MXPA00003908A - Thermally stable polyetheramines - Google Patents

Abstract

A laminate structure comprises one or more layers of an organic polymer and one or more layers of a hydroxy-functionalized polyetheramine, wherein the hydroxy-functionalized polyetheramine layer is adhered directly to a contiguous organic polymer layer without an adhesive layer therebetween. The hydroxy-functionalized polyetheramine is prepared by reacting (1) a difunctional amine with (2) a diglycidyl ether or diepoxy-functionalized poly(alkylene oxide) under conditions sufficient to cause the amine moieties to react with the epoxy moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties and then treating the reaction product with a monofunctional nucleophile which is not a primary or secondary amine.

Description

SUBSTANTIAL INTERPOLYMERS IN SULPHONATED RANDOMIZES, MIXTURES WITH THEMSELVES AND ARTICLES MADE OF THEM The present invention relates to sulfonated interpolymers of aromatic monomers of α-olefin / vinyl or vinylidene or vinylidene monomers of aliphatic or hindered cycloaliphatic or a combination thereof; salts thereof; and mixtures thereof. The preferred sulfonated interpolymer is a sulfonated substantially random ethylene / styrene interpolymer. The interpolymers of the aromatic monomer of α-olefin / vinyl or vinylidene or aliphatic or cycloaliphatic hindered vinylidene monomer or a combination thereof are well known as described by Stevens et al. In EP 0 416 815 A2. Polyamide polymers and α-olefin polymers and copolymers are also well known. It is often convenient to prepare polymer blends so that a polymer blend having properties or characteristics not available to the polymers alone is obtained. This is true for blends of polyamides and polymers and copolymers of α-olefins. However, said polymers are incompatible and a suitable compatibilizer must be employed before the mixtures can be used. It has now been found that the sulfonated interpolymers of aromatic α-olefin / vinyl or vinylidene monomers or hindered aliphatic or cycloaliphatic vinylidene monomers or a combination thereof and salts thereof are suitable compatabilizers for blends of polyamides and polymers and copolymers of α-olefins. The interpolymers containing the sulfonated salts exhibit improved mechanical properties at elevated temperatures compared to the interpolymers before being sulfonated and subsequently converted to the salt. SUMMARY OF THE INVENTION One aspect of the present invention pertains to a surface sulfonated article prepared from a substantially random interpolymer comprising: (1) from 1 to 65 mole percent of polymer units derived from (a) at least an aromatic vinyl or vinylidene monomer, or (b) a combination of at least one aromatic vinyl or vinylidene monomer containing an aromatic ring Ar, and at least one aliphatic or cycloaliphatic hindered vinylidene monomer; and (2) from 35 to 99 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (3) from zero to 20 mole percent of polymeric units derived from a diene containing from 4 to 20 carbon atoms; and wherein from 0.001 to 30 mole percent of the polymer units contained in the interpolymer contain one or more groups represented by the formula -SO3"M wherein M is hydrogen, NH4 + or a metal of group 1, 2, 7, 11 or 12 in ionic form Another aspect of the present invention relates to a substantially random interpolymer having a sulfonated aromatic or cycloaliphatic ring or a sulfonated polymer backbone or a combination thereof, wherein the interpolymer is formed of monomeric components comprising (1) from 1 to 65 mole percent of (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one vinyl or vinylidene aromatic monomer and at least one vinylidene monomer aliphatic or hindered cycloaliphatic vinylidene, and (2) from 35 to 99 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms, and (3) optionally, from zero to 20 percent m olar of a diene containing from 4 to 2 carbon atoms; and wherein from 0.1 to 65 mole percent of the aromatic or cycloaliphatic rings contained in said sulfonated ether polymer contains a group represented by the formula -SO3"M wherein M is hydrogen, NH4 + or a metal of group 1, 2, 7 , 11 or 12 in ionic form Another aspect of the present invention pertains to a compatibilized mixture of polymers comprising: (A) from 1 to 99 weight percent of at least one polyamide; (B) from 1 to 99 weight percent of at least one "mer" olefin polymer derived from aromatic vinyl monomers, aromatic vinylidene, hindered aliphatic vinylidene, cycloaliphatic vinylidene or a combination thereof; and (C) from 1 to 99 weight percent of at least one substantially random sulfonated interpolymer ring formed of monomeric components comprising (1) from 1 to 65 mole percent of (a) at least one aromatic vinyl monomer or vinylidene, or (b) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic hindered vinylidene monomer; and (2) from 35 to 99 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (3) optionally, from zero to 20 mole percent of a diene containing from 4 to 20 carbon atoms; and wherein from 0.05 to 30 mole percent of the aromatic or cycloaliphatic rings contained in said sulfonated interpolymer contains one or more groups represented by the formula -SO3"M wherein M is hydrogen, NH4 + or a metal of group 1, 2, 7, 11 or 12 in ionic form or combination thereof Another aspect of the present invention pertains to a modified interpolymer composition having a service temperature greater than at least 5 ° C, preferably 20 ° C a 50 ° C, more preferably 50 ° C to 150 ° C higher than the unmodified interpolymer, the unmodified interpolymer comprising (A) from 1 to 65 mole percent of polymeric units derived from at least one aromatic vinyl monomer or vinylidene; and (B) from 35 to 99 mole percent polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; said modified polymer resulting from (1) subjecting said unmodified interpolymer to sulfonation so as to provide the resulting sulfonated interpolymer with 0.1 to 5 weight percent of -SO3H groups; and (2) reacting the sulfonated interpolymer of step (1) with an NH4 + or a Group 1, 2, 7 or 12 metal compound capable of reacting with the product of step (1) to convert at least some, preferably from 1 to 100, more preferably from 50 to 100 mole percent, still more preferably from 100 mole percent of the -SO3H groups pendent to the -SO3"M groups where M is NH4 + or a Group 1, 2 metal , 7, 11 or 12 in ionic form In the above compositions, the total number of monomer units in the polymers is 100 mole percent and the total polymer content of the mixtures is 100 percent by weight. The present invention may comprise, consist essentially of, or consist of any of two or more of said interpolymers, polymers, or copolymers listed herein.In addition, interpolymers, polymers or copolymers include those formed of monomer components comprising , consist essentially of, or consist of, any of two or more of the polymerizable monomers listed.

