EP1169389A1

EP1169389A1 - Compositions of an interpolymer and polyphenylene ether resin

Info

Publication number: EP1169389A1
Application number: EP00910173A
Authority: EP
Inventors: Adrianus J. F. M. Braat; Benny David; Juraj Liska; Glen D. Merfeld; John Bennie Yates, Iii
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1999-04-02
Filing date: 2000-02-14
Publication date: 2002-01-09
Also published as: KR20010112375A; CN1353739A; AU3231100A; AR032582A1; JP2002541293A; WO2000060002A1

Abstract

The invention generally relates to novel compositions comprising (i) at least one substantially random interpolymer containing (a) ethylene; (b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and (c) optionally, one or more polymerizable C3 to C20 olefinic monomers, and (ii) at least one polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25 °C. In a preferred embodiment, the compositions are substantially free of elastomeric block copolymer resins. The invention also relates to processes to manufacture the blends as well as articles made from the blends.

Description

COMPOSITIONS OF AN INTERPOLYMER AND POLYPHENYLENE ETHER RESIN

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention generally relates to novel compositions comprising (i) at least one substantially random interpolymer containing (a) ethylene; (b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and (c) optionally, one or more polymerizable C₃ to C₂₀ olefinic monomers, and (ii) at least one polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C. In a preferred embodiment, the compositions are substantially free of elastomeric block copolymer resins, such as polystyrene- poly(butadiene)-polystyrene block copolymers, polystyrene- poly(ethylenebutylene)-polystyrene block copolymers and polystyrene- poly(ethylenepropylene) block copolymers and the like.

The invention also relates to processes to manufacture the blends as well articles made from the blends.

2. Brief Description of the Related Art

Polyphenylene ether resins (hereinafter "PPE") are commercially attractive materials because of their unique combination of physical, chemical, and electrical properties. It is known in the art that the properties of the PPE can be materially altered by forming compositions with other polymers and many such PPE compositions have been disclosed in the prior art.

Blends of PPE and polyolefins are of great interest because they can potentially bring some of the chemical resistance of the polyolefins to the PPE. In turn, PPE can potentially add improved temperature resistance, flame retardance, electrical properties, dimensional stability, surface adhesion, thermo-oxidative stability and flame retardance to polyolefin resins. However, such blends very often suffer from limitations of their own, apart from the limitations of the individual resins, due to the relative incompatibility of the PPE and the polyolefin resin, especially in those blends where one of the resins is present in an amount of more than about 3% by weight, based on 100% by weight of the two combined. In such instances, the beneficial property aspects which one resin could possibly confer on the other may not be fully realized.

The prior art has generally sought to improve the properties of these blends. Elastomeric materials such as polystyrene-poly(butadiene)-polystyrene block copolymers and polystyrene-poly(ethylenebutylene)-polystyrene block copolymers as well as polystyrene-poly(ethylenepropylene) have been used to improve the compatibility of PPE and polyolefin resins and to increase morphological stability of the composition in the melt. These systems are relatively inefficient because they require high levels of the elastomeric materials to give a substantial effect. Additionally, the elastomeric materials typically dissolve into the PPE phase and reduce the many desirable attributes of the PPE. In large part due to the deficiencies of the current state of the art, commercialization of PPE-polyolefin compositions has been limited. It is therefore apparent that a need continues to exists for the development of compositions of PPE and polyolefins as well as for methods to manufacture such compositions. SUMMARY OF THE INVENTION

The needs discussed above have been generally satisfied by the discovery of a novel compositions comprising (i) at least one substantially random interpolymer containing (a) ethylene; (b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and (c) optionally, one or more polymerizable C₃ to C₂₀ olefinic monomers, and (ii) at least one PPE having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C.

The PPE is preferably prepared by a process comprising oxidative coupling in a reaction solution at least one monovalent phenol species using an oxygen containing gas and a complex metal catalyst to produce a PPE having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, more preferably within the range of about 0.08 dl/g to about 0.15 dl/g, as measured in chloroform at 25°C; removing at least a portion of the complex metal catalyst with an aqueous containing solution; and isolating the PPE through devolatilization of the reaction solvent.

The description that follows provides further details regarding various embodiments of the invention.

DESCRIPTION OF THE DRAWINGS

Not applicable

DETAILED DESCRIPTION OF THE INVENTION

The term "terpolymer" is used herein to indicate a polymer wherein three different monomers are polymerized to make the terpolymer. The term "interpolymer" is used herein to indicate a polymer wherein two or more, preferably three or more different monomers are polymerized to make the interpolymer.

The term "substantially random" in the substantially random interpolymer comprising ethylene, one or more vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, and preferably one or more C₃ to C₂₀ olefinic monomers as used herein means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method, Academic Press New York, 1977, pp. 71-78. Preferably, the substantially random interpolymer does not contain more than 15 percent of the total amount of vinylidene aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the Carbon-13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.

Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001 , 0.001 , 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.

The substantially random interpolymers of the present invention preferably comprise at least three different monomers.

In a preferred embodiment, the substantially random interpolymers of the present invention comprise (1 ) from about 19.5 to about 98.5, preferably from about 25 to about 95, more preferably from about 30 to about 94 mole percent of ethylene; (2) from about 0.5 to about 60, preferably from about 1 to about 55, more preferably from about 1 to about 50 mole percent of one or more aromatic vinylidene monomers or hindered aliphatic vinylidene monomers, and (3) from about 1 to about 80, preferably from about 4 to about 65, more preferably from about 5 to about 50 mole percent of one or more C₃ to C₂₀ olefin monomers. It is to be understood that the total amount of (1 ), (2) and (3) is 100 mole percent.

The number average molecular weight (Mn) of the interpolymers of the present invention is usually greater than about 1 ,000, preferably from about 5,000 to about 1 ,000,000, more preferably from about 10,000 to about 500,000.

The present invention particularly concerns the following terpolymers: ethylene/styrene/propylene; ethylene/styrene/4-methyl-1 -pentene; ethylene/styrene/hexene-1 ; ethylene/styrene/octene-1 ; and ethylene/styrene/norbornene as well as terpolymers of ethylene/styrene/butene-1 and ethylene/styrene/vinylbenzocyclobutene.

Suitable alpha -olefins, or combinations of alpha -olefins, which can be employed as olefinic monomer(s) (3) include for example, those containing from 3 to about 20, preferably from 3 to about 12, more preferably from 3 to about 8 carbon atoms. Suitable olefinic monomers which can be employed as olefinic monomer(s) (3) include strained ring olefins such as norbornene. Particularly suitable as olefinic monomer(s) (3) include propylene, 4-methyl-1- pentene, pentene-1 , hexene-1 and octene-1. Butene-1 or vinylbenzocyclobutene can be utilized in combination with other alpha -olefins or olefinic monomers such as, for example, propylene, hexene-1 , octene-1, or norbornene, or any other combination except for the above noted combination of ethylene/styrene/butene-1 or ethylene/styrene/vinylbenzocyclobutene.

