthtes per grant oi at least about 0 30 deciliter pei gram Also within tins range, the initial intrinsic MSCOSII\ nrø> be up to about 0 46 deciliter per gram, or tip to about 040 decihtei per giam Initial intrinsic Mt,cosιt\ is defined as the intnmic Mscot.it> of the poMan lene ethei) puor to melt mixmg w ith the other components of the composition, and final mtπnsic \ jscosits is defined as the intrinsic MSCOSII) of the poh (an lene ether) after melt mixing \sith the other components of the composition As understood b\ one of ordma.% skill in the ait the \iscosits of the poh (an lenc ether) mas be up to 30% highes after melt mixing The percentage of ineicase can he calculated In tϋθ^χ(final inUmssc uscosit\ ~ initial mtπnsic Mscosih )/imtial intrinsic \ iscosit>

The poh (an lone ether) is generalh used in amounts of I O weight percent to Ψ> ^ w eight percent W ithin this ianoc, the poh (an lenc ether) can he used m amounts gi eater than oi equal to 20 weight peicent, or, moie specificalh , greatei Uian or equal to 30 weight peicent Also withm this range, the poh (an lene ether) can be used in amounts of less than oi equal to ¹Xt w eight peicent ou more specificaih . less than or equal to H^ w eight percent, or, e\ en more specificalh . less than or equal to SO weight percent Weight percent is with respect to the total weight of the composition

The composition mas . optjonaih . include a pols UΛem l aromatic J The term "poh (aikem I aiomaticV as used heieni includes poK mers prepared h\ methods known in the ait including bulk, suspension, and emulsion pohmen/ation, which contain at least 2^% b> w eight of structural units deriv ed from an alkens l aromattc monomer of the formula

wherein R* is hydrogen, C _I -CB alkyl. or halogen; Z³ is vinyl, halogen or Cj-Cs alkyl: and p is 0. ] , 2. 3. 4, or 5 More specifically, alkenyl aromatic monomers include styrene. chlorostyrene, and vinyl toluene. The poly (alkenyl aromatsc)s include homopolymers of an alkenyl aromatic monomer, random copolymers of an aJkenyl aromatic monomer such as slyrene. with one or more different monomers such as acrylonimle, butadiene, alpha-methylstyrene, ethyivmylben/ene. dn ioylbenzene and maieic anhydride; unhydrogenated and hydrogenated block copolymers of an alkenyl aromatic and a conjugated diene; and rubber-modified polyfalkenyl aromatic)s.

When the poly(aikenyl aromatic) is a unhydrogenated or hydrogenated block copolymers of an aikenyi aromatic and a conjugated diene, the conjugated diene may be. for example. 1,3-butadiene. 2-methyi-1.3-butadiene. 2.3-di methyl- 1,3-butadiene, or 13~pentadiene. The arrangement of the po1y(alkenyl aromatic) and poiy(conjugated diene) blocks may be a linear structure (e.g., di block, tri block, tetrablock copolymers), or a radial teleblock structure with or without a branched chain. When the polyCalkeny) aromatic) is a hydrogenated block copolymer, the ρoiy(co.rjjugated diene} blocks may be partially or fully hydrogenated, so that about 10 Io 100% of the unsaturated bonds in the aliphatic chain moiety derived from the conjugated diene are reduced. The poiy(aikenyi aromatic) may be partially hydrogenated to selectively reduce pendant (rather than in-chain) aliphatic double bonds. Specific unhydrogenated block copolymers include slyrene-hutadiene di block copolymers, styrene-butadiene-styrene triblock copolymers, styrene-isoprene di block copolymers, and styrene-isoprene-sfyrene triblock copolymers. Specific hydrogenated block copolymers include stvrene-Cethylene-hutylene) di block copolymers. styrene-(ethylene-butylene)-styrene triblock copolymers, styrene- (butadiene-butylene)-slyrene triblock copolymers, and partially and fully hydrogenated styrene-isoprene-styrene triblock copolymers. Suitable unhydrogenated and hydrogenated block copolymers are further described in U.S. Patent Nos. 6.855,767 and 6.872.777 to Adedeji et al

When the poly{alken> l aiOmalic) is a rubber-modified poly(alkeoyl aromatic), it may comprise (a) a homopoiymer of an alkenyl aromatic, and (b) a rubber modifier in the form of a blend with the homopoiymer. or a graft on the homopoiymer, or a combination thereof, wherein the rubber modifier can be a polymerization product of at least one C₄-Cj₀ non-aromatic dieπe monomer, such as butadiene or isoprene, and wherein the rubber-modified poly (alkenyl aromatic) comprises about 98 weight percent to about 70 weight percent of the homopoiymer of an alkenyl aromatic monomer aid about 2 weight percent to about 30 weight percent of {he rubber modifier, specifically about 88 weight percent to about 94 weight percent of the homopoiymer of an alkenyl aromatic monomer and about 6 weight percent to about 12 weight percent of the rubber modifier. These rubber-modified polystyrenes are commercially available as. for example, GEH 1897 from GE Plastics, and EB 6755 or MA5350 from Chevron Phillips Chemical Company

In one embodiment, the poly(a!keny! aromatic) resin is selected from rubber-modified polystyrenes, atactic homopolysiyrenes, syndiotactic polystyrenes, block copolymers of an alkenyl aromatic and a conjugated diene, hydrogenaied block copolymers of an alkenyl aromatic and a conjugated diene. and combinations thereof In one embodiment, the pory(aike.nv.l aromatic) comprises an atactic bomopolystyrene having a weight average molecular weight of about 50,1*00 to about 1 ,500,(.HK* atomic mass units. In one embodiment, the poiy(alkenyi aromatic) comprises a rubber- modified polystyrene having a weight average molecular weight of about 50,000 to about 1 ,500.000 atomic mass units. Fn one embodiment; the pαlyf alkenyl aromatic) comprises a styrene-buiadiene-styrene lribloek copolymer having a butadiene content of about 60 weight percent to about 90 weight percent In one embodiment, the poSvCalkenyl aromatic) comprises a radial telebiock styreiie-buladiene block copolymer.

The stereoreguiarity of the poly{alketwl aromatic) can be atactic or syndiotactic. In one embodiment, the po!y{alkenyl aromatic)s include atactic and syndiotactic homopolystyrenes. Suitable atactic homopolystyrenes are commercially available as. for example, EB33OO from Chevron Phillips Chemical Company, and 168M and 168MO from INEOS Sfyrenies, Suitable syndiotactic homopolysiyrenes may be prepared according to methods described in U.S. Patent Nos. 5,189,125 and 5,252,693 to lshihara et a!., 5,254,647 to Yamamoto et a!.. 5,272,229 to Tomotsυ et al, and 5.294.685 to Watanabe et al. When present the poiy(alkenγl aromatic) is generally used in an amount of about 10 weight percent to about 70 weight percent Within this range, the poly{a!kenyl aromatic) can be greater than or equal to about 20 weight percent; and more specifically greater than or equal to about 3*) weight percent. Also within this range, the pøly{alkenyl aromatic) is less than or equal Io about 65 weight percent and more specifically less than or equal to about 60 weight percent. Weight percents are based on a total weight of the composition.

As briefly mentioned above, the pll sensitive compound is selected such that it is at least partially extraclabie from the composition and changes color upon addition Io a basic solution or an acidic solution. In one embodiment, the pH sensitive compound is selected and is present in an amount such that if the composition itself were added to the same basic solution or acidic solution, no color change in the composition would be observed. In this embodiment, a color change is observed only after extracting the pH sensitive compound and adding the extracted pH sensitiv e compound to the basic solution or the acidic solution In another embodiment, the pϊi sensitive compound is selected and is present in an amount such that if the composition itself were added Io the same basic solution or acidic solution, a color change in {he composition would be observed. In one embodiment, the pH sensitive compound significantly affects the color of the resin composition as produced. In this embodiment, the types and amounts of other colorants may be adjusted to produce a resin composition having the desired color characteristics.