Detailed Description of the Invention Any reference in the present to metals of a particular group refers to the "new" groups of the periodic table of the elements exhibited in CRC Handbook of Chemistry and Phvsics, 71th ed. The term "hydrocarbyl" means any aliphatic, cycloaliphatic, aromatic, aliphatic substituted with aryl, cycloaliphatic substituted with aryl, aromatic substituted with aliphatic or aromatic substituted with cycloaliphatic groups. The aliphatic or cycloaliphatic groups are preferably saturated. Likewise, the term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen ligation between it and the carbon atom to which it is attached. The term "interpolymer" is used herein to denote a polymer wherein at least two different monomers are polymerized to form the interpolymer. This includes copolymers, terpolymers, etc. The term "mer (s)" means the polymerized unit of the polymer derived from the indicated monomer (s). The term "plurality" as used herein means two or more. When referring to polymers containing monomers or monomer units derived therefrom, it really means that the polymer contains monomer residues resulting from the polymerization of the monomers indicated to form the polymer. The term "substantially random" in the substantially random interpolymer comprising an α-olefin and an aromatic vinyl or vinylidene monomer or hindered aliphatic vinylidene monomer as used herein, means that the distribution of the monomers of said interpolymers can be describe by the Bernoulli statistical model or by a Markovian statistical model of the first or second order, as described by JC Randall in POLYMER SEQUENCE DETERMINATION. Carbon 13 NMR Method. Academic Press New York, 1977, pgs. 71-78. Preferably, the substantially random interpolymer comprising an α-olefin and an aromatic vinyl or vinylidene monomer, contains no more than 15 percent of the total amount of aromatic vinyl or vinylidene monomer in vinyl or vinylidene aromatic monomer blocks. of 3 units. More preferably, the interpolymer was not characterized by a high degree of isotacticity or unionism. This means that in the 13C NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and the methine carbons representing the divalent radical meso sequences or divalent radical race sequences should not exceed 75 one hundred of the area of the total peak of the methylene of main chain and methine carbons. Any numerical value recited herein includes all values of the value less than the upper value in increments of one unit as long as there is a separation of at least two 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 and time, for example is 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., be expressly listed in this specification. For values that are less than one, a 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 it should be considered that all possible combinations of the numerical values between the lowest value and the highest value listed are expressly stated in this application in a similar way. In the modified polymers of the present invention, from 0.001 to 100, preferably from 0.01 to 10, more preferably from 0.05 to 5 molar percent of aromatic or cycloaliphatic groups contained in the polymer contain a -SO3M group wherein M is hydrogen, NH4 + or a metal of group 1, 2, 7, 11 or 12 of the periodic table of the elements. For anti-blocking of pellets, 0.05 to 1 molar percent are preferred. For higher service temperature, 0.1 to 5 weight percent is preferred, 0.2 to 2.5 weight percent being more preferred. For compatibilization, 0.05 to 20 mole percent is preferred. Suitable interpolymers for sulfonation to form the sulfonated polymers of the present invention include, but are not limited to, substantially random interpolymers prepared by polymerizing one or more α-olefin monomers with one or more vinyl or vinylidene aromatic monomers, or or more hindered aliphatic or cycloaliphatic vinylidene monomers, or a combination thereof, and optionally with other ethylenically polymerizable unsaturated monomer (s). Suitable α-olefin monomers include, for example, α-olefin monomers containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. Such preferred monomers include ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 and octene-1. Ethylene or a combination of ethylene with C2-8 α-olefins are more preferred. These α-olefins do not contain an aromatic mer. Suitable vinylidene or vinylidene aromatic monomers which can be used to prepare the interpolymers used in the mixtures include, for example, those represented by the following formula: Ar I (CH2) "R - C = C (R2) 2 wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 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 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C 1-4 alkyl, and C 1-4 haloalkyl; and n has a value from zero to 4, preferably from zero to 2, even more preferably from zero. Illustrative vinyl or monovinyl lead aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable monomers include styrene and derivatives thereof substituted with lower alkyl or halogen. Preferred monomers include styrene, α-methylstyrene, derivatives substituted with lower alkyl (C, -C 4) or styrene phenyl ring, such as, for example, ortho-, meta-, and para-methylstyrene, the halogenated styrenes in the ring, para-vinyltoluene or its mixtures. A most preferred aromatic monovilidene monomer is styrene. By the term "aliphatic or hindered cycloaliphatic vinylidene compounds" is meant the addition polymerizable vinylidene monomers corresponding to the formula: A1 I R ~ C = C (R2) 2 wherein A1 is a sterically bulky aliphatic or cycloaliphatic substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 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 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. By the term "sterically bulky" is meant that the monomer having this substituent is usually