Suitable vinylidene aromatic monomers for use as component (2) include, for example, those represented by the following formula I:

Ar (CH₂)_n

1 I 2

I R— C=C(R²)₂

wherein R¹ is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R² is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C -alkyl, and C -haloalkyl; and n has a value from zero to about 6, preferably from zero to about 2, more preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, alpha- methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, and the like. Particulariy suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, alpha -methyl styrene, the lower alkyl- or phenyl- ring substituted derivatives of styrene, such as ortho-, meta-, and para- methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof, and the like. A more preferred monovinylidene aromatic monomer is styrene. Suitable "hindered aliphatic or cycloaliphatic vinylidene monomers" for use as components (2) include addition polymerizable vinylidene monomers corresponding to the following formula II:

R³ „ R^-C=C(R²)₂

wherein R¹ is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; each R² is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to about 4 carbon atoms, preferably hydrogen or methyl; and R³ is a sterically bulky, aliphatic substituent of up to 20 carbons; or alternatively R¹ and R³ together form a ring system. By the term "sterically bulky" it is meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations. Preferred hindered aliphatic or cycloaliphatic vinylidene monomers are those in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted. Examples of such substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyi, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbomyl, and the like. Most preferred hindered aliphatic or cycloaliphatic vinylidene compounds are vinyl cyclohexane and the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially suitable is vinyl cyclohexane.

The substantially random interpolymers of the present invention may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art. The polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.

The substantially random interpolymers of the present invention can be prepared as described in U.S. application Ser. No. 545,403 filed Jul. 3, 1990 (corresponding to EP-A-0,416,815) by James C. Stevens et al., both of which are incorporated herein by reference in their entirety. Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from - 30°C. to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization. While preparing the. substantially random interpolymers of the present invention as will be described hereinafter, an amount of atactic vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinylidene aromatic monomer. The presence of vinylidene aromatic homopolymer is in general not detrimental for the purposes of the present invention and may be tolerated. The vinylidene aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non- solvent for either the interpolymer or the vinylidene aromatic homopolymer. In one embodiment of the invention, it is preferred that no more than 25 weight percent, preferably less than 15 weight percent based on the total weight of the interpolymers of vinylidene aromatic homopolymer is present in the interpolymer blend component.

Examples of suitable catalysts and methods for preparing the substantially random interpolymers of the present invention are disclosed in U.S. application Ser. No. 545,403, filed Jul. 3, 1990 now pending (EP-A-416,815); U.S. application Ser. No. 702,475, filed May 20, 1991 (EP-A-514,828) now abandoned; U.S. application Ser. No. 876,268, filed May 1 , 1992, (EP-A- 520,732) now U.S. Pat. No. 5,721 ,185; U.S. application Ser. No. 241 ,523, filed May 12, 1994 now U.S. Pat. No. 5,470,993; as well as U.S. Pat. Nos. 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321 ,106; 5,347,024; 5,350,723; 5,374,696; 5,399,635; 5,556,928; and 5,872,201 all of which patents and applications are incorporated herein by reference.

The substantially random interpolymers of the present invention can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. Further preparative methods which may be applicable for the interpolymers of the present invention have been described in the literature. Longo and Grassi (Makromol. Chem., Volume 191 , pages 2387 to 2396 [1990]) and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCI₃) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am.Chem.Soα.Div. Polym. Chem.) Volume 35, pages 686,687 [1994]) have reported copolymerization using a TiCI₄/NdCI₃/AI(iBu)₃ catalyst to give random copolymers of styrene and propylene. Lu et al (Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCI4/NdCI3/MgCI2 /AI(Et)3 catalyst. Sernetz et al. (Macromol. Chem. Phys., v 197, pp 1071-1083, 1996) have described copolymerization of styrene with ethylene using Me₂Si(Me₄C) (N-tert- butylJTiClz/methylaluminoxane. Another suitable method includes the method disclosed for the manufacture of alpha-olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene described in U.S. Pat. No. 5,244,996, assigned to Mitsui Petrochemical Industries Ltd. All of the above are incorporated herein by reference.

The PPE employed in the present invention are known polymers comprising a plurality of structural units of the formula III

wherein each structural unit may be the same or different, and in each structural unit, each Q¹ is independently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹. Most often, each Q¹ is alkyl or phenyl, especially C_1-4 alkyl, and each Q² is hydrogen.

Both homopolymer and copolymer PPE are included. The preferred homopolymers are those containing 2,6-dimethyl-1 ,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2, 3, 6-trimethyl-1 ,4-phenylene ether units. Also included are PPE containing moieties prepared by grafting vinyl monomers or polymers such as polystyrenes and elastomers, as well as coupled PPE in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly(phenylene ether) chains to produce a higher molecular weight polymer, provided a substantial proportion of free OH groups remains. Also included are PPE 's containing a functional endgroup, obtained, for example, from reaction with a reactive compound having the functional endgroup.

The intrinsic viscosity (hereinafter "I.V.") of the PPE is most often in the range of about 0.05-0.60 dl./g., preferably about 0.08-0.20 dl./g., more preferably in the range of about 0.10-0.14 dl./g., as measured in chloroform at 25°C. As the I.V., a measure of molecular weight, decreases the physical properties of the compositions becomes enhanced in many ways. For example, compositions wherein the PPE has an I.V. in the range of about 0.10-0.14 dl./g., typically exhibit a higher heat resistance than compositions wherein the PPE has an I.V. substantially higher (e.g., an I.V of greater than about 0.38 dl/g) than this range. Although not wishing to be bound by any theory, it is thought that the solubility of the PPE in the interpolymer has increased as the molecular weight, as indicated by I.V., has decreased. Additionally, because of improved viscosity matching, a more uniform dispersion would be obtained which would contribute to enhanced physical properties. It has been shown that PPE with a low I.V. offers improvements in flame retardance performance as correlated with faster rates of char formation. Preferred low molecular weight PPE include generally those that have a number average molecular weight within the range of about 1250 to about 7000 and a weight average molecular weight within the range of about 2500 to about 15,000, as determined by gel permeation chromatography, with a preferred number average molecular weight within the range of about 1750 to about 4000 and a weight average molecular weight within the range of about 3500 to about 9,000, as determined by gel permeation chromatography. Correlation of PPE's Tg and molecular weight is very specific and related to PPE structure. For illustration, Tg drops only 35% at ten fold drop of molecular weight. That means, the retention of heat properties is extraordinary and beneficial for the application where a high flow is important (low IV PPE) while retaining heat properties.