The solvent that is used to extract the pH sensitive compound cat) be the same as or different from the basic solution or the acidic solution, as long as the pH sensitive compound is at least partially soluble in the solvent, ϊn one embodiment, the solvent is a poor solv ent for the polyCarylene ether), for this embodiment, suitable solvents include, for example, ketones having three Io ten carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and mixtures thereof; ethers, such as 1 ,2-dimetlioxyelhane, letrahydrofυran (THF), 1 ,4-dioxane, and the like, and mixtures thereof; nitriles, such as, acetonitrile and the like, and mixtures of the foregoing solvents, ϊn another embodiment, the solvent is a good solvent for the po!y(ary!ene ether). For this embodiment, suitable solvents include, for example, aromatic hydrocarbons such as hen/ene. toluene, xylenes, and the like; chlorinated aromatic hydrocarbons such as ehloroben/ene, dichloroben/.enes, and the like; and chlorinated aliphatic hydrocarbons such as dichloromelhane (methylene chloride). tfichloromethaπe (chloroform), teirachiorometliane (carbon tetrachloride), dichioroethanes. tnchloroethan.es, and the like; and mixtures thereof.

The pH sensith e component can be selected to change color under basic conditions (e g . phenotphthaSeni and tln molphthalein) or acidic conditions (e.g , bronioths niol blue) While a \ ariely of acids or bases can he added to the soh em to make a basic or acidic solution, in one embodiment, the acids or bases are selected to allow for ease in authentication such that special handling or testing equipment is not needed. Accordingly- pellets, molded articles, and the like that are manufactured using the composition can be readily authenticated at the manufacturing facility , warehouse, and the like.

Suitable bases include bases that yield a solution having a pϊl of greater than 8, more specificalh a pH greater than 10. For example, suitable bases include, but are not limited to. sodium bicarbonate, borax, calαυrn carbonate, magnesia, ammonia, potassium carbonate, sodium carbonate, potassium In dro.xide. sodium In dro.xide. and lime, and combinations thereof. Hie basic solution is typically aqueous, although solutions in lower alcohols such as methanol and eihanol mas also be used.

Suitable acids include acids that yield a solution having a pH less than o. more specifically a pH less than or equal to 3. For example, suitable acids include, but are not limited to, acetic acid, citric acid, nitric acid, hydrochloric acid, sulfuric acid, tartaric acid, phosphoric acid, alum, and combinations thereof. ^'The acidic solution is typically aqueous, although solutions in lower alcohols such as methanol and ethanol may also be used.

In one embodiment, the pH sensitiv e compound is present in amount that will not detrimentally affect the heat resistance, flow, and other mechanical properties of the composition so much as to render them unsuitable for their intended purpose For example, the pH sensith e compound is generally used in an amount of about 0.0 J weight percent to about 40 weight percent Within this range, the pH. sensitive compound can be greater than or equal KJ about U 03 w eighs percent or greater than Oi equal to 0 1 w eight percent, or gi eater than or equal to about 0 15 w eight pes cent AKo uUhϋi this range, the pH sensiine compound is less than or equal Io about 30 weight percent, or less than or equal Io about 2^ weight percent, or less than or equal to about 10 w eight percent, or less than or equal to about 5 weight percent or less than OΪ equal to about 2 weight peicent. oi less than or equal to I weight percent, or less than or equal to about O 75 weight percent, or less than or equal to about O 5 w eight percent W eight percents are based on the total w eight of the composition Selection of the amount of pH scnsiux o compound max depend on \ aπabies including the j denim of the pH sensitive compound, the t> pes and amounts of olhci components in the composition, and whethei the composition is meant to he blended w ith additional components before being used to form an article For example, a htghei concentration of the pϊ 1 sensitiv e compound max be used when the composition ΪS intended for use as a poh (ar> 1ene ether) concentrate that ss blended w ith another resm before being used for article formation

In one embodiment, the pH sensitis e compound is selected to be coloiiess at a neutral pϊ l or to be colorless as extruded The lack of color of the pH sensitn e compound allows the composition tυ be authenticated without affecting the color of the composition Stated another wax , the composition containing the pH sensitπ e compound adopts am color that a composition absent the pH sensun e compound v ouid adopt Since sesin color can be a kex part of a compam ^*s brand identification, the pTI scnsiux o compound can adx antageoush he mcoiporatod into the resin fot authentication purposes xuthout adv erseh affecting the eoioi of the resin In anolhei embodiment, the pH of the compound itself can be adjusted such that the pH sensitiv e compound can be blended with a coloring package of the composition to obtain the desired color for the compam 's brand

One embodiment is a method of authenticating a resin composition or an article, comprising at least partialh extracting a pH sensitive compound from the tesiπ composition oi the aiticle with a solx ent, v herein the resin composition or the article comprises a pol\ (aπ lene ether) and the pH sensitiv e compound, mixing the soh ent hav ing the extracted pϊ J sensitiv e compound with an acidic solution oi a basic solution to form an observation mixture; and observing the observation mixture to determine if a predetermined color change occurred in the observation mixture. For example a resin sample containing fhymolphthalein and having an exposed surface area of ai least about 2*) square centimeters mas¹ be immersed in and agitated with 50 milliliters of acetone at 23"C for 30 minutes. An aliquot (10 milliliters) of the acetone may then be removed using a pφet and added to a 20 milliliter via! atop a sheet of white paper and containing 5 milliliters of an aqueous sodium hydroxide solution of pH 10, as indicated using an EMD ColorPbast* pH strip. A color change in the solution from colorless to pink indicates the presence of the thymolphthaJein. In particular, an increase (relative to pure solvent plus aqueous base) in absorbance of at least 0.05 absorbance units per centimeter path length at 592 .nanometers (λ_mκi of the basic form of ihynioiphthalein) indicates the presence of the pH-sensitive compound and therefore the authenticity of the poIyCarylene ether) contained in the composition.

One embodiment is a method of authenticating a resin composition or an article, comprising, at least partially extracting a pH sensitive compound from the resin composition or the article with a solvent, wherein me solvent is selected from the group consisting of acetone, tetrahydrofuran, methyl ethyl ketone, methyl isobutvl ketone, 1 ,2-dimethoxyethane. acetoiiitrile, 1 ,4~dioxane, and combinations thereof; and wherein the resin composition or the article comprises about 10 to about 90 weight percent of a poly(arylene elher) comprising 2.6-dimethyl-1.4-phenylene ether units; about 10 to about 70 weight percent of a poly{alkenyl aromatic) selected from the group consisting of homopolymers of an alkenyl aromatic monomer, random copolymers of an alkenyl aromatic monomer with one or more different monomers, υnhydrogenated and hydrogenated block copolymers of an alkenyl aromatic and a conjugated diene; rubber-modified poly(alkenyl aromatic)s, and combinations thereof; and about 0.01 weight percent to about 1 weight percent of the pH sensitive compound; wherein the pH sensitive compound is capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added to a basic or acidic solution; wherein the pϊ i sensitive compound is selected from the group consisting of thymol phthalein, phenol phthalein. methyl violet, thymol blue, methyl yellow-, bromophenoi blue, congo red, methyl orange, litmus, bromocresoi purple, phenol red, thymol blue, alizarin Yellow R, indigo carmine, and combinatory {hereof; mixing the solvent having the extracted pH. sensitive compound with an acidic solution or a basic solution to form an observation mixture; and observing the observation mixture to determine if a predetermined color change occurred in the observation mixture,

hi one embodiment, the pH sensitise compound changes color as a function of pJH. That is, the intensity of the color can vary with the pH or the color itself can be different at different pϊl ranges. Multiple pH sensitive compounds can be employed that change color at different pϊi ranges. For example, an extract from a resin containing both bromothymol blue (e.g., changes yellow at pH 6.0 and below, and changes blue at pH 7.6 and above) and phenoiphthalein (changes from colorless at pH 8.0 and below, and red at pH 10 and above) would be expected fo change from yellow to blue to violet as the pH of the solution is changed from 6.0 to 10.0, In another embodiment, two different pH sensitive compounds are employed to achieve the same color, whose extracts are then differentiated upon introduction of an acid or base.