unable to polymerize by addition by normal Ziegler-Natta polymerization catalysts at a comparable rate with ethylene polymerizations. A-olefin monomers containing from 2 to 20 carbon atoms and having a linear aliphatic structure such as propylene, butene-1, hexene-1 and octene-1 are not considered as hindered aliphatic monomers. Preferred aliphatic or cycloaliphatic hindered vinylidene compounds are monomers in which one of the carbon atoms having ethylenic unsaturation is tertiary or substituted quaternary. Examples of such substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclo-octenyl, or derivatives substituted with alkyl or aryl rings thereof, tert-butyl, norbornyl. The most preferred aliphatic vinylidene or hindered cycloaliphatic compounds are the different derivatives substituted with isomeric vinyl rings of cyclohexene and substituted cyclohexenes and 5-ethylidene-2-norbornene. In particular, 1-, 3-, and 4-vinyl-cyclohexene are suitable. Other optional polymerizable ethylenically unsaturated monomers include deformed ring olefins such as norbornene substituted with C 1-10 alkyl or Cß-10 aryl with an illustrative interpolymer being ethylene / styrene / norbornene. The number average molecular weight (Mw) of the polymers and interpolymers is usually greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. Polymerizations and removal of unreacted monomers at temperatures above the autopolymerization temperature of the respective monomers may result in the formation of some amounts of homopolymer polymerization products resulting from free radical polymerization. For example, while the substantially random interpolymer is prepared, an amount of aromatic vinyl or vinylidene aromatic homopolymer can be formed due to the homopolymerization of the aromatic vinyl or vinylidene monomer at elevated temperatures. The presence of the aromatic vinyl or vinylidene homopolymer, in general, is not detrimental to the purposes of the present invention and can be tolerated. The aromatic vinyl or vinylidene homopolymer can be separated from the interpolymer, if desired, by extraction techniques, such as selective precipitation of solution with a non-solvent for the interpolymer or vinylidene or vinylidene aromatic homopolymer. For the purpose of the present invention it is preferred that it be present no more than 20 weight percent, preferably less than 15 weight percent based on the total weight of the aromatic vinyl or vinylidene homopolymer interpolymers. Substantially random interpolymers can be prepared as described in the application of E.U.A. Number 07 / 545,403 filed July 3, 1990 (corresponding to EP-A-0,416,815) by James C. Stevens et al., And is the Application of E.U.A. No. 08 / 469,828 filed June 6, 1995. Preferred operating conditions for said polymerization reactions are pressures from atmospheric to 3,000 atmospheres and temperatures from -30 ° C to 200 ° C. Examples of suitable catalysts and methods for preparing the substantially random interpolymers are described in the application of E.U.A. No. 07 / 545,403, filed July 3, 1990 corresponding to EP-A-416,815; Application of E.U.A. No. 07 / 702,475, filed May 20, 1991 corresponding to EP-A-514,828; Application of E.U.A. No. 07 / 876,268, filed May 1, 1992 corresponding to EP-A-520,732; Application of E.U.A. No. 08 / 241,523, filed May 12, 1994; Application of E.U.A. No. 60 / 034,819, filed December 19, 1996; as well as the Patents of E.U.A. 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; 5,460,993 and 5,556,928. Particularly suitable catalysts include, for example, dimethyl [N- (1-di-methylethyl) -1, 1-dimethyl-1 - [(1, 2,3,4, 5-eta.) -1,5, 6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silanaminate (2 -) - N] -titany and (t-butylamido) dimethyl (tetramethylcyclopentadienyl) si-cyanthiol (II) 1, 3 -pentadiene. The substantially random α-olefin / vinyl or vinylidene aromatic interpolymers 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). Substantially random interpolymers comprising at least one a-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrade described in the application of E.U.A. No. 08 / 708,809 filed on September 4, 1996, by Francis J. Timmers et al. These interpolymers contain additional signals with intensities greater than three times the peak-to-peak noise. These signals appear on the scale of chemical change 43.75-44.25 ppm and 38.0-38.5 ppm. Specifically, higher peaks are observed at 44.1, 43.9 and 38.2 ppm. A proton test NMR experiment indicates that the signals in the chemical change region are methine carbons and the signals in the 38.0-38.5 ppm region are methylene carbons. In order to determine the carbon 13 NMR chemical changes of the described interpolymers, the following procedures and conditions are employed. A polymer solution of five to ten percent by weight in a mixture consisting of 50 volume percent of 1,1, 2,2-tetrachloroethane-d 2 and 50 volume percent chromium tris (acetylacetonate) 0.10 was prepared. molar in 1, 2,4-trichlorobenzene. The NMR spectra were acquired at 130 ° C using a reverse gate decoupling sequence, a pulse width of 90 ° and a pulse delay of five seconds or more. The spectra are quoted for methylene signal isolated from the assigned polymer at 30,000 ppm. It is thought that these new signals are due to sequences involving two final end-to-end vinyl aromatic monomers preceded and followed by at least one α-olefin insert, eg, ethylene / styrene / styrene tetrad / ethylene wherein the styrene monomer insertions of the tetrads occur exclusively in a 1.2 (end-to-end) form. It is understood by someone skilled in the art that for said tetrads involving an aromatic vinyl monomer other than styrene and an α-olefin other than ethylene; that the ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene tetrad will give rise to similar carbon-NMR peaks but with slightly different chemical changes. These