The PPE are typically prepared by the oxidative coupling of at least one monohydroxyaromatic compound such as 2,6-xylenol, 2,3,6-trimethylphenol, or mixtures of the foregoing. Catalyst systems are generally employed for such coupling and they typically contain at least one heavy metal compound such as a copper, manganese, or cobalt compound, usually in combination with various other materials.

It will be apparent to those skilled in the art from the foregoing that the PPE contemplated in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features.

The polymerization of the phenolic monomer may be carried out by adding the phenolic monomer or monomers to a suitable reaction solvent and preferably, a copper-amine catalyst. It is preferred to carry out the polymerization in the presence of a cupric or cuprous salt-secondary amine catalyst such as, for example, cupric chloride and di-n-butylamine. The polymerizations are advantageously carried out in the presence of an inorganic alkali metal bromide or an alkaline earth metal bromide. The inorganic bromides may be used at a level of from about 0.1 mole to about 150 moles per 100 moles of phenolic monomer. These catalyst materials are described in U.S. Pat. No. 3,733,299 (Cooper et al.). Tetraalkylammonium salts may also be employed as promoters if desired. These promoters are disclosed in U.S. Pat. No. 3,988,297 (Bennett et al.).

The primary, secondary or tertiary amine component of the catalyst complex generally correspond to those disclosed in U.S. Pat. Nos. 3,306,874 and 3,306,875 (Hay). Illustrative members include aliphatic amines, including aliphatic mono- and di-amines, where the aliphatic group can be straight or branched chain hydrocarbon or cycloaliphatic. Preferred are aliphatic primary, secondary and tertiary monoamines and tertiary diamines. Especially preferred are mono-, di- and tri(lower) alkyl amines, the alkyl groups having from 1 to 6 carbon atoms. Typically, there can be used mono-, di- and tri- methyl, ethyl, n-propyl i-propyl, n-butyl substituted amines, mono- and di- cyclohexylamine, ethylmethyl amine, morpholine, N-(lower) alkyl cycloaliphatic amines, such as N-methylcyclohexylamine, N.N'-dialkylethylenediamines, the N.N'-dialkylpropanediamines, the N.N.N.'-trialkylpentanediamines, and the like. In addition, cyclic tertiary amines, such as pyridine, alpha-collidine, gamma picoiine, and the like, can be used. Especially useful are N,N,N\N'- tetraalkylethylenediamines, butane-diamines, and the like.

Mixtures of such primary, secondary and tertiary amines may be used. A preferred mono alkyl amine is n-butyl amine; a preferred dialkyl amine is di-n- butyl amine; and a preferred trialkyl amine is triethylamine. A preferred cyclic tertiary amine is pyridine. The concentration of primary and secondary amine in the reaction mixture may vary within wide limits, but is desirably added in low concentrations. A preferred range of non-tertiary amines comprises from about 2.0 to about 25.0 moles per 100 moles of monovalent phenol. In the case of a tertiary amine, the preferred range is considerably broader, and comprises from about 0.2 to about 1500 moles per 100 moles of monovalent phenol. With tertiary amines, if water is not removed from the reaction mixture, it is preferred to use from about 500 to about 1500 moles of amine per 100 moles of phenol. If water is removed from the reaction, then only about 10 moles of tertiary amine, e.g., triethylamine or triethylamine, per 100 moles of phenol need be used as a lower limit. Even smaller amounts of tertiary diamines, such as N.N.N'N'-tetramethylbutanediamine can be used, down to as low as about 0.2 mole per 100 moles of phenol.

One unexpected advantage in using PPE having an I.V. in the range of about 0.08 to about 0.20 dl/g is that the level of amine incorporation is relatively low when made by the methods as described herein. For example, when using dibutylamine (DBA) in the polymerization process, the level of DBA incorporated into high molecular weight (e.g., 0.48 I.V.) PPE is generally between about 0.9 to about 1.0% by weight based on the weight of the PPE. Conversely, the level of DBA incorporated into low molecular weight (e.g., 0.11 I.V.) PPE is generally between about 0.15 to about 0.28% by weight based on the weight of the PPE. It is desirable to have the amine level very low on the PPE to minimize the amount that becomes thermally liberated during subsequent processing and can adversely affect properties of the composition as well as taste and odor. Thus, the present invention includes compositions of at least one interpolymer and a PPE having an incorporated amine level of less than about 0.3% by weight based on the weight of the PPE. Also included are compositions of at least one interpolymer and a low I.V. PPE having enhanced branching as compared to high molecular weight PPE.

Typical examples of cuprous salts and cupric salts suitable for the process are shown in the Hay patents. These salts include, for example, cuprous chloride, cuprous bromide, cuprous sulfate, cuprous azide, cuprous tetramine sulfate, cuprous acetate, cuprous butyrate, cuprous toluate, cupric chloride, cupric bromide, cupric sulfate, cupric azide, cupric tetramine sulfate, cupric acetate, cupric butyrate, cupric toluate, and the like. Preferred cuprous and cupric salts include the halides, alkanoates or sulfates, e.g., cuprous bromide and cuprous chloride, cupric bromide and cupric chloride, cupric sulfate, cupric fluoride, cuprous acetate and cupric acetate. With primary and secondary amines, the concentration of the copper salts is desirable maintained low and preferably varies from about 0.2 to 2.5 moles per 100 moles of monovalent phenol. With tertiary amines, the copper salt is preferable used in an amount providing from about 0.2 to about 15 moles per 100 moles of the monovalent phenol.

Cupric halides are generally preferred over cuprous halides for the preparation of the copper amine catalyst because of their lower cost. The use of the copper (I) species also greatly increases the rate of oxygen utilization in the early stages of the polymerization reaction and the lower oxygen concentration in the head space of the reactor helps in reducing the risk of fire or explosion in the reactor. A process for the preparation and use of suitable copper-amine catalysts is in U.S. Pat. No. 3,900,445 (Cooper et al.).