Jn one embodiment, the pf-ϊ sensitive compound comprises thvmoiphthalein, phenol phthaSeio, or a combination thereof. Specific pH sensitive compounds, include, but are not limited to. methyl violet, thymol blue, methyl yellow. bromophenol blue, congo red, methyl orange, litmus, bromocresol purple, phenol red, thymol blue, alizarin Yellow R, Indigo carmine, and combinations thereof Selection of a suitable pH. sensitive compound may depend on several factors. If the authentication test is to be conducted on a molded article that must remain in service after the authentication test, then the pH sensitive compound should be selected so that exposure to solvent aud basic or acidic solution will not significantly affect the required properties of the resin. For example, the excellent stability of poly(arylene ether)/po1y(alkenyl aromatic) compositions to basic solutions makes phenoiphthalein and thvmolphthalein good choices since they change color in basic solution. If destructive testing is possible (e.g., on replaceable resin pellets), the pellets may be partially or fully dissolved in the solvent, and the pH sensitive compound may have a lower extinction coefficient m its visibly colored form, or it may be used at a reduced concentration in the resin. In order to avoid changes in the color of the composition as it is processed and articles containing it are molded, it may be preferable to choose a pH sensitive compound that changes color outside the pH range of about 6 to about 8. especially because trace impurities or additiv es in the composition may inadvertently trigger the color change. The thermal stability of the pH sensitive compound mas- also be considered. Thermal stability of candidate pH sensitive compounds may be determined by thermogravi metric analysis (TGA) or differential scanning calorimelry (DSC). For example, broniothymoi blue exhibits a degradation temperature of 220⁰C as measured by DSCl indicating that it is not a good choice for resin compositions that are compounded or molded at or above 220⁴¹C. Thymoiphthalein and phenolphthalem vvere shown by DSC and T(JA to undergo only melting at 255°C and 265°C, respectively, and weight loss m TOA was only significant starting at about 280-290⁰C. These pH sensitive compounds are therefore suitable for use in relatively heat resistant resin compositions

Jn various embodiments, the composition can aJso include effective amounts of at least one additive such as arøi-oxidanis, drip retardants, dyes, pigments, colorants, stabilizers, small particle mineral fillers such as clay, mica, and talc, visual effects additives, antistatic agents, plasticizers, lubricants, glass fibers (long, chopped or milled), carbon fibers, carbon fibrils {including single-wall nanolubes and multi-wall nanotubes) and combinations comprising at least one of the foregoing. In one embodiment, the composition comprises at least one additive chosen from magnesium oxide, zinc oxide, zinc sulfide, pentaerythritoi beta-laurylthi ©propionate, mineral oil. st> rene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, block copolymers of ethylene oxide and propylene oxide, polytetrafluoroethylene encapsulated in styrene-acrylonitrile copolymer (^"TSAN"). terpene phenol resins, butylated tripheny! phosphate, resorcinol bis(diphenyl phosphate), tridecyi phosphite. tπs(2_;4-di-t-buty!pheny!) phosphite, cis-13-docosen.oic amide (erucamide), sodium alky J sulfonates, polyethylene, clay, and glass fibers. These additives are known in the art. as are their effective levels and methods of incorporation. Effective amounts of the additives van widely, but they can be present in a total amount up to about 60% or more by weight, of the total weight of the composition. In general, additives such as antioxidants, flame retardants, drip retardanls, dyes, pigments, colorants, stabilizers, antistatic agents, plasticizers, lubricants, and the like are present in amounts of about 0.01 weight percent to about 5 weight percent of the total weight of the composition, while small particle mineral fillers and glass fibers comprise about I weight percent to about 60 weight percent of the total weight of the composition.

One embodiment is a resin composition comprising: about 10 to about 90 weight percent of a polyCarylene ether) comprising 2,6-dinieihy1-J ,4-phenylene ether units; about i O to aboiit 70 w eight percent of a poh Calkenyl aromatic) selected from the group consisting of homopolymers of an alke.ny.1 aromatic monomer, random copolymers of an alkenyl aromatic monomer with one or more different monomers, uπhydrogenated and hydrogenated block copolymers of an alkenyi aromatic and a conjugated diene; rubber-modified poK '(alkenyi aromalic)s, and combinations thereof; and about 0.01 weight percent to about 40 weight percent of a pH sensitive compound capable of providing a color change when the pH. sensitive compound is at least partially extracted from the resin composition and is added to a basic or acidic solution; wherein the pH sensitive compound is selected from the group consisting of t^'hymolphthalein, phenolphthalein, methyl violet, thymol blue, methyl yellow. bromophenoi blue, congo red, methyi orange, litmus, bromocresol purple, phenol red. thymol blue, alizarin Yellow R, Indigo carmine, and combinations thereof; wherein ail weight percents are based on the total weight of the composition.

One embodiment is a pory(ary1ene ether) concentrate, comprising: a poly(arylene ether), and about 0 5 to about 40 weight percent of a pH sensitive compound, based on the total weight of the concentrate. Within the range of about 0.5 to about 10 weight percent, the pH sensitive compound amount may be at least about I weight percent, or at least about 2 weight percent.

The concentrate may, optionally, further comprise a flame retardant. Suitable flame retard ants include, for example, phenyl bisdodecyl phosphate, phenyl bisπeopeπtvl phosphate, phenyl bis(.>,5,5'-triniethylhexyl) phosphate, ethyl dipheπyl phosphate. 2-ethylhexyi di(p-toiyl) phosphate, bis(2-elhyihexyl) p-tolyl phosphate, tritoiyl phosphate. bis{2-ethyiheχyl) phenyl phosphate, tri(nonylphenyl) phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, mphenyl phosphate, di butyl phenyl phosphate. 2-chloroefhyi diphenyl phosphate, p-tolyl bis{2.5,5'- trirøethylhexyl) phosphate. 2-eihylhexyl diphenyl phosphate, resorcinol

phosphate), hydroquinone bisfdiphenyl phosphate), bisphenol A bis(diplienyl phosphate), and the like, and combinations thereof Other suitable flame relardants are described, for example, in U.S. Patent No. 6.486.244 to Adedeji et al When present the flame retardanl may be used in an amount of about 5 to about 50 weight percent, based on the total weight of the concentrate. Within this range, the flame retardanl amount may be at least about 10 weight percent, or at least about 15 weight percent, or at least about 20 weight percent.

In one embodiment, the concentrate is provided in a particulate form that facilitates intimate blending with other resins. Thus, the polyCarylene ether) concentrate may be provided in a form such that at least 50 weight percent of the concentrate has particle size less than about 2.8 millimeters by about 2.8 millimeters and wherein less than 5% by weight of the concentrate has a panicle size less than about 75 micrometers by about 75 micrometers. The weight fraction of particles having a particle size greater than about 2.8 millimeters by about 2.8 millimeters may be determined as the weight traction retained on an ASTM El 1 No. 7 sieve (having a mesh size of 2 8 millimeters). The weight fraction of particles having a particle size less than about 75 micrometers by about 75 micrometers may be determined as the weight fraction retained on an ASTM E S S No. 200 sieve (having a mesh size of 75 micrometers). Methods of preparing polyCarylene ether) compositions having such particle size characteristics are described, for example, in U.S. Patent ^"Nos. 6.096,821 and 6,258,879 to Adedeji et at.

The composition can be prepared by melt mixing or a combination of dry blending and melt mixing. Melt mixing can be performed in single- or twin-screw type extruders or similar mixing devices, which can apply a shear to the components. All of the components of the composition may be added initially to the processing system, in an embodiment hi which the poly(arylene ether) is to be blended with an at least partially incompatible resin (e.g., polyaniide or polyester), the polyCarylene ether) may be precompounded with a eompatibilizing agent to form a functioπalized poly(arylene ether). The functionali/.ed polyCarylene ether) is then compounded with the other components. For example, the pH sensitive compound can be added at the same time as the polyCaryiene ether) or added downstream of the poly{arylene ether). Advantageously, by adding the pH sensitive compound downstream, the pH sensitiv e compound is exposed to less heat history, which can cause the pH sensitive compound to degrade.