interpolymers are prepared by carrying out the polymerization at temperatures from -30 ° C to 250 ° C in the presence of said catalysts as represented by the formula wherein: each Cp is independently, each time it is presented, a substituted cyclopentadienyl group which is linked by a bond p to M; E is C or Si; M is a metal of group IV preferably Zr or Hf, more preferably Zr; each R is independently, each time it occurs, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, which contains up to 30, preferably from 1 to 20, more preferably from 1 to 10 carbon atoms or silicon; each R 'is independently, each time it occurs, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbon Isi which contains up to 30, preferably from 1 to 20, more preferably from 1 to 10 carbon atoms or silicon or two R 'groups which together can be 1, 3-butadiene substituted with C1-10 hydrocarbyl; m is 1 or 2; and optionally, but not preferably, in the presence of an activating cocatalyst. Particularly suitable cocatalysts include, for example, ammonium, sulfonium, phosphonium, oxonium, ferrocenium or silyl salts of tetrakis (pentafluoro-phenyl) borate, tris pentafluorophenyl) borane, an aluminoxane or trialkylaluminum-modified aluminoxane or a combination thereof. Particularly, suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each time it occurs, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl containing up to 30, preferably from 1 to 20, more preferably from 1 to 10 carbon atoms, silicon atoms or two R groups together they form a divalent derivative of said group. Preferably, R, independently each time it occurs, is (including where all isomers are appropriate) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two of said R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic ((dimethylsilanedi-yl) bis (2-methyl-4-phenylindenyl)) zirconium dichloride, ((dimethylsilanedi-yl) bis (2-methyl-4-phenylindenyl)) zirconium 1, 4-d if eni racemic I-1, 3-butadiene, ((dimethylsilanedi-yl) bis (2-methyl-4-phenyl) n-zen) zirconium dialkyl of racemic C1-4, (dimethylsilanedi-yl) bis ( Racemic C1-4-dialkyl 2-methyl-4-phenylene) zirconium, or any combination thereof The additional preparative methods for the interpolymer component (A) 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 and others (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995]) reported the use of a system catalyst based on methylalumoxane (MAO) and cyclopentadienyltytanium trichloride (CpTiCl3) to prepare an ethylene-styrene copolymer Xu and Lin (Polvmer Preprints, Am. Chem. Soc, Div. Polvm. Chem.) Volume 35, pages 686, 687 [1994]) have reported copolymerization using a MgCl2 / TiCl4 / NdCI3 / AI (iBu) 3 catalyst to give random copolymers of styrene and propylene. Lu et al. (Journal of Applied Polvmer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl4 / NdCI3 / MgCl2 / AI (Et) 3 catalyst. Sernetz and Mulhaupt, (Macromol. Chem. Phys., V. 197, pp. 1071-1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler-Natta catalysts of Me2Si (Me4Cp ) (N-tert-butyl) TiCl2 / methylaluminoxane. The manufacture of interpolymers of α-olefin / vinyl aromatic monomers such as propylene / styrene and butene / styrene are disclosed in U.S. Patent No. 5,244,996 issued to Mitsui Petrochemical Industries Ltd. Interpolymers containing cycloaliphatic monomer residues that are usually hindered prepare by subjecting an interpolymer containing residues of aromatic monomers of monovílideno to hydrogenation thereof by converting some or all of the aromatic rings to cycloaliphatic rings that can be saturated (for example, cyclohexane ring) or unsaturated (cyclohexene rings). The interpolymers of one or more α-oiefins and one or more vinyl or monovinylidene aromatic monomers, or one or more vinylidene aliphatic or hindered cycloaliphatic monomers, or a combination thereof, employed in the present invention, are substantially random polymers. These interpolymers contain from 0.5 to 65, preferably from 1 to 55, more preferably 2 to 50 mole percent of at least one aromatic vinyl or vinylidene monomer or hindered aliphatic or cycloaliphatic vinylidene monomer or a combination thereof, and from 35 to 99.5, preferably from 45 to 99 , more preferably from 50 to 98 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. The interpolymers can be sulfonated by any suitable means known in the art to sulfonate aromatic ring compounds. A suitable method is that described by Turbuk in the U.S. Patent. 3,072,618. The polymer is sulfonated by contacting the polymer with a sulphonation complex comprising the reaction product of 2 to 4 moles of sulfur trioxide and 1 mole of a lower trialkyl phosphate or phosphite, at a temperature of 25 ° C to 100 ° C. ° C, preferably 50 ° C to 83 ° C, more preferably 75 ° C to 83 ° C for a few seconds to several hours followed by recovery of the resulting sulfonated polymer. Sulfur trioxide can also be supplied in the form of chlorosulfonic acid or fuming sulfuric acid. Particularly suitable trialkyl phosphates include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphate, hydrogen phosphate, diethyl hydrogen phosphate, phosphite. of dimethyl hydrogen, diethyl hydrogen phosphite, methyl dihydrogen phosphate, ethyl dihydrogen phosphate, methyl dihydrogen phosphite, ethyl dihydrogen phosphite, any combination thereof. A particularly preferred method of sulfonation is that described by H. S. Makowski, R.D. Lundberg, and G. H. Singhal in E.U.A. 3,870, 841. In this method, a mixed anhydride prepared by mixing sulfuric acid with acetic anhydride at a temperature of -70 ° C to 130 ° C (preferably between -20 and 20 ° C) followed by the addition of this mixture to a solution of the polymer in a chlorinated solvent, such as, for example, dichloroethane, methylene chloride, chloroform, tetrachloroethane, trichloroethane or combinations thereof at a temperature of -20 ° C to 100 ° C.