A faster initial reaction rate with the copper (I) based catalyst also results in less accumulation of unreacted monomer and a reduction in the amount of undesirable tetramethyldiphenylquinone produced. The tetramethyldiphenylquinone, a backward dimer, is believed to incorporate into the PPE through equilibration reactions. The equilibration reactions lead to a drop in the intrinsic viscosity of the PPE due to the decrease in molecular weight of the PPE from the incorporation of the dimer. Minimization of the tetramethyldiphenylquinone during the oxidation coupling is desirable so as to avoid the drop in molecular weight and the accompanying difficulties in having to build to a higher than desired molecular weight to offset the loss during equilibration of the backward dimer. Additionally, by minimizing the amount of tetramethyldiphenylquinone formed and consequently minimizing the amount of tetramethyldiphenylquinone incorporated into the backbone of the PPE, a PPE polymer change that is predominantly hydroxyl monofunctional is possible. By "hydroxyl monofunctional" is meant that one end of the polymer chain, i.e. the "head end", is a 2,6-dimethyl phenol with the polymer chain extending from the 4-position. The other end, i.e. the "tail end", has the hydroxyl on the 2,6-dimethyl phenol connected into the polymer and hence is non-functional. In a preferred embodiment, the utilized PPE is at least 70%, preferably at least 85%, most preferably, at least 95% by weight hydroxyl monofunctional. Additionally, in another preferred embodiment, the utilized PPE had in the reaction mixture less than a 10% drop, preferably less than a 5% drop, most preferably less than a 3% drop in I.V. during an equilibration step after the oxidative polymerization of the phenolic monomers.

One advantage of the formation of tetramethyldiphenylquinone during the reaction process is that it affords the possibility to redistribute various compounds into the PPE. Through redistribution, a wide range of functionalized phenolic compounds can be introduced to afford an equally wide range of functionalized PPE. For example, after the end of the oxidative coupling reaction as determined by the desired molecular weight of the PPE, at least one phenolic compound may be added to the reaction mixture and allowed to circulate while maintaining the temperature preferably between about 20° and about 150°C, preferably between about 60° and 80°C. The reaction mixture is maintained at temperature for about 30 to about 90 minutes, although longer times are possible. During this redistribution step, the flow of oxygen has been preferably halted as the oxidative coupling has been completed. Generally, higher redistribution conversions are obtained under air as opposed to nitrogen.

The functionalized phenolic compound may be chosen from the following illustrative list:

A) phenolic compounds with formula

wherein R¹ represents a hydrogen-atom or an alkyl group and X represents an allyl group, an amino group, a protected amino group (e.g., protected by a tertiary-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group, wherein R¹ is an alkyl group when X represents an hydroxy group or an ester group .wherein X may be separated from the phenol ring through an alkyl group and wherein the total number of carbon atoms in the alkyl groups attached to the phenol ring is not more than six;

B) bisphenol compounds with formula

wherein each X, independently of the other X represents a hydrogen atom, an allyl group, an amino group, a protected amino group (e.g., protected by a tertiary-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group, with the proviso that not more than one X group represents a hydrogen atom, R² and R³ represent an hydrogen atom or an alkyl group with 1-6 carbon atoms and each R⁴ represents independently of the other R⁴ a hydrogen atom, a methyl group or an ethyl group;

C) a phenolic compound with at least one of the formulas:

wherein m and n have values from 2-20;

D) phenolic compounds with formula

wherein x has a value of 12-20 and y has a value of 1-7 or a derivative thereof;

E) multifunctional phenolic compounds with formula

wherein R⁵ represents a hydrogen atom, an alkyl group, an allyl group, an amino group, a protected amino group (e.g., protected by a tert-butyl carbonate), a carboxyl group, a hydroxy group, an ester group or a thiol group; or

F) phenolic compounds with amino groups with formula

wherein R⁶ represents independently of one another a hydrogen atom, an alkyl group or a methylene phenol group.

At the end of the redistribution, the functionalized PPE has a lower intrinsic viscosity, and hence a lower molecular weight, than does the PPE at the end of the oxidative coupling reaction. The degree of the decrease is determined at least in part by the amount of phenolic compound utilized and the amount of catalyst, e.g., tetramethyldiphenylquinone, present. In a preferred embodiment, the functionalized PPE has a weight average molecular weight of at least 1000, preferably between about 3000 and about 70,000 as compared to polystyrene standards. In another preferred embodiment, the functionalized PPE has an intrinsic viscosity of between about 0.05 dl/g and 0.50 dl/g, preferably between about 0.08 dl/g and 0.30 dl/g, more preferably between about 0.08 dl/g and about 0.15 dl/g as measured in chloroform at

30°C. The PPE may have a bi-modal distribution of molecular weights. It should be clear that the present invention also includes reaction products between the PPE and substantially random interpolymer. Such reaction products include, but are not limited to, random copolymers of PPE and the interpolymer and block copolymers of PPE and the interpolymer as well as variations of the foregoing. It is thought that even low levels of the copolymers can improve the compatibility between the resins. Improved compatibility can reduce delamination tendencies and improve the physical properties of the compositions. Also included in the present invention are compositions comprising PPE, the substantially random interpolymer, and copolymers of PPE and at least one polyolefin.

The polymerization reaction is preferably performed in a solvent. Suitable solvents are disclosed in the above-noted Hay patents. Aromatic solvents such as benzene, toluene, ethylbezene, xylene, and o-dichlorobenzene are especially preferred, although tetrachloromethane, trichloromethane, dichloromethane, 1 ,2-dichloroethane and trichloroethylene may also be used. The weight ratio between solvent and monomer is normally in the range from 1:1 to 20:1 , ie. up to a maximum 20-fold excess of solvent. The ratio between solvent and monomer is preferably in the range from 1 :1 to 10:1 by weight.

The process and reaction conditions for the polymerization, such as reaction time, temperature, oxygen flow rate and the like are modified based on the exact target molecular weight desired. The endpoint of the polymerization is conveniently determined with an in-line viscosity meter. Although other methods such as making molecular weight measurements, running to a predetermined reaction time, controlling to a specified endgroup concentration, or the oxygen concentration in solution may also be utilized.

The temperature to carry out the polymerization stage of the invention generally ranges from about 0°C. to about 95°C. More preferably, the temperature range is from about 35°C. to about 45°C with the higher reaction temperature near the end of reaction. At substantially higher temperatures, side reactions can occur leading to reaction by-products and at temperatures substantially lower, ice crystals form in the solution.

Many diverse extractants or chelating agents may be used in the practice of the invention to complex with the catalyst after the end of the polymerization reaction. For example, sulfuric acid, acetic acid, ammonium salts, bisulfate salts and various chelating agents may be used. When these materials are added to a PPE reaction solution, the copper-amine catalyst becomes poisoned and further oxidation does not take place. Many different materials may be used but it is preferred to employ those chelating agents that are disclosed in U.S. Pat. No. 3,838,102 (Bennett et al.).

The useful chelating agents include polyfunctional carboxylic acid containing compounds such as, for example, sodium potassium tartrate, nitrilotriacetic acid (NTA), citric acid, glycine and especially preferably they will be selected from polyalkylenepolyamine polycarboxylic acids, aminopolycarboxylic acids, aminocarboxylic acids, aminopolycarboxylic acids, aminocarboxylic acids, polycarboxylic acids and their alkali metal, alkaline earth metal or mixed alkali metal-alkaline earth metal salts. The preferred agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and their salts. Especially preferred are ethylenediaminotetraacetic acid or a mono-, di-, tri- and tetrasodium salt thereof and the resulting copper complex can be referred to as a copper carboxylate complex.