After the poly(arylene ether)-eøntaimng composition is formed, it is ts'pically formed into strands, which are cut to form pellets. The strand diameter and the pellet length are typically chosen to prevent or reduce the production of fines (particles that have a volume less than or equal to 50% of the pellet) and for maximum efficiency in subsequent processing such as profile extrusion. An exemplary pellet length is about 1 millimeter (ran) to about 5 mm and an exemplary pellet diameter is about 1 mm to about 5 mm.

Fn one embodiment, a composition comprising a poly{aryleiie ether) is blended with a concentrate comprising a polymer resin and a pH sensitive compound For example, in this embodiment, an article manufacturer could purchase polyCarylene ether) pellets, melt blend them with a concentrate comprising a polymer resin and a pU sensitive compound, and use the blend Io produce po!y{ary!ene ether)-containmg articles that could subsequently be authenticated, ϊn one embodiment the polymer resm used to form the concentrate has a glass transition temperature or a melting temperature less than or equal to about 1 7O⁰C. or less than or equal to about 165"C. or less than or equal to about 160⁰C, or less than or equal to about 155X.

In one embodiment, the polymer resin used to form the concentrate is chosen from polystyrenes, hydrocarbon waxes, hydrocarbon resins, fatty acids, polyolefins. polyesters, lluoropolymers. epoxy resins, phenolic resins, rosins and rosin derivatives. terpene resins, aery late resins, polyamides, and the like, and combinations thereof.

Suitable polystyrenes include homopoiystyrenes having a weight average molecular weight of about LOOO to about 300.000 atomic mass units. Within this range, the w eight average molecular weight may be at least about 2,000 atomic mass units. Also within this range, the weight average molecular weight may be up to about 200,000 atomic mass units, or up to about 100,000 atomic mass units. The term "hydrocarbon wax" is understood to mean a wax composed solely of carbon and of hydrogen Suitable hydrocarbon waxes include, for example, rnicrocrystalJine waxes, polyethylene waxes, Fischer-Tropsch waxes, paraffin waxes, and combinations thereof.

Suitable hydrocarbon resins include aliphatic hydrocarbon resins, hydrogen ated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, hydrogenated aliphatic/aromatic hydrocarbon resins, eycioaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, hydrogenated cycioaiiphatic/aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene-phenol resins, rosins and rosin esters, hydrogenated rosins and rosin esters, and mix lures of two or more thereof. As used herein, "hydrogenated'^', when referring to the hydrocarbon resin, includes fully, substantially, and partially hydrogenated resins. Suitable aromatic resins include aromatic modified aliphatic resins, aromalic modified cycloafiphatic resins, and hydrogenated aromatic hydrocarbon resins having an aromatic content of about 1 to about 30%. Any of the above resins may be graded with an unsaturated ester or anhydride using methods known in the art. Such grafting can provide enhanced properties to the resin. In one embodiment, the hydrocarbon resin in a hydrogenated aromatic hydrocarbon resin. Suitable hydrocarbon resins are commercially available and include, for example, EMFR resins. OPPERAΦ resins, and EMFR resins available from ExxonMobil Chemical Company: ARKON* and SIiPER ESTERS rosin esters available from Arakawa Chemical Company of Japan; SYLVARESΦ polyterpene resins, styrenated terpene resins and terpene phenolic, resins available from Arizona Chemical Company; SYLVATACf? and SYLVAIJTEΦ rosin esters available from Arizona Chemical Company; NORSOLEN ES: aliphatic aromatic resins available from Cray Valley; DER TOPHENE* terpene phenolic resins and DERCOLYTE* polyterpene resins available from DRT Chemical Company; EASTOTAC* resins, PlCCOTACiK¹ resins, REGALfTEΦ and REGALREZ* hydrogenated cycioaiiphatic/aromatic resins available from Eastman Chemical Company: WINGTACK® resins available from Cϊoodyear Chemical Company: PICCOLYTBΦ and PERMAL YN # polyterpene resins, rosins and rosin esters available from Eastman Chemical Company; coumerotie/indene resins available from Neville Chemical Company: QUiNTONF*- acid modified Cj resins, Cy'C'9 resins, and acid-modified C5/C9 resins available from Nippon Zeon/. and CLEARON-S) hydrogenated terpene resins available from Yasuhara.

Suitable fatly acids include, for example, oleic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid, montanic acid, and combinations thereof.

Suitable poly olefins include, for example, poly ethylenes, polypropylenes, elhylene- vinyi acetate copolymers, and combinations tiiereof. In one embodiment, ihe poiyolefin is a low-density polyelliy ϊetie having a weight-average molecular weight of about 5.000 lo about 4Oj⁾OO atomic mass units. Within this range, the weight average molecular weight may be up to about 30,000 atomic mass units, or up to about 2Oj)OO atomic mass units. In one embodiment, the polymer resin comprises a homopolystyrene having a weight average molecular weight of about 1 ,000 to about 300,000 atomic mass units, and a low-density polyethylene having a weight average molecular weight of about 5,000 to about 40,000 atomic mass units.

Suitable polyesters include, for example, ihe condensation copolymerization products of dibasic acids (including anhydrides and acid esters) and aliphatic diols. Suitable dibasic acids include, for example, fεrephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, hiphem lene dicarboxyiic acid, letrahydroterephthalic acid, letrahydroisophlhalic acid, letrahydrophthalic acid, hydronaphlhaiene dicarboxylic acid, cyciohexanedicarboxylic acid, cyclopentyidicarboxylic acid, cyclooctyldicarboxylic acid, glutaric acid, sebacic, adipic acid, pimeSic acid, maSonie acid, fumarie acid, monoesters and di esters of the foregoing, and mixtures thereof Suitable aliphatic diols include, for example, ethylene glycol, propylene glycol, bufylene glycol. l ,3~propaϊiedioS. 1 ,3-butanedioL 1 ,4-biitanediol, dipropylene glycol. L5-penlaoediol, 1.6-hexanediol. dielhylene glycol, L4-cvc!ohexaoediol, 1.4- cyciohexanediπiethanoL neopentvl glycol, 1 ,8-octajiediol, iJ O-decanediol, 1 ,12- dodecanediol, diethyl ene glycol, triethylene glycol, tetraethylene glycol, and combinations tiiereof. Suitable ftuoropolymers include, for example, poiytetraftuoroethylene, ethyiene- tetrafluoroethylene copolymers, polyvinyidene fluoride, and combinations thereof

Suitable epoxy resins include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, epoxy novolacs. vinyl cyciohexane dioxide, oligomers of the foregoing epoxy resins, and combinations {hereof. Suitable epoxy resins are commercially available as, for example, EPON*? 828, EFON(K 825, D E Il. 317, EPONl, 100 IF, ERL422L and EPON-R- 871 , all from Dow Chemical: and ARALDITE)S GT7071 from Ciba Specialty Chemicals.

Suitable phenolic resms include, for example, novoiac resins, resol resins, phenol - formaldehyde resins, novolacs, phenol-acetaldehyde resins, resorcinoi-forniaJdehyde resins, phenol-furfural resins, polyvinyl phenol polymers, and combinations thereof

Suitable rosin and rosin derivatives include, for example, tall oil rosins, gum rosins, wood rosins, hydrogenated rosins, rosin esters, and combinations thereof.

Suitable terpene resins include, for example, polymers of beta-pinene. polymers of alpha-pinene. polymers of d-limonene. terpene-phenoi resins, aromatic-modified terpene resins, and combinations thereof.

Suitable aery late resins include, for example, homopolymers and copolymers of alky] (meth)acrylate monomers such as methyl acrylate. methyl methacryϊate, ethyl acryJate, ethyl methacn late, and the like.