Salts of these sulfonated polymers can be prepared by reacting the sulfonated polymer with a metal salt in a suitable solvent at temperatures of 20 ° C to 100 ° C, preferably 40 ° C to 100 ° C, more preferably 60 ° C to 80 ° C for a time to convert essentially all the SO3H groups to the metal salt (SO3Me where Me is the metal), usually 0.01 to 240, preferably 1 to 60, more preferably 5 to 30 minutes. I am suitably a metal from the group of 1, 2, 7, 11 or 12 of the Periodic Table of the Elements. The amount of metal salt employed is that which is sufficient to substantially convert all the sulfonate groups to the metal salt, usually from 1 to 1.5, preferably from 1 to 1.1, more preferably from 1 mole of metal salt per mole of sulfonate group present in the polymer. The amount of solvent employed is that amount sufficient to create a substantially homogeneous mixture, which may vary from 5 to 95, preferably from 10 to 80, more preferably from 15 to 75 weight percent based on the combined weight of the mixture. Suitable metal salts that can be used herein include the salts formed of group 1, 2, 7, 11 or 12 metals, as well as ammonium salts (NH 4 +) and a C 2 to C 20 carboxylic acid, preferably C2 to C10. Particularly suitable metals of group 1, 2, 7, 11 or 12 include Na, K, Li, Co, Cu, Mg, Ca, Mn, or Zn. Also suitable are the hydroxides of said metals. Particularly suitable salts and hydroxides include the hydroxides, acetates, hexanoates and oxides of Na, Li, K, Ca, Mg, Cu, Co, Zn, Al, NH 4 + and any combination thereof. Also suitable are the hydrates of the aforementioned salts. Suitable polyamides which can be used herein as the mixture component (A) include, for example, polymeric amides prepared by both condensation and ring-opening polymerization represented by the following structures: open ring condensation polyamide Often, these are given the common name of Nylon. For the open ring polyamides, R ^ is preferably hydrogen, but may be an aliphatic hydrocarbon group. For open-ring polyamides, R2 is an aliphatic hydrocarbon. Open-ring polyamides include polymers such as polyamide 6, where 6 is the number of carbons between the N atoms in the main chain (R ^ H, R., = 5). Materials of this type include nylon 6, nylon 11 and nylon 12. The polyamides will also be prepared by condensation methods, such as the reaction between a diamine and a diacid (or diacid derivative). The material structures prepared by this method are designated numerically with the number of carbons between the N atoms of the diamine portion followed by the number of carbon atoms in the diacid portion. For example, the polymer prepared from 1,6-diamino hexane and adipic acid is described as polyamide 66 (^ H, R1 = 6, R3 = 4) or nylon 66. For condensation polyamides, R2 can be an aliphatic or aromatic group difunctional, and R3 may be an aliphatic or difunctional aromatic group. R2 and R3 may be the same or different. Polyamides of this type include polyamide 46, 66, 69, 610 and 612. Olefin polymers suitable for use as component (B) in the mixtures according to the present invention are aliphatic α-olefin homopolymers or interpolymers, or interpolymers of one or more aliphatic α-olefins and one or more non-aromatic monomers interpolymerizable therewith or chlorinated polyethylene (PEC). Preferred olefinic polymers for use in the present invention are homopolymers or interpolymers of an aliphatic α-olefin, including cycloaliphatic having from 2 to 18 carbon atoms. Suitable examples are homopolymers of ethylene or propylene and interpolymers of two or more α-olefin monomers. Other preferred olefinic polymers are interpolymers of ethylene and one or more other α-olefins having from 3 to 8 carbon atoms. Exemplary monomers that can be polyepped therein include 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The olefinic polymeric components (a) may also contain, in addition to the α-olefin, one or more non-aromatic monomers interpolymerizable therewith. Such additional interpolymerizable monomers include, for example, diolefins, ethylenically unsaturated carboxylic acids (both mono- and difunctional) as well as derivatives of these acids, such as esters and anhydrides. Illustrative of said monomers are acrylic acid, methacrylic acid, vinyl acetate and maleic anhydride. The olefinic polymers can be further characterized by their degree of long or short chain branching and the distribution thereof. A class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator which results in the traditional long chain branched low density polyethylene (LDPE). The LDPE employed in the present composition usually has a density of less than 0.94 g / cc (ASTM D 792) and a melt index of 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes (as determined by the method of ASTM D 1238 test, condition l). Another class is linear olefin polymers that have an absence of long chain branching, such as traditional linear low density polyethylene polymers (heterogeneous LDPE) or linear high density polyethylene (HDPE) polymers made using Ziegler polymerization processes. , for example, US Patent No. 4,076,698 (Anderson et al.), Sometimes called heterogeneous polymers. HDPE consists mainly of linear polyethylene chains. The HDPEs employed in the present composition usually have a density of at least 0.94 grams per cubic centimeter (g / cc) as determined by ASTM D 1505 Test Method and a melt index (ASTM-1238)., condition I) on the scale from 0.01 to 100 and preferably from 0.1 to 50 grams per 10 minutes. The heterogeneous LDPEs employed in the present composition generally have a density of 0.85 to 0.94 g / cc (ASTM D 792) and a melt index (ASTM-1238, condition I) on the scale of 0.01 to 100 and preferably 0.1 to 50. grams for 10 minutes. Preferably the PEBDL is an interpolymer of ethylene and one or more other α-olefins having from 3 to 18 carbon atoms, more preferably 3-8 carbon atoms, the preferred comonomers include 1-butene, 4-methyl-1 -pentene, 1-hexene, and 1-octene. An additional class is that of uniformly branched or homogeneous polymers (homogeneous LDPE). Homogeneous polymers contain non-long chain branches and have only branches derived from the monomers (if they have more than two carbon atoms). Homogeneous polymers include those formed as described in the U.S. Patent. 