The chelated metallic catalyst component can be extracted with the water produced in the polymerization reaction by through the use of a liquid/liquid centrifuge. The preferred extraction liquid for use in the process of the invention is an aqueous solution of lower alkanol, i.e., a mixture of water and an alkanol having from 1 to about 4 carbon atoms. Generally from about 1% to about 80% by volume of an alkanol or glycol may be employed. These ratios may vary from about 0.01 :1 to about 10:1 parts by volume of aqueous liquid extractant to discrete organic phase.

The reaction media generally comprises an aqueous environment. Anti- solvents can also be utilized in combination with the aqueous media to help drive the precipitation of the copper (I) species. The selection of an appropriate anti-solvent is based partially on the solubility co-efficient of the copper (I) species that is being precipitated. The halides are highly insoluble in water, log K_[splvalues at 25°C. are - 4.49, - 8.23 and - 11.96 for CuCI, CuBr and Cul, respectively. Solubility in water is increased by the presence of excess of halide ions due to the formation of, e.g., CuCI₂, CUCI₃ , and CuCI₄ and by other complexing species. Non-limiting examples of anti-solvents would comprise low molecular weight alkyl and aromatic hydrocarbons, ketones, alcohols and the like which in themselves would have some solubility in the aqueous solution. One skilled in the art would be able to select an appropriate type and amount of anti-solvent, if any was utilized.

After removal of the catalyst, the PPE containing solution is concentrated to a higher solids level as part of the isolation of the PPE. The PPE can be readily functionalized prior to and/or during this solvent removal process by addition of at least one functionalizing agent, also known as compatibilizers or functionalizers. The location of the addition of at least one functionalizing agent will depend on several factors such as the stability of the agent, the volatility of the agent to the isolation conditions, the flexibility of the equipment for addition points, and the like. For functionalizing agents that are volatile in the isolation process, addition of the functionalizing agent prior to solvent removal is often preferred so as not to remove the functionalizing agent before it has functionalized the PPE. For less volatile functionalizing agents, greater flexibility in the location of the addition is possible. It is also possible to add functionalizing agent at several points during the process. In one embodiment, the functionalizing agent includes compounds having both (i) a carbon-carbon double bond or a carbon-carbon triple bond and (ii) at least one species of the group consisting of carboxylic acids, acid anhydrides, acid amides, acid esters, imides, amines, ortho esters, hydroxyls and carboxylic acid ammonium salts. Illustrative compounds useful to accomplish the functionalization of the PPE include maleic anhydride, fumaric acid, maleimides such as N-phenylmaleimide and 1 ,4-phenylene-bis-methylene- alpha , alpha '-bismaleimide, maleic hydrazide, methylnadic anhydride, fatty oils (e.g., soybean oil, tung oil, linseed oil, sesame oil), acrylate ortho esters and methacrylate ortho esters, unsaturated carboxylic acids such as acrylic, crotonic, methacrylic acid and oleic acid, unsaturated alcohols such as allyl alcohol and crotyl alcohol and unsaturated amines such as allylamine and trialkyl amine salts of unsaturated acids such as triethylammonium fumarate and tri-n-butylammonium fumarate. Examples of such typical reagents for preparing useful functionalized PPE are described in U.S. Pat. Nos. 4,315,086, 4,755,566, 4,888,397, and 5,247,006.

Non-polymeric aliphatic polycarboxylic acids are also useful for preparing functionalized PPE. Included in the group of species, are, for example, the aliphatic polycarboxylic acids, and acid esters represented by the formula:

(R^lO)_rnR(COOR")_n(CONR"^,R^lv)_s

wherein R is a linear or branched chain, saturated aliphatic hydrocarbon of from 2 to 20, preferably 2 to 10, carbon atoms; R¹ is selected from the group consisting of hydrogen or an alkyl, aryl, acyl, or carbonyl dioxy group of 1 to 10, preferably 1 to 6, most preferably 1 to 4, carbon atoms, with hydrogen being especially preferred; each R" is independently selected from the group consisting of hydrogen or an alkyl or aryl group of from 1 to 20 carbon atoms preferably from 1 to 10 carbon atoms; each R'" and R^ιv is independently selected from the group consisting essentially of hydrogen or an alkyl or aryl group of from 1 to 10, preferably from 1 to 6, most preferably 1 to 4, carbon atoms; m is equal to 1 and (n + s) is greater than or equal to 2, preferably equal to 2 or 3, and n and s are each greater than or equal to zero; and wherein (OR¹) is alpha or beta to a carbonyl group and at least two carbonyl groups are separated by 2 to 6 carbon atoms. Obviously, R', R", R"¹ and R^ιv cannot be aryl when the respective substituent has less than 6 carbon atoms.

Illustrative of suitable polycarboxylic acids are citric acid, malic acid, and agaricic acid; including the various commercial forms thereof, such as, for example, the anhydrous and hydrated acids. Illustrative acid esters useful herein include, for example, acetyl citrate and mono- and/or di-stearyl citrates and the like. Suitable acid amides useful herein include, for example, N,N'- diethyl citric acid amide; N,N'-dipropyl citric acid amide; N-phenyl citric acid amide; N-dodecyl citric acid amide; N,N'-didodecyl citric acid amide and N- dodecyl malic acid amide. Derivatives of the foregoing polycarboxylic acids are also suitable for use in the practice of the present invention. Examples of suitable functionalizing compounds can be found in U.S. Pat. Nos. 4,315,086, 4,755,566, 4,873,286 and 5,000,897.

Other useful functionalizing agents useful in the process of the invention for preparing functionalized PPE include compounds containing an acyl functional group and at least one species of the group consisting of carboxylic acids, acid anhydrides, acid esters, acid amides, imides, amines, ortho esters, hydroxyls and carboxylic acid ammonium salts. Non-limiting examples include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride acid chloride, 1-acetoxy-acetyl-3,4-dibenzoic acid anhydride, terephthalic acid acid chloride, and reactive triazines including epoxyalkyl chlorocyanurates and chloroaryloxytriazines. Additional examples can be found in U.S. Pat. Nos. 4,600,741 and 4,642,358.

The amount of the above mentioned functionalizing agents that is required to appropriately functionalize the PPE is that which is sufficient to improve the compatibility between the various components in the final composition. As previously discussed, indications of improved compatibility include resistance to lamination, improved physical properties such as increased tensile and impact properties and a stabilized morphology between the blend component phases under static or low shear conditions.