Suitable poly amides belong to a generic family of resins known as nylons, characterized by the presence of an amide group (--C(O)NIi--). Nylon-6 and nylon- 6.6 are the generally preferred poly amides and are available from a v ariety of commercial sources. Other poly amides, however, such as nylon-4,6, nylon- 12. nylon- 6, 10, nylon 6,9, nylon 6/6T and nylon 6/V6T with mamine contents below about 0.5 weight percent, as well as others, such as the amorphous nylons, may be useful for particular applications. Mixtures of various polyamides. as well as various poly amide copolymers, are also useful. Polyamides can be obtained by a number of well known processes such as those described m U.S. Pat. Nos. 2,071 ,250, 2.071 ,251 , 2, 130,52.1 and 2,130,948 to Carotliers; 2,241 ,322 and 2,312,966 to Hanford: and 2,512,606 to Boiton el ai. Nylon-6, for example, is a polymerization product of caprolactam. Nyion-6,6 is a condensation product of adipie acid and L6-diarainohexane. Likewise, nylon 4,6 is a condensation product between adipic acid and 1 ,4-diaminobutane. Besides adipic acid, other useful diacids for the preparation of nylons include a/.elaic acid, sebacic acid, dodecane diacid. as well as terephthalie and isophihalic acids, and the like. Other useful diamines include ra-x>lyetie diamine, dι-(4- aminophenyl)methane. di-(4-aminoeyelohexyl)mefhane; 2.2-di-(4- aminophemi)propane. 2,2~di-(4-aminocyclohexyl)propane, among others. Copolymers of caprolactam with diacids and diamines are also useful.

After a composition comprising a poiyfarylene ether) and a pH sensitive compound is formed, it may be converted to articles using thermoplastic processes including, for example, injection molding, blow molding, extrusion, sheet extrusion, film extrusion, profile extrusion, pultrusion. compression molding, thermoforming, pressure forming, hydroforming, vacuum forming, foam molding, and the like

Exemplary articles include all or portions of the following articles, electrical components, fluid engineering components, automotive exterior parts, automotive underhood parts, consumer electronics, televisions, flexible industrial parts, wire coatings, materials for electronics fabrication, autoclavable articles for healthcare, and low-smoke materials for building and construction.

It is briefly noted that articles made using the composition can be authenticated. Stated another way, embodiments are envisioned where the pH sensitive article is employed to authenticate an article rather than the raw materials used to make the article. In this embodiment, the pH sensitive compound may be added during formation of the composition or formation of the article. There may be an advantage to adding the pH sensitive compound during formation of the article, because temperatures employed in forming articles, e.g., molding temperatures, are typically less than those employed m melt blending used to form pellets, as discussed above. As such, adding the pH sensitive compound during formation of the article can minimize degradation of the pH sensitive compound. in one embodiment, an article ma\ be surface coated w Uli a pH sensiln e compound to allow subsequent authentication of the article Thus, one embodiment is a method of authenticating an article, comprising at least partially extracting a pH sensitiv e compound from the surface of an article with a solv ent, wherein the article ^ the pioduct of sohent coating with a pH sensitn e compound a surface of an article comprising a poMan lene ether). mi\mg the so! vent haung the extracted pi 1 seiisstiΛ e compound with an acidic solution or a basic solution to form an obsen atton mixture, and observ ing {he observation mixture to determine if a predetermined color change occuitred m the observation mixture Solvent coating with a pH sensitn e compound may comprise appK nig to a surface of the article a solution comprising the pU sensitiv e compound and a soh em and removing solvent fiom the suiface of the article Suitable soh ents for soh em coating include those soh ems described abo\ e in the context of extracting a pi 1 sensitive compound from aα article Ia addition, suitable soh ents for soh em coatings comprise CrCVi alkanols such as, for example, methanol, ethanol. n-propanol. isopropanol, and the like

The follow my non-hmitmg examples further illustrate the \ aπous embodiments described herein

FXAMPI. E 1

This working example empk>> cd the matenals listed m Table I The ajnυiunts emplυ\ ed in the Examples are in w eight percent based on the total w eight of the composition, unless otherwise stated

15

A base powder blend was prepared comprising 48.6 parts by weight (pbw) 0,46 IV PPE, 48.6 pbw rubber-modified polystyrene (also known as high-impact polystyrene or HiPS). 1.45 pbw polyethylene, 0.145 pbw zinc oxide, 0.145 pbw- zinc sulfide, and 0.972 pbw tridecylphosphite. AIi components were dry blended and shaken for 3 minutes hi a paint shaker prior to extrusion. The resulting dry blend was added to the feed throat of the extruder, extruded at 29ϋ°C. and cut into pellets. The extruder was a 24-miilimeler. 8-barrel, twin-screw, co-rotating Prism extruder having a 28: i length-to-diameter CL. D) ratio. Plastic color chips of 2 inches x 3 inches x 0.100 inch (5.08 centimeters x 7.62 centimeters x 0.254 centimeter) dimensions were molded from the pellets at 300⁰C, with a molding tool temperature of 88^'''C.

The Example 1 powder blend composed an additional OJ part by weight thymolphthaJein, which was added at the dry blending stage. The molded plaques were light tan and opaque in color, indicative of natural resin. A plastic color chip was placed m a glass jar having a 2 inch (5.08 centimeter) inner diameter, containing about 50 milliliters (mL) acetone. The jar was capped, and the mixture was allowed to stand for 30 minutes. The jar was agitated initially for 5 seconds, again for 5 seconds at 15 minutes, and again for five seconds at 30 minutes. An aliquot (10 ml.) of the acetone was then removed using a pipet and added to a 20 mL glass vial that was atop a sheet of white paper and that contained 5 mL of a NaOH/ water solution of pH 10, as measured using a pH strip. A color change from colorless to light blue was observed. The plaque was removed from the extraction/developing chamber and allowed to air dry. ft looked substantially identical to an unexposed chip in color. although the 60 degree gloss value of the polished chip side was reduced from 90 to 25, The 60 degree gloss value was measured according to ASTM D523 using a BYK- Gardner micro- TRI -gloss meter.

EXAMPLE 2

In this example, the powder blend comprised 0.03 part by weight thyrnolphthaJein. The same procedure for Example 1 was employed. A color change was not detectable by visual observation. The plaque was removed from the extraclion/dev eloping chamber and allowed Io air dry. Again, the chip looked substantially the same as the unexposed chip in colon although the 60 degree gloss value of the polished chip side was similarly reduced as described in Example S .

EXAMPLE 3

In this example, the powder blend comprised 0.1 part by weight phenoϊphJJialεdn. The same procedure for Example 1 was employed. A color change from colorless to pink was visually observed. The plaque was remov ed from the extraction/developing chamber and allowed to air dry. ft looked substantially identical to an unexposed chip in color, although the 60 degree gloss value of the polished chip side was similarly reduced as described in Example \ .

EXAMPLE 4

The powder blend comprised 0.03 part by weight phenolphthaJein. The same procedure for Example 1. was employed. A color change was not detectable by visual observ ation. The plaque was removed from the extraction/developing chamber and allowed Io air dry. Il looked substantially identical to an unexposed chip in color, although the 60 degree gloss value of the polished chip side was similarly reduced as described in Example 1.

EXAMPLES 5-8

In these examples, the powder blends respectively comprised 0.03 part by weight (Ex. 5). 0. 1 part by weight (Ex. 6). 0.5 part by weight (Ex. 7). and 1.0 part by weight (Ex. 8) ihymolphthaiein. The same procedure was followed as for Example i with the exception {hat the solvent was changed from acetone to tetrahydrofuran ( THF). A color change was visually observed in each of examples 5-8. which indicated that varying the solvent can lead to a wider range in using the pH sensitive compound. For example, when acetone was used in Example 2, the color change was not clearly observed, whereas a color change was clearly observed using tetrahydrofuran solvent in Example 5.

Advantageously, the composition comprising the pH sensitive compound is capable of being authenticated without the use of spectroscopy or other expensive equipment. Moreover, since the pll sensitive compound can be disposed in the composition or article in such a manner that a person observing the composition could not observe a physical difference in appearance of a composition with the pH sensitive compound from one without the pH sensitive compound, a covert method of authenticating the composition is obtained. Additionally, since the color sensitive material is present in an amount less than or equal to about 1 weight percent of the total composition, minimal loss of mechanical properties is observed in the composition. Moreover, as readily understood by those skilled in the art, any loss in the mechanical properties or πieit flow properties can be overcome by adjusting, for example, the ratio of pøly(arylene ether) to the polyfalkenyl aromatic).