3,645,992 (Elston) and those formed using the so-called single-site catalysts in a batch reactor having relatively high olefin concentrations (as described in U.S. Patent Nos. 5,026,798 and 5,055,438 (Canich). uniformly branched / homogeneous are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule and wherein the interpolymer molecules have a similar ethylene / comonomer ratio within this interpolymer The homogeneous PEBDL used in the present composition it generally has a density of 0.85 to 0.94 g / cc (ASTM D 792), and a melt index (ASTM-1238, condition I) on the scale of 0.01 to 100, and preferably 0.1 to 50 grams per 10 minutes. PEBDL is an interpolymer of ethylene and one or more other α-olefins having 3 to 18 carbon atoms, preferably 3-8 carbon atoms The preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. In addition, there is the class of substantially linear olefin polymers (POSL) which can advantageously be used in the component (a) of the mixtures of the present invention. These polymers have a processability capacity similar to PEBD, but the stre and rigidity of PEBDL. Similar to traditional homogeneous polymers, the substantially linear ethylene / α-olefin interpolymers have only a single melting peak that opposes traditional heterogeneous linear polymerized ethylene / α-olefin Ziegler interpolymers having two or more melting peaks (determined using differential scanning calorimetry). Substantially linear olefin polymers are described in U.S. Pat. Nos. 5,272,236, 5,278,272 and 5,665,800. The density of POSL as measured according to ASTM D-792 is generally from 0.85 g / cc to 0.97 g / cc, preferably from 0.85 g / cc to 0.955 g / cc, and especially from 0.85 g / cc to 0.92 g / c. DC. The melt index (12), according to ASTM D-1238, Condition 190 ° C / 2.16 kg (also known as l2), of the POSL is generally 0.01 g / 10 min. at 1000 g / 10 min., preferably 0.01 g / 10 min, at 100 g / 10 min., and especially 0.01 g / 10 min. at 10 g / 10 min. Also included are the ultra low molecular weight ethylene polymers and ethylene / α-olefin interpolymers having l2 melt index greater than 1,000, or a number average molecular weight (Mw) less than 11,000. The POSL can be a homopolymer of C2-C20 olefins, such as ethylene, propylene, 4-methyl-4-pentene, etc., or it can be an interpolymer of ethylene with at least one C3-C20 α-olefin or C2-C20 acetylenically unsaturated monomer or C4-C18 diolefin, or a combination thereof. POSL can also be an interpolymer of ethylene with at least one of the C3-C20 α-olefins, diolefins or acetylenically unsaturated monomers above, or a combination thereof, in combination with other unsaturated monomers. Especially preferred olefin polymer components (a) comprise PEBD, HDPE, heterogeneous and homogeneous PEBDL, POSL, polypropylene (PP), especially isotactic polypropylene and hardened rubber polypropylenes or ethylene-propylene (EP) interpolymers, or chlorinated polyolefins ( PEC), or any combination thereof. The mixtures of the present invention usually comprise from 1 to 99, preferably from 50 to 95 and more preferably from 70 to 85 weight percent of the component (A); from 1 to 99, preferably from 5 to 50 and more preferably from 15 to 30 weight percent of component (B); and from 0.1 to 99, preferably from 0.1 to 20 and more preferably from 1 to 10 weight percent of component (C). The percentages are based on the total amount of the polymers constituting the mixtures and the mixtures comprise a total amount of 100 weight percent of components (A), (B) and (C). The mixtures of the present invention can be prepared by any suitable means known in the art such as, but not limited to, dry blending in a pellet form in the desired proportions followed by melting mixing, for example, in extruder screw, Herschel mixer or Banbury mixer. The dry-blended aggregate pellets can be melt processed directly into a final solid state article, for example, by injection molding. Alternatively, the mixtures can be made by direct polymerization, without isolation of the mixed components, using for example one or more catalysts in one reactor or two or more reactors in series or in parallel. Additives such as antioxidants (for example, hindered phenols such as, for example, IRGANOX® 1010), phosphites (for example, IRGAFOS® 168), UV stabilizers, adhesion additives (for example, poly-isobutylene), additives Antiblock, dyes, pigments and fillers may also be included in the interpolymers employed in the blends of the present invention, to the extent that they do not interfere with the improved properties discovered by the applicants. The additives are used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used is that amount which prevents the polymer, or mixture of polymers, from undergoing oxidation at the temperatures and environment employed during the manufacture, storage and final use of the polymers. Said amounts of antioxidants are usually in the range of 0.05 to 10, preferably 0.1 to 5, more preferably 0.1 to 2 weight percent based on the weight of the polymer or polymer mixture. Similarly, the amounts of any of the other additives listed are functionally equivalent amounts such as the amount to give the polymer or polymer mixture an anti-blocking property, to produce the desired amount of filler loading to produce the desired result, to provide the color desired from the dye or pigment, etc. Such additives can normally be employed in the range of 0.05 to 50, preferably 0.1 to 35, more preferably 0.2 to 20 weight percent based on the weight of the polymer or polymer blend. However, in the case of fillers, up to 90 weight percent may be employed based on the weight of the polymer or polymer blend. The blends of the present invention can be used to produce a wide scale of manufactured articles such as, for example, but not limited to, calendered sheet, blown films and injection molded parts. The mixtures can also be used in the manufacture of fibers, foams or networks. The mixtures of the present invention can also be used in adhesive formulations. The sulfonated surface articles of the present invention can be used in a wide range of applications, such as, to form polymer pellets having improved material that handle characteristics as demonstrated by a decrease in the tendency of the pellets to adhere. The sulfonation of surfaces can also be used to improve the solvent resistance of the molded parts in applications such as, for example, automotive parts. The sulfonation of surfaces can also be used to improve the paint quality of the parts, improve the adhesion of parts to the polar substrates, such as, for example, glazing, metal and polar polymers, as well as to improve the barrier properties of articles to gases. An additional application is to decrease the tackiness of molded parts, so as to decrease the adhesion tendency of the films and molded parts. The randomly sulfonated interpolymers of the present invention can be used to produce a wide scale of manufactured articles such as, for example, but not limited to, calendered sheet, blown films and injection molded parts. They can be used as compatibilizers of mixtures of third components in polyolefin / polyester or nylon blends. Randomly sulfonated samples can also be used to give polymers with improved compatibility with polar materials such as, for example, asphalt. Randomly sulfonated samples also exhibit improved temperature resistance compared to non-sulfonated samples that allow them to be used in high heat applications. Randomly sulfonated samples can also be used as elastomers at high heat. Sulfonated samples may also be more susceptible to sealing by radio frequency (RF) treatments.