An effective amount of the above mentioned functionalizers, based on the amount of the PPE, is generally up to about 8% by weight, and is preferably from about 0.05% to about 4% by weight. In the most preferred embodiments, the amount of functionalizing agent is in the range of about 0.1 % to about 2.0% by weight based on the amount of the PPE. The actual amount utilized will also depend on the molecular weight of the functionalizing agent, the number and type of reactive species per molecule of functionalizing agent and the degree of compatibility that is desired in the final resin blend composition.

Depending on the target I.V. desired for the compositions, various techniques for isolating the PPE are useful. When the final I.V. of the PPE to utilized is greater than about 0.28 dl/g, standard solvent based techniques, e.g., precipitation of the PPE containing reaction solution into a non-solvent followed by collection and drying of the PPE are useful. Conversely, using standard non-solvent techniques typical for PPE having I.V.'s greater than 0.28 dl/g are not generally useful for isolation of lower molecular weight PPE due to the small PPE particle size and friability of the particles. Very low yields are often obtained with undesirable fractionation of oligomeric species. A total isolation process is preferred for isolating the PPE. As part of the total isolation, a portion of the solvent is preferably removed in order to reduce the solvent load on the total isolation equipment.

Concentration of the PPE containing solution is accomplished by reducing the pressure in a solvent flash vessel while preferably increasing the temperature of the PPE containing solution. Pressures of about 35 to 50 bar are desirable with solution temperatures increased to at least 200°C, preferably of at least 230°C. A solids level of PPE of at least 55%, preferably of at least 65% or higher is desirable.

The isolation of the PPE is typically carried out in a devolatilizing extruder although other methods involving spray drying, wiped film evaporators, flake evaporators, and flash vessels with melt pumps, including various combinations involving these methods are also useful and in some instances preferred. As previously described, total isolation is preferably from the viewpoint that oligomeric species are not removed to the same degree as with precipitation. Likewise, isolation yields are extremely high and are near quantitative. These techniques require however that the catalyst removal be completed in the prior process steps as any catalyst remaining in solution will necessarily be isolated in the PPE.

Devolatilizing extruders and processes are known in the art and typically involve a twin-screw extruder equipped with multiple venting sections for solvent removal. In the practice of the present invention, it is preferred when isolating PPE having an I.V. of about 0.28 or less that the preheated concentrated solution containing the PPE be fed into the devolatilizing extruder and maintained at a temperature less than about 275°C, and preferably less than about 250°C, and most preferably between about 185- 220°C with pressures in the vacuum vent of less than about 1 bar. The resultant solvent level is reduced to less than about 1200 ppm, preferably less than about 600 ppm, and most preferably less than about 400 ppm.

Another advantage of using a devolatilizing extruder is the extremely high yield of PPE achieved in the process. For example, a PPE yield of over 99% have been obtained even for PPE having a low I.V. whereas in the precipitation process known in the art, the yield of similar low I.V. PPE was less than 90%. Thus, the present process preferably comprises PPE obtained through a devolatilization process to remove the solvent. A devolatilizing extruder typically affords a method to prepare low molecular weight polyphenylene ether resin, typically within the intrinsic viscosity range of about 0.08 dl/g to about 0.20 dl/g, in a yield of over 90%, preferably over 95%, more preferably over 98% and most preferably over 99%, based upon the amount of monovalent phenol utilized in the oxidative coupling.

When using a devolatilization extruder for the total isolation of the PPE, traditional underwater or water spray cooling of strands of extrudate followed by chopping the extrudate into pellets often gives unacceptable results presumably due to the low melt strength and inherent brittle nature of low molecular weight PPE. It was found that special pelletization techniques can overcome these difficulties. Useful techniques include die-face pelletization, including underwater pelletization and flaking, declining angle strand pelletization using water spraying, and vibration drop pelletization with underwater pelletization especially suitable.

Underwater pelletization also results in a significantly lower color in the PPE as compared to the standard stranding with water/air cooling followed by pelletization techniques. Yellowness index (Yl) numbers of less than 30, and even less than 25 are achievable as compared to Yl > 50 achieved with the standard stranding technique. It should be apparent that the present invention includes compositions comprising (i) at least one interpolymer and (ii) at least one polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g, preferably within the range of about 0.08 dl/g to about 0.20 dl/g, as measured in chloroform at 25°C. wherein the PPE was made by a process that affords a method of preparing a PPE with a Yl of less than about 30, preferably less than about 25.

Another unexpected benefit of underwater pelletization of PPE, especially low I.V. PPE, is that very low (less than about 3% by weight) fines, defined as pellets (i.e. particles) of less than 850 microns in size, could be obtained. It should be clear that the present invention includes a method to reduce the number of fines having a particle size less than about 850 micron in polyphenylene ether wherein the method comprises underwater pelletization of the polyphenylene ether resin. A preferred embodiment includes a method to prepare the compositions of the invention wherein the method comprises reducing the number of PPE fines having a particle size less than about 850 micron to less than about 3%, preferably less than about 1.5% by weight based on the total weight of the pellets and mixing the PPE with at least one interpolymer.

The relative amounts of PPE and interpolymer in the composition can vary widely from 1-99 parts by weight PPE to 99-1 parts by weight interpolymer. For many commercial applications, it is preferred that the level of PPE be adjusted such that the PPE remains a dispersed phase within the interpolymer as a continuous phase. In other preferred embodiments, it is preferred to use a relatively minor proportion of PPE, e.g., up to about 20% by weight.

The compositions of the present invention can be prepared by a variety of methods involving intimate admixing of the materials with any additional additives desired in the formulation. Suitable procedures include solution blending and melt blending. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. Examples of equipment used in such melt compounding methods include: co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment. In some instances, the compounded material exits the extruder through small exit holes in a die and the resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.

All of the ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other. It is also sometimes advantageous to employ at least one vent port in each section between the feed ports to allow venting (either atmospheric or vacuum) of the melt. Those of ordinary skill in the art will be able to adjust blending times and temperatures, as well as component addition location and sequence, without undue additional experimentation. Additionally, concentrates containing relatively high levels of PPE in the interpolymer may be used that are let down to the desired lower level of PPE with additional interpolymer by, for example, a converter manufacturing sheet products or articles are also contemplated. By relatively high level of PPE is meant a concentrate that contains at least 20%, preferably at least 30% by weight, more preferably at least 40% by weight PPE based on the weight of the concentrate. Such concentrates may be primarily composed of the polyphenylene ether resin and the interpolymer or may be composed of another resin such as, for example, a polystyrene resin. The concentrate may also contain one or more of the additives and/or stabilizers as follows.