EXAMPLE 9

This example describes the preparation of a concentrate of a pH sensitive compound in a poiyCarylene ether)-compatible resin. The concentrate was prepared by melt kneading 5 weight percent phenolphthalein m rubber-modified polystyrene obtained as GEH HIPS from GE Plastics. Melt kneading was conducted on a 24-miilimeter. co-rotating twin-screw PRISM extruder operating at 232°C (45O⁰F). The extrudate was cooled and pelletked.

EXAMPLE 10

This example illustrates the use of a concentrate of pϊi sensitive compound in a poSvCarySene ether)~compatible resin to authenticate a poSvCarylene ether) composition. A melt-kneaded blend was prepared using 60 grams of the 5 weight percent phenolphthalein concentrate pellets from Example 9 and I H(K) giams of a black -col Oi ed, flame-ietarded Mend of pϋK (2 6-dinielh\ i-L4-phcm lene clhcr). rubber-modified poh stv reue and additn es obtained as NORYΪ * SF I -701 fi om Gb Plasties The meit-kneadmg pioceduie of Example <> was emplo\ ed, and the iesuhmg pellets were used to injection mold chips hav ing dimensions 2 inches \ ^"ϊ inches \ 0 1 18 inch (5 08 centimeters \ 7 62 centimeters \ 0 100 centimeter) Λ piece measuring 2 niches \ 0 5 inches \ 0 J i 8 inch (5 08 centimeters x 1 27 centimeters x 0 ^00 ceniimetei ) was cut from the chip and added to a 20 milhhtei scmiillation \ ial To this Ma! λ%ab added 7 milliliters tctrahx drofuran soh ent The ua! \\ &> then capped agitated b\ shaking for s seconds and allowed to sit for >0 minutes at room tempeiatuie \ 2 milliinei teti <ύϊ\ drofuran solution diiqυoi was then iemm ed from the M a! using a pi pet and added to a cieai 20 milliliter Λ ial lυ this test \ ial w as then added 2 milliliters of a pϊl 10 aqueous NaOI i solution -\ Λλlute precipitate was obseπed but there was no color change l he remaining ^ milliliters tetrah\ drofuran solution and the icM piece weie allow ed to MI in the capped MaI for I H homs A 2 milliliter aliquot w as then remov ed and added to a clean 20 milliliter \ial To this test uaS was then added 2 milliliters of the NaOH solution Λ white precipitate \\as> ob&cned and the SIUJIΛ turned pink With agitation of the MaL the pink color faded to white \n additional 2 milliliter of the \aOH solution was added and the pink colυr ietumed lhe pmk color w as maintained ev en aftei agitation of the ual ϊ his expenmeiit shows that a poh (ar\ 1ene ether) resin composition ma\ be made authenti eatable just pnor to molding h\ adding a small amount of a concentrate of a pH Hcnsitn e compound in a ρn)\ (an lone ether }-comρatibSe icsin

FXΛMPI F 1 1

flm example show s that a poh {arv leiic ether) resm composition ma\ be made authenticatabSe h\ direct addition of a pH sensitive compound (j e without first mcoiporatmg the pH ^ensUn e compound into a iesm concentiate) 4 melt-kneaded blend wat> piepaxed using > gϊams of phenolphthaicm powdei and 180t> giams \()RYL ϋ SE 1-70] The pelleti/ed blend \\a»s used to injection mold chips hαwng dimensions 2 inches x ^"ϊ inches \ ii l l u inch (> ⁽>8 centtmetets \ 7 62 centimeters \ 0 300 cenUmeteO -\ piece measuung 2 inches \ 0 5 inches \ O i I S inch {5 08 centimeters \ 1 27 centimeters \ 0.300 centimeter) w as cut from the chip and added KJ a 20 milliliter scintillation \ ia1 To this vial was added 7 milliliters tetrahydrofuran sol \ ent The vial was then capped, agitated by shaking for 5 seconds, and allowed Io sit for 30 minutes at room temperature, A 2 milliliter tetrahydrofuran solution aliquot w as then remo ed using a pi pet and added to a clean 20 milliliter ual To this test uai was then added 2 milliliters pi J H) NaOlI solution A white precipitate was observ ed, but there was no color change. The remaining 5 milliliters letrahydrofuran solution and the test piece w ere allowed to sit in the capped via! for I X hours A 2 milliliter aliquot w as then iemov ed and added to a clean 20 milliliter x ial. To this test uaϊ w as then added 2 milliliters of NaOH solution. A white precipitate was observ ed, and the slurry turned pini With agitation of the viaL the pink color faded to white. An additional 2 milliliters NaOH solution was added, and the pink color returned. The pink color was maintained ev en after agnation of the ual Tins experiment shows that a poKian lene ether) resin composition ma> be made authentieatable b> adding a small amount of pH sensitiv e compound. Together with Example 10. it also shows that similar authentication results are obtained when a pTI sensitix e compound is incorporated in a polyCarylene ether) composition directly or via a resin concentrate.

EXAMPLE 12

The procedure of Example 10 was used, except that the concentrate was blended not with NORYLV SE1-70I but with NORYL if N190X-701 , which K an organophosphate flame- retarded blend of poly{2.6-diroeιh\ !-1.4-phen> iene ether), rubber-modified poh se rene, rubber impact modifier, and addith es Similar authentication results were obtained, in that a color change was observ ed on mixing pH 10 aqueous ^aOH solution with a tetrahv drofuran solution that had contacted the molded composition for I H hours, but not with a tetrahydrofuran solution that had contacted the molded composition for only 30 minutes.

EXAMPLE 13 This procedure of Example i i was used, except that the pH sensitive compound was blended directly not with NORYL* SEI -70? but with NORYL* N190X-701, Similar authentication results were obtained, in that a color change was observed on mixing a pH 10 aqueous NaOl-I solution with a letrahydrofuran. solution that had contacted the molded composition for 18 hours, but not with a tetrahydrofuran solution that had contacted the molded composition for only 30 minutes.

EXAMPLES 14-17

These examples illustrate that a molded article may be made aulhenticatahle by application of a surface coating of a pH sensitive compound. Chips having dimensions 2 inches x 3 inches x 0.100 inch (5.08 centimeters x 7.62 centimeters x 0.254 centimeter) were molded from two colored blends of po1yf2.6-dimetliyl-1.4- phenyiene ether) and rubber-modified polystyrene: blend L in which the color is derived from a pigment, and blend 2, in which the color is derived from dyes. Two solutions of 5,2 weight percent phenolphthaiein in solvent were prepared: one in acetone and one in ethanoS.

The molded chips were coated with pf-i indicator as follows. A chip was placed on a flat surface, and two milliliters of the ethanol or acetone solution of pH indicator was added drop-wise to the face of the chip until it was completely covered with solution. The chips were then dried (i.e.. solvent was driven off) by blowing a stream of nitrogen gas over the solution-coated chip. The chips coated with acetone solution remained tacky even when dried for several minutes, whereas the chips coated with ethanol solution dried rapidly and were not tacky. The combinations of resin type and coating solvent are summarized in Table 2.

From each coated chip, a section having dimensions 3 inches x 0.5 inch x 0.100 inch (7.62 centimeters x 1.27 centimeters x 0.254 centimeter) was cut out and placed in a 20 milliliter glass vial with 5 milliliters of acetone, and agitated for 5 seconds. After 2 minutes, a 2 milliliter aliquot of each acetone solution was added to a corresponding empty vial. The aliquots corresponding to Examples 15 and 17 had a noticeably grey color. To each vial was added 1 -2 milliliters of an aqueous pH 10 NaOH solution. Each solution turned a deep pink, although the samples for Examples 15 and 1.7 were darker, presumably due to the combined absorbances of the pH indicator and extracted colorants.

These examples show that molded articles may be authenticated by first solvent coating them with a pH sensitive compound and subsequently extracting the pH sensitive compound from the surface of the article, Ethanoi is a particularly useful solvent for the solvent coating process. The examples also show that the authentication method may be used even when the resin composition contains extract ahl e col orants.

Table 2

This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over {he conflicting term from the incorporated reference.

Claims

CLAIMS:

1. A resin composition comprising:

a poiy(aryiene ether); and

a pH sensitive compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added to a basic or acidic solution.