The following examples are illustrative of the present invention, but should not be construed as limiting the scope of the invention in any way. TEST METHODS The following test methods were used. The Shear Stress Storage Module (G ') was determined with a RDA-II dynamic mechanical spectrometer from Rheometrics Inc. to obtain the EMD data. A temperature sweep was run from about -70 ° C to 200 ° C at 5 ° C / step with an equilibrium delay of 30 seconds in each step. The oscillatory frequency was 1 radian / s with a self-tensioning function of 0.1 percent deformation initially, increased in positive settings of 100 percent as long as the torque decreased to 4 g-cm. The maximum deformation was set at 26 percent. Parallel 7.9-mm plate fittings with an initial space of 1.5 mm at 160 ° C (the sample was inserted into the RDA-II at 160 ° C) were used. The "clamping" function was used at 160 ° C and the instrument was cooled to -70 ° C and the test was started. (The Hold function corrects thermal expansion or contraction when the test chamber heats up or cools down). A nitrogen environment was maintained during the experiment to minimize oxidative degradation. The Degree of Sulfonation was determined by elemental analysis or X-ray fluorescence spectroscopy. Ion chromatography was used to determine the sulfur content in the sample. The sulfur content was carried out by combustion of the polymer to convert any sulfur in the sample to sulfate, and the sulfate was quantified using ion chromatography (Cl). The content of Li was evaluated by first digesting the sample in a mixture of sulfuric acid / hydrogen peroxide and the Li content was quantified by flame atomic absorption analysis (AA-flame). Determination of Sulfur Percentage by X-ray Fluorescence Spectroscopy The weight percentage of sulfur in the ESI sample was determined by x-ray fluorescence spectroscopy. All measurements were carried out using the Philips PW1480 wavelength dispersive x-ray spectrometer. This instrument was equipped with a scandium / molybdenum X-ray tube. All measurements were carried out in a helium atmosphere. The samples were hot-pressed into disc and placed in FRX cups with a 6.3 micron polypropylene film. The cup was covered with a microporous film. Cups and films were obtained from Chemplex Industries, Inc. Measurements for sulfur were made in triplicate in the sulfur channel. The intensities were averaged for the analysis of fundamental parameters. A water target was measured to correct the sweep and contamination of films. Total sulfur was quantified using fundamental parameter analysis (PF). A certified sulfur normal of 1 percent or a normal sulfur of 0.5 percent in oil base was used for quantification. A PC version of the fundamental parameters program, PCFPW, was used for the calculations. Determination of the concentration of Sulfur in the Pellet Surface of ESI by X-Ray Photoelectron Spectroscopy (EFX) The pieces of the pellets of the samples were mounted on a sample holder, using double-sided tape. The surface and volume of the pellets were analyzed. Photoelectron spectroscopy (EFX) was carried out in a Physícal Electronics (PHI) 5600 system. The A1 Ka monochromatographed X-ray source (1486.6 eV) was operated at 250 W and the power was regulated at 14 kV. An analysis area of 800 x 2000 μm was used with the samples mounted at a photoelectric takeoff angle of 68 ° in relation to the surface of the sample. The sample load was minimized using an electronic flood gun and the loading of the spectra was referenced using the C 1s peak at 284.8 eV. The spectra were recorded with the collection optics in "minimum area mode" with a solid photoelectronic collection angle of ± 7 °. The step energy and stage size (in eV) were 93.9 / 0.4 for the spectrum under study. Other collection parameters were recorded electronically with the spectra. All the manipulation of the spectra was done with the PHl-ACCESS software, revision 5.4B. Peak areas were measured using an integrated fund. The elemental sensitivity factors provided in the software were used to calculate atomic percentages. The limit of detection is approximately 0.05 percent atomic. Aqua Surface Contact Angle Measurement (pH 7) on ESI Sample Plates Contact angle measurements were made using a Model G-II Kernco goniometer (Kernco Instruments Co. Inc., 420 Kenazo Street, El Paso, TX 79927) that has been improved by Krüss USA (9305-B Monroe Road, Charlotte, NC 28270). The system now essentially is the automatic contact angle measuring system ACAMS-40 from Krüss. The sample was illuminated with a fiber optic light source and the droplet image was displayed on a video monitor. The image was displayed on a computer screen using Krüss G40 software and contact angle measurements were obtained by digital integration of the video image. A drop of water was applied to the sample plate molded by compression using a micro-syringe and the volume of the drop is approximately 0.4 microliters. The contact angle measurements were obtained following the procedures described in the operation procedure of the Contact Angle Measuring System G40 supplied by Krüss E.U.A. Determination of ESI Pellet Locking Trend The ESI sample pellets (125 grams are sufficient to completely fill the cylinder) were loaded onto a stainless steel cylinder (diameter 120 mm x 52 mm). The cylinders were constructed by cutting a stainless steel tube in half (lengthwise) and the two halves of the cylinder were clamped by a clamp. The cylinders were lined with TEFLON ™ coated paper. The filled cylinders were loaded onto a sample rack and a guided piston was placed on top of the pellets in the cylinder. The diameter of the piston foot was 50mm. The weight of the piston was 0.85 Kg, and 2.25 Kg. A weight was placed on the top of the piston head to give a total force of 3.10 Kg. The samples were loaded in the oven and the samples were compacted at 45 ° C for 24 hours. After 24 hours, the samples were removed from the oven. The weights of the samples were then removed and the samples allowed to cool to room temperature (at least one hour). The cylinder was then disassembled carefully. The resulting polymer disks that were generated by compaction overnight (usually 50 mm in diameter x 75-100 mm in height) were compressed between two flat plates using a computer-controlled Instron Instru-Met / Sintech equipped with a cell Compression load. The Instron was operated on the compression model at a rate of 1 mm / min. The discs were compressed until the pellet cylinder will fail or until a force of 45 kg or a percent deformation of 50 percent is reached. The force required to cause the cylinder to fail was recorded.