Additives such as antioxidants (e.g., hindered phenols such as, for example, IRGANOX Registered TM 1010), phosphites (e.g., IRGAFOS Registered TM 168)), U.V. stabilizers, cling additives (e.g., polyisobutylene ), antiblock additives, colorants, pigments, fillers, carbon fibers, carbon fibrils, and the like can also be included in the compositions of the present invention, to the extent that they do not interfere with the enhanced properties of the compositions.

The additives are employed in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant employed is that amount which prevents the polymer from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers. Such amounts of antioxidants is usually in the range of from about 0.01 to about 10, preferably from about 0.05 to about 5, more preferably from about 0.1 to about 2 percent by weight based upon the weight of the polymer. Similarly, the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer antiblocking, to produce the desired amount of filler loading to produce the desired result, to provide the desired color from the colorant or pigment. Such additives can suitably be employed in the range of from about 0.05 to about 50, preferably from about 0.1 to about 35 more preferably from about 0.2 to about 20 percent by weight based upon the total weight of the polymers. However, in the instance of fillers, they could be employed up to about 90 percent by weight based on the total weight of the polymers.

In one embodiment, the compositions may further comprise at least of the following optional thermoplastic resins such as, for example, polyolefins, polyetherimides, polyethersulfones, polysulfones, , polyphenylsulfone, syndiotactic or isotactic polystyrenes, polyamides, polyesters, styrenic resins, polsiloxanes, ABS, polyvinyl chloride, polyurethanes, thermoplastic elastomers, and polyarylene sulfides. Especially useful are compositions further comprising polyolefins such as, for example, polyethylene and polypropylene produced by either Ziegler-Natta or metallocene type catalysts. It should be noted that the present invention also includes compositions that are substantially free of the aforementioned resins. By substantially free of is meant compositions that contain less than about 5% by weight, preferably less than 3% by weight, most preferably essentially none of the aforementioned resins based on the total weight of the composition.

The compositions of the present invention can be utilized to produce a wide range of fabricated articles such as, for example but not limited to, films, sheets or as a components of a multilayered structure resulting from calendering, blowing, casting or (co-)extrusion operations.

The compositions can find utility in the form of fabricated articles produced, for example, by rotation molding, compression molding, injection molding, blow molding, calendering, sheet extrusion, profile extrusion, or thermoforming operations.

The compositions can also be used in the manufacture of fibers, foams and lattices. The compositions of the present invention can also be utilized in adhesives, adhesive formulations and adhesive/sealant applications.

All patents and references cited by reference are incorporated herein by reference.

Examples

The following examples are illustrative of specific embodiments of the invention and are not to be construed as limiting the scope of the invention.

Ethylene/styrene/propylene interpolymers may be prepared by methods known in the art such as found in U.S. 5,872,201. A twin-screw extruder or a single screw extruder may be utilized to melt compound the PPE with the interpolymer. It is important to control the temperature and shear of the molten compositions so as to minimize the degradation of the interpolymer. Concentrates of PPE and another material, preferably interpolymer, may also be used directly in calendering, injection molding, blowing, casting, or (co)extrusion operations. Addition of PPE to the interpolymers improves the heat resistance of the interpolymers as well as altering the rheological characteristics. For example flow properties can be enhanced and viscosity matching can be used to control blend morphology.

Better compatibility between the PPE and interpolymer can be obtained with interpolymers containing styrene incorporation as compared to interpolymers not containing styrene or containing a styrene content that is too low to enhance the compatibility of the PPE with the interpolymer. By better compatibility is meant reduced delamination tendencies and enhanced physical properties such as, for example, tensile strength and tensile elongation. It is unexpected that interpolymers that are not characterized by a high degree of either isotacticity or syndiotacticity can be combined with PPE to achieve a composition having, an acceptable level of compatibility based upon the prior art teachings of the necessity to have a block copolymer present for this purpose.

Varying the styrene content and the molecular weight of the interpolymer affords a widely varying assortment of physical properties as well as varying degrees of compatibility with the PPE. Changes in the PPE I.V. also affects the physical properties of the composition with improved compatibility between the PPE and the interpolymer generally obtained with PPE having an I.V. less than about 0.3 dl/g, preferably less that about 0.2 dl/g, and most preferably less than about 0.15 dl/g. It should be clear that the present invention includes a method for improving the compatibility between PPE and a substantially random interpolymer wherein the method comprises at least one of varying the molecular weight and/or styrene content of the interpolymer and/or varying the molecular weight of the PPE and/or varying the weight ratio of the interpolymer and PPE.

Claims

CLAIMS:What is claimed:

1. A composition comprising:

(i) at least one substantially random interpolymer comprising:

(a) ethylene;

(b) one or more aromatic vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and

(c) optionally, one or more polymerizable C₃ to C₂₀ olefinic monomers, and

(ii) at least one polyphenylene ether resin.

2. The composition of Claim 1 wherein the interpolymer comprises:

(a) ethylene;

(c) one or more polymerizable C₃ to C₂₀ olefinic monomers.

3. The composition of Claim 1 wherein the interpolymer comprises: (1) from about 19.5 to about 98.5 mole percent of ethylene; (2) from about 0.5 to about 60 mole percent of one or more aromatic vinylidene monomers or hindered aliphatic vinylidene monomers, and (3) from about 1 to about 80 mole percent of one or more C₃ to C₂₀ olefin monomers, wherein the total amount of (1 ), (2) and (3) is 100 mole percent.

4. The composition of Claim 1 wherein the interpolymer comprises: (1 ) from about 25 to about 95 mole percent of ethylene; (2) from about 1 to about 55 mole percent of one or more aromatic vinylidene monomers or hindered aliphatic vinylidene monomers, and (3) from about 4 to about 65 mole percent of one or more C₃ to C₂₀ olefin monomers, wherein the total amount of (1 ), (2) and (3) is 100 mole percent.

5. The composition of Claim 1 wherein the interpolymer comprises: (1) from about 30 to about 94 mole percent of ethylene; (2) from about 1 to about 50 mole percent of one or more aromatic vinylidene monomers or hindered aliphatic vinylidene monomers, and (3) from about 5 to about 50 mole percent of one or more C₃ to C₂₀ olefin monomers, wherein the total amount of (1 ), (2) and (3) is 100 mole percent.

6. The composition of Claim 1 wherein the substantially random interpolymer does not contain more than 15 percent of the total amount of vinylidene aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units.

7. The composition of Claim 1 wherein the substantially random interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity.

8. The composition of Claim 1 wherein in a Carbon-13 NMR spectrum of the substantially random interpolymer, the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences is less than 75 percent of the total peak area of the main chain methylene and methine carbons.