2. The resin composition of Claim I . wherein the poiy(aryiene ether) comprises a plurality of staictural units of the formula

wherein for each structural unit each Q¹ is independently halogen, primary or secondary Cj-Ci:? alkyl. Cj-Cu aniinoalkyl, Cj-Cu hvdroxyalkyl. aryl. CrCj? haloalkyl, CpCj > hydrocarbyloxy. or CpCo halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms: and each Q¹ is independently hydrogen, halogen, primary or secondary- C₁-Ci; alkyl. Ci-Cn arninoaikyl. Ci-Cn hydroxy alky I, arvi, Ci-C]?. haloalkyl. Ci-Cj ₂ hydrocarbyloλ} , or Ct-Cjj halohydrocarbylox}-^" wherein at least two carbon atoms separate the halogen aid oxygen atoms.

3. The resin composition according to any of Claims 1 - 2, wherein the poly(aryleoe ether) comprises 2,6-dimethy]-L4-phenylene ether units.

4. The resin composition according to any of Claims 1 - 3. wherein the pH sensitive compound is stable at temperatures up to about 280^*C,

5. The resin composition according to any of Claims I - 4, further comprising a poiy(alkeny i aromatic ).

6 Hie resin composition according to any of Claims I - 5. further comprising a poiyamide or a poiyoleAn

7, The resin composition according to any of Claims i - 6, wherein the pli sensitive compound is present in an amount of about 0 ⁽Jl weight percent to about 40 w eight percent based on a total weight of the composition.

S The resin composition of Claim 7. wherein the amount of pH sensitive compound is about 0.1 veight percent to about I weight percent.

9 The re&m composition according to am of Claims 1 - K wherein the pH sensith e compound comprises th\ røolphthalein, phenolphthalein, or a combination thereof

10 The resin composition according to any of Claims 1 - *>. wherein the pH sensitiv e compound is selected from the group consisting of methv I \iolet. thymol blue, metliyl yellow , bromophenol blue, congo red. nieth\ l orange, litmus, bromocresol purple, phenol red, thymol blue, ali/arin Yellow R. indigo carmine, and combinations thereof.

1 1. The resin composition according to any of Claims J - 10. further comprising a second pM sensitive compound.

12. The resin composition according to any of Claims 1 - 1 1. wherein the pH sensitive compound is colorless at a neutral pH

13 The resin composition according to any of Claims 1 - 12, wherein the pH sensitn e compound is capable of changing to multiple colors as a function of pϊi

14. An article comprising the resin composition according Io any of Claims i - 13.

15. A resin composition comprising;

about 10 to about 90 weight percent of a poh (arv1ene ether) comprising 2.6- dimethy1-S .4-phenylene ether units; about H) lo about 70 weight percent of a poly(a1keiiy1 aromatic) selected from the group consisting of homopolymers of an alkenyl aromalic monomer, random copolymers of an alkenyl aromatic monomer with one or more different monomers, unhydrogenated and hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene: rubber-modified poly(alkeny! aroniatic)s. and combinations thereof; and

about 0.01 weigh I percent to about 40 weight percent of a pH sensitive compound capable of providing a color change when the pH sensitive compound is at least partially extracted from the resin composition and is added Io a basic or acidic solution; wherein the pH sensitive compound is selected from the group consisting of thymolphthaiein. phenol phthalein. methyi violet, thymol blue, methyi yellow, bromopheno! blue, congo red, methyl orange, litmus, brαmocresol purple, phenol red. thymol blue, alizarin Yellow R. Indigo carmine, and combinations thereof;

wherein all weight percents are based on the total weight of the composition.

16. The resit* composition according to Claim 15, further comprising a second pl ϊ sensitive compound.

17 The resin composition according to any of Claims 15 - .16, wherein the pH sensitive compound is colorless at a neutral pϊl

18. The resin composition according to any of Claims 15 - 17, wherein the pH sensitive compound is capable of changing to multiple colors as a function of pH.

19. An article comprising the resin composition according to any of Claims 15 -

18.

20. A poly(arylene ether) concentrate, comprising:

a poMarylene ether), and

about 0.5 to about 40 weight percent of a pH sensitive compound, based on the total weight of the concentrate.

2! . The polyf^'arylene ether) concentrate of claim 20, further comprising about 5 to about 5 weight percent of an organic phosphate flame retardant.

22. The poly(arylene ether) concentrate according to any of Claims 2*) - 21, wherein the poly(arylene ether) comprises a plurality of structural units of the formula

wherem for each structural unit, each Q* is independently halogen, primary or secondary CrCt₂ alkyl, CrCt:? aniinoai^'kyi CrCi ? hydroxyalkyi, aryl, CrCn haloalkyl. C₁-C n hydrocarbyloxy, or CrCu- halohydrαcarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q^" is independently hydrogen, halogen, primary or secondary Cj-Cja aikyl, CpC₁-; aminoalkyl, CpCu hydroxy alkyl, aryt CrCu haSoalkyl, Ci-Cu hydrocarbyloxy\ or Ci-Cu halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

23. The poly(ary1ene ether) concentrate according to any of Claims 20 - 22, wherein the poMarylene ether) comprises 2,6-dimethyl-l ,4~pheiiy!ene ether units.

24. The poiyCarylene ether) concentrate according to any of Claims 20 - 23, wherein the pH sensitive compound is stable at temperatures up to about 280⁰C.

25. The poly(arylene ether) concentrate according to any of Claims 20 - 24. further comprising a poiy(alkenv! aromatic).

26. The poiy(arylene ether) concentrate according to any of^" Claims 20 - 25, further comprising a polyamide or a poly olefin.

27 The poly{ary!ene ether) concentrate according to any of Claims 20 ~ 26, wherein the pH sensitive compound comprises thymoiphfhaSehi, phenoiphthalein, or a combination thereof. 28 The polMaπ iene ether) concentrate according to am of Claims 20 -

27. wheiein the pH sensitiv e compound is selected from the group consisting of rnetlrv l v iolet, thλ mol blue, methλ l > cllow, bromophenol blue, congo red. meth> l oiange, litmus, biomociesol purple, phenol led. ιh\ mol blue, ali/aπn Yellow R- Indigo carmine, and combinations theieof

2'⁾ The poh (an lene ether) concentrate according to am of Claims 20 -

28. further comprising a second pH sensitn e compound

30 The poh (an lene ether) concentiate according to am of Claims 20 -

29. wherein the pH setisUn e compound is coloiϊess at a neutral pH

31 The polMaπ iene ether) concentrate according to am of Claims 20 -

30. wherein the pli sensitn e compound is capable of changing to multiple colors as a function of pi I

32 Λ method of making a iesin composition, comprising

melt mixing a poh (an lene ether) and a pH sensitiv e compound capable of providing a color change when the pH sensitiv e compound is at least paitialh extracted fiom the jtfsin composition and is added to a basic or acidic solution

33 The method of Cϊaim 32. furthet composing melt mixing a poMaikem l aromatic) w ith the poh (an, lene ether) and the pH sensitπ e compound

34 The method according to am of Claims 32 - 33. Λ\ herein the poh (an lene etliei) and the poMaikero l aioinabc) are nidi mixed io form a first melt blend, and the pH sensniΛ e is added to the first melt Mend to form a second melt blend

3^s? The method according to am of Claims 32 - 34, wherein the pH sensitiv e compound comprises ths molphthalein. phenolphihalein. or a combination thereof

36 ϊhe method according tυ am of Claims 32 - 35, wherein the pH sensitiv e compound is selected from the group consisting of mcthx l \ iolet. thx mol blue. meth\ l > ellow . bromophenol blue, congo red. meth> l orange, litmus. bromocresol purple, phenol red, thymol blue, ali/arin Yellow R, indigo carmine, and combinations thereof.

37. The method according to am of Claims 32 - 36, further comprising a second pH sensitiv e compound

38 The method according Io any of Claims 32 - 37, wherein the pH sensitive compound is colorless at a neutral pH.

39. The method according to any of Claims 32 - 38, wherein the pH &ensitiv e compound is capable of changing to multiple colors as a function of pH

40 A method of authenticating a resin composition or an article, comprising

at ieast partial!} extracting a pH sensitive compound from the resin composition or the article with a so! vent, wherein the res, in composition or the article comprises

a polyf arylene ether), and

the pH sensitύ e compound;

mixing the solvent Inning the extracted pH sensitive compound with an acidic solution or a basic solution to form an observation mixture: and

observing the observation mixture to determine if a predetermined color change occurred in the obser\ atiori mixture,

41. The method of Claim 40. wherein the polv(arylene ether) comprises a plurality of structural units of the formula

wherein for each structural unit, each Q' is independently halogen, primary or secondary Cj-C^ alkyl, Ci-Cu aminoalkyL Ci-Crj hydroxy alkyl, ar> l, CpCf_> haloalkyl. CyC}₂ hydrocarbyloxy, or CrC^ halohydrocarbyloxy wherein a* least two carbon atoms separate the halogen and oxygen atoms; and each Q² is independently hydrogen, halogen, primary or secondary Ct-C 12 aJkyl, CpCo aminoalkyl, C_t-Ct2 hydroxy alkyl, aryt CrCu haloalkxi. Ci-Cu hvdrocaxfoyloxy, or Ci-Cu lialohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

42. The method according to any of Claims 40 - 41, wherein the poly{aryiene ether) comprises 2j>-dimethy)-i ,4-pheny .terse ether units

43. The method according to any of Claims 40 - 42. wherein the pH sensitive compound comprises thymol phthalein. phenol phthalein. or a combination thereof.

44. The method according to any of Claims 40 - 43, wherein the pH sensitive compound is selected from the group consisting of methyl violet, thymol blue, methyl yellow, bromophenol blue, congo red. methyl orange, litmus. faromocresol purple, phenol red, thymol blue, alizarin Yeilow R. ϊndigo carmine, and combinations thereof.

45 The method according to any of Claims 40 - 44, further comprising a second pH sensitive compound.

46. The method according to any of Claims 40 - 45. wherein the pH sensitive compound is colorless at a neutral pH.

47. The method according to any of Claims 40 - 46. wherein the pll sensitive compound is capable of changing to multiple colors as a function of pH.

48. The method according to any of Claims 40 - 47, wherein the pH sensitive compound is present in an amount of about 0.01 weight percent to about 40 weight percent based on a total weight of the composition.

49. The resin composition according to any of Claims 40 - 48. wherein the pH sensitive compound is present in an amount of about 0.1 weight percent to about 40 weight percent based on a total weight of the composition.

50. The method according to any of Claims 40 - 49. wherein the solvent is selected from the group consisting of acetone, letrahydrofuran, methyl ethyl ketone. methyl isobutyl ketone. 1 ,2-dimethoxyethane. acetonitrile, 1.,4-dioxaπ.e, and combinations thereof.

5 J , The method according to any of Claims 40 - 50. wherein the solvent comprises acetone.

52. The method according to any of Claims 40 - 51, wherein the solvent having the extracted pH sensitive compound is mixed with the acidic solution, and wherein the acidic solution comprises acetic acid, citric acid, nitric acid, hydrochloric acid. sulfuric acid, tartaric acid, phosphoric acid, alum, or a combination thereof,

53. The method according to any of Claims 40 - 52, wherein the solvent having the extracted pH sensitive compound is mixed with the basic solution, and wherein the basic solution comprises sodium bicarbonate, borax, calcium carbonate, magnesia, ammonia, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, and lime, or a combination thereof.

54. The method according to any of Claims 40 - 53, wherein the predetermined color change comprises an absorbanee change of at least 0.05 absorbance units per centimeter path length at the maximum absorbance of an acidic or basic form of the pH sensitive compound.

^ A method of authenticating a resin composition or an article, comprising:

at least partial!}' extracting a pH sensitive compound .from the resin composition or the article with a solvent, wherein the solvent is selected from the group consisting of acetone, tetraliydrofurai. methyl ethyl ketone, methyl isobutyl ketone, 1.2- dunethoxyethane. aeetomtrile, 1,4-dioxane, and combinations thereof; and wherein the resin composition or the article comprises

about 10 to about Vt) weight percent of a polyCarySene ether) comprising 2.6-dimethyi- 1 ,4-phenySene ether units: about H) lo about 70 weight percent of a poly(a1kenv1 aromatic) selected from the group consisting of homopoϊymers of an alkenyl aromatic monomer, random copolymers of an alkemi aromatic monomer with one or more different monomers, unhydrogenaied and hydrogenated block copolymers of an alkenyl aromatic and a conjugated diene: rubber-modified pohialkenyl aroniatic)s, and combinations thereof; and

about 0.01 w eight percent to about 40 weight percent of the pH semith e compound, wherein the pH sensith e compound is capable of prov iding a color change when the pH sensitive compound is at least partially extracted from {he resin composition and is added to a basic or acidic solution; wherein the pH sensitiv e compound is selected from the group consisting of thvmolphthaiein, phenolphthaiem, methyl uolet th\ mol blue, methyl yellow, bromophenol blue, congo red. methy l orange, litmus. bromocresol purple, phenol red, thymol blue, ah/arm Yellow R. hidigo carmine, and combinations thereof;

nnxing the solvent hav ing the extracted pϊl sensitiv e compound with an acidic solution or a basic solution to form an obsen ation mixture, and

observing the obsen ation mixture to determine if a predetermined color change occurred in the obsen ation mixture

56. A method of forming an aυthenti eatable poh {aryleαe ether) composition, comprising:

melt blending a poMarylene ether) and a concentrate comprising a polymer resin and a pH sensitiv e compound.

57. The method of claim 56. w herein the polymer resin has a glass transition temperature or a melting temperature iess than or equal to about 170^vC

58. The method according to any of Claims 56 - 57, wherein the pols mer resin is selected from the group consisting of poK sls renes, hydrocarbon waxes, hv drocarbon resins, fatty acids, polyolefins, polyesters. Ouoropolymers, epox> resins, phenolic resins, rosins and rosin derivatives, terpene resins, acrylaie resins, poiyamides, and combinations thereof.

59. A method of forming an aulhenticatable poly{arylene ether) composition, comprising:

melt blending

a poly(arylene ether), and

a concentrate comprising a polystyrene and a pH sensitive compound selected from the group consisting of ihymolphthalein, phenolphthalein, methyl violet, thymol blue, methyl yellow, hromophenol blue, congo red. methyl orange, litmus, bromocresol purple, phenol red, thymol blue, alizarin Yellow R, Indigo carmine, and combinations thereof

60. A method of authenticating an article, comprising:

at least partially extracting a pH sensitive compound from the surface of an article with a solvent, wherein the article is the product of solvent coating with a pH sensitive compound a surface of an article comprising a poly(arylene ether):

mixing the solvent having {he extracted pH sensitive compound with an acidic solution or a basic solution to form an observation mixture: and

observing the observation mixture to determine if a predetermined color change occurred in the observation mixture

61. The method of claim 60, wherein said solvent coating with a pH sensitive compound comprises

applying Io a surface of the article a solution comprising the pH sensitive compound and a solvent comprising Cj -Q alkanol: and

removing solvent from the surface of the article.

62. The method according to any of Claims 60 - 61 , wherein said pH sensitive compound selected from the group consisting of thymolphthalein. phenoiphfhaiein. methyl violet, thymol blue, methyl yellow, bromophenol blue, congo red. methyl orange, litmus, bromocresoi purple, phenol red, thymol blue, alizarin Yellow R, Indigo carmine, and combinations thereof.

63. The method according to any of Claims 60 - 62, wherein the predetermined color change comprises an absorhance change of at least 0.05 absorbance units per centimeter path length at the maximum absorbance of an acidic or basic form of the pH sensitive compound.

64. The method according to any of Claims 60 - 63, wherein the pM sensitive compound comprises thymolphthalein. phenol phfalein. or a combination thereof.

65. The method according to any of Claims 60 - 64. further comprising a second pH sensitive compound.

66 The method according to any of Claims 60 - 65, wherein the pH sensitive compound is colorless at a neutral pH.

67. The method according to any of Claims 66 - 67, wherein the pH sensitive compound is capable of changing to multiple colors as a function of pll.