9. The composition of Claim 1 wherein the interpolymer comprises a terpolymer of at least one combination selected from the group consisting of ethylene/styrene/propylene; ethylene/styrene/4-methyl-1 -pentene; ethylene/styrene/hexene-1 ; ethylene/styrene/octene-1 ; ethylene/styrene/norbornene; ethylene/styrene/butene-1 ; and ethylene/styrene/vinylbenzocyclobutene.

10. The composition of Claim 1 wherein the interpolymer comprises a terpolymer of at least one combination selected from the group consisting of ethylene/styrene/propylene; ethylene/styrene/4-methyl-1 -pentene; ethylene/styrene/hexene-1 ; ethylene/styrene/octene-1 ; and ethylene/styrene/norbornene.

11. The composition of Claim 1 wherein the polyphenylene ether resin is a dispersed phase within the interpolymer.

12. The composition of Claim 1 wherein the polyphenylene ether resin is present in an amount up to about 50% by weight based upon the weight of the composition.

13. The composition of Claim 1 wherein the polyphenylene ether resin is present in an amount up to about 20% by weight based upon the weight of the composition.

14. The composition of Claim 1 wherein the polyphenylene ether resin has an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g as measured in chloroform at 25°C.

15. The composition of Claim 1 wherein the polyphenylene ether resin has an intrinsic viscosity within the range of about 0.08 dl/g to about 0.20 dl/g as measured in chloroform at 25°C.

16. The composition of Claim 1 wherein the compositions is substantially free of elastomeric block copolymer resins.

17. The composition of Claim 1 wherein the compositions is substantially free of elastomeric block copolymer resins of the group consisting of polystyrene- poly(butadiene)-polystyrene block copolymers, polystyrene- poly(ethylenebutylene)-polystyrene block copolymers and polystyrene- poly(ethylenepropylene) block copolymers.

18. The composition of Claim 1 wherein the polyphenylene ether resin comprises a functionalized polyphenylene ether resin.

19. The composition of Claim 1 wherein the polyphenylene ether resin comprises a functionalized polyphenylene ether resin made through redistribution of a functionalized phenolic compound.

20. The composition of Claim 1 wherein the polyphenylene ether resin comprises a polyphenylene ether resin that has been functionalized prior to solvent removal, during solvent removal, or prior to and during solvent removal by addition of at least one functionalizing agent.

21. The composition of Claim 1 wherein the polyphenylene ether resin comprises a polyphenylene ether resin that has an incorporated amine content of less than about 0.3% by weight based on the weight of the polyphenylene ether resin.

22. The composition of Claim 1 wherein the polyphenylene ether resin is made from at least 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6- trimethylphenol.

23. The composition of Claim 1 wherein the polyphenylene ether resin is made by a process comprising oxidative coupling in a reaction solution at least one monovalent phenol species using an oxygen containing gas and a complex metal catalyst to produce a polyphenylene ether resin having an intrinsic viscosity within the range of about 0.05 dl/g to about 0.60 dl/g as measured in chloroform at 25°C; recovering the complex metal catalyst with an aqueous containing solution and isolating the polyphenylene ether resin through devolatilization of the reaction solvent.

24. The composition of Claim 23 wherein the process produces a polyphenylene ether resin having an intrinsic viscosity within the range of about 0.08 dl/g to about 0.20 dl/g as measured in chloroform at 25°C.

25. The composition of Claim 23 wherein the process further comprises an equilibration of a metal chelating agent with the complex metal catalyst.

26. The composition of Claim 23 wherein the intrinsic viscosity of the polyphenylene ether resin after the equilibration has less than a 10% change in intrinsic viscosity as before the equilibration.

27. The composition of Claim 23 wherein the devolatilization is accomplished at least in part with a devolatilization extruder.

28. The composition of Claim 27 wherein the devolatilization extruder is at least partly operated at between about 185-220°C.

29. The composition of Claim 27 wherein the reaction solvent has a solids level of at least about 65% before feeding into the devolatilization extruder.

30. The composition of Claim 23 wherein the polyphenylene ether resin has less than about a 10% drop in intrinsic viscosity after an equilibration step following the oxidative coupling.

31. The composition of Claim 23 wherein the polyphenylene ether resin has less than about a 10% change in intrinsic viscosity after an equilibration step following the oxidative coupling and after a thermal treatment at 200°C for about 0.2 minutes to about 20 minutes.

32. The composition of Claim 23 wherein the monovalent phenol species comprises 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6- trimethylphenol.

33. The composition of Claim 23 wherein the polyphenylene ether resin has an incoφorated amine content of less than about 0.3% by weight based on the weight of the polyphenylene ether resin.

34. The composition of Claim 23 wherein the devolatilization is accomplished at least in part with a devolatilization extruder and an underwater pelletizer.

35. The composition of Claim 23 wherein the polyphenylene ether resin has a residual volatiles level of less than about 600 ppm based on the weight of the polyphenylene ether resin.

36. The composition of Claim 27 wherein at least a portion of the interpolymer is added into the devolatilization extruder.

37. The composition of Claim 1 further comprising at least one thermoplastic resins of the group consisting of polyolefins, polyetherimides, polyethersulfones, polysulfones, polyphenylsulfone, syndiotactic or isotactic polystyrenes, polyamides, polyesters, styrenic resins, polsiloxanes, ABS, polyvinyl chloride, polyurethanes, thermoplastic elastomers, and polyarylene sulfides.

38. The composition of Claim 1 further comprising at least of the following polyolefins selected from the group consisting of polyethylene and polypropylene.

39. The composition of Claim 1 further comprising polyethylene, polypropylene, or polyethylene and polypropylene.

40. The composition of Claim 23 further comprising polyethylene, polypropylene, or polyethylene and polypropylene.

41. The composition of Claim 1 wherein the interpolymer is in the form of a concentrate comprising the interpolymer and at least one other resin.

42. A fabricated article comprising the composition of Claim 1.

43. The fabricated article made of Claim 42 wherein the fabricated article is made by at least one of rotation molding, compression molding, injection molding, blow molding, calendering, sheet extrusion, profile extrusion, or thermoforming operations.

44. A fiber, foam, or lattice comprising the composition of Claim 1.

45. An adhesive formulation comprising the composition of Claim 1.

46. A method to prepare a composition comprising:

(i) at least one substantially random interpolymer comprising:

(a) ethylene;

(ii) at least one polyphenylene ether resin; wherein said method comprises a concentrate of the interpolymer with the polyphenylene ether resin.

47. A composition consisting essentially of:

(i) at least one substantially random interpolymer consisting essentially of:

(a) ethylene;

(ii) at least one polyphenylene ether resin.

48. The composition of Claim 47 wherein the interpolymer consisting essentially of:

(a) ethylene;

(c) one or more polymerizable C₃ to C₂₀ olefinic monomers.