The CBD (Differential Scanning Calorimetry) data were obtained using a CBD-7 from Perkin-Elmer. The samples were pressed by melting into thin films and placed on aluminum trays. The samples were heated to 180 ° C in the CBD and kept there for 4 minutes to ensure complete fusion. The samples were then cooled to 10 ° C / min at -30 ° C and heated to 140 ° C at 10 ° C / min. Dvnatup. An indication of fracture stiffness was determined by ASTM D-3763-86. The TSS (Higher Service Temperature) was determined using a thermomechanical analyzer model AMT 7 by Perkin Elmer. A probe force of 102 grams and a heating rate of 5 ° C / min was used. The penetration of the probe into the sample as a function of temperature was measured. The TSS was defined as the temperature at which the penetration is 1 mm. The test specimen was a disk with a thickness of approximately 2 mm and a diameter of approximately 5 mm, prepared by melt processing at 205 ° C and air cooling at room temperature. Tension properties were determined by ASTM D638 at a test speed of 0.508 cm / min. The impact of Dvnatup was determined by ASTM D3763-86. The impact of Izod (slotted) was determined by ASTM 256-81.

The Crystalline Fusion Point (Tf) was determined; j_a_ Glass Transition Temperature (Tv); and Crystallinity by differential scanning calorimetry (CBD). The samples were heated at a rate of 10 ° C / minute and the crystalline melting point was observed in an endothermic peak, for which a peak melting point was recorded. The energy integration below this peak was compared with that known for the 100 percent crystalline base polymer (polyamide 6, 100 J / g, polyethylene, 277 J / g, polypropylene, 209 J / g). The glass transition temperatures were observed as deflections in the heat flux response and the glass transition temperature was recorded as the midpoint of the heat flux curve. The Fusion Temperature. Tf, it's the same as the crystalline melting point. The Scanning Electron Microscopy data was determined by the following procedure. Injection molded strain specimens were grooved with a shaver and subsequently submerged in liquid nitrogen. The samples were then fractured in a compact tension mode. Freeze fracture morphology of palladium-coated samples was examined with Sita S-400 from Hitachi operating at 10 KV. Digital image analysis was carried out in a series of microscopes to determine particle size and particle size distribution. EXAMPLE 1 A. Preparation of Ethylene / Octene / Styrene Interpolymer (EOS) (57.9 / 29.5 / 15.6 weight percent I / O).

The ethylene / 1-octene / styrene interpolymers were formed using (tert-butylamido) di-methyl (tetramethyl-h5-cyclopentadienyl) silane dimethyltitanium (+4) catalyst and tris (pentafluorophenyl) borane cocatalyst in a ratio of one to one according to the following general procedure. A stirred two liter reactor was charged with the desired amounts of mixed alkane solvent (ISOPAR ™ -E available from Exxon Chemicals Inc.), styrene monomer, 1-octene monomer. The hydrogen was then added to the reactor by differential pressure expansion (the pressure difference indicated by delta) of a 75 mL addition tank. The content of the reactor was heated to the desired temperature followed by saturation with ethylene at the desired pressure. The desired amounts of catalyst and cocatalyst were mixed in toluene and the resulting solution was transferred to a catalyst addition tank and injected into the reactor. The polymerization was allowed to proceed with ethylene on demand. Additional charges of catalyst and cocatalyst, if used, were prepared in the same manner and added to the reactor periodically. After the operation time, the polymer solution was removed from the reactor and cooled with isopropyl alcohol. The hindered phenol antioxidant (IRGANOX ™ 1010 available from Ciba Geigy Corp.) was added to the polymer solution. The volatiles were removed from the polymers in a vacuum oven at 120 ° C for about 20 hours. It was found that substantially random interpolymers contain small amounts of amorphous polystyrene homopolymers. Preparation Conditions for Substantially Random Interpolymers of E / O / S The properties of the EOS, EOS-1 and EOS-2 polymers are given in Table 1. B. Sulfonation of Example 1A (SEOS-1). 50 g of EOS-1 were dissolved in 500 mL of dichloroethane in a one liter flask and the mixture was heated at 83 ° C until the polymer was fluffed and then 100 mL of cyclohexane was added. The sulfonation agent was prepared by cooling 100 mL of dichloroethane in an ice bath and adding 7 mL of 95 percent sulfuric acid and 23 mL of acetic anhydride thereto. 70 mL of this sulfonating agent was added to the flask and the reaction was allowed to proceed to reflux for 3.5 hours. This polymer was precipitated in 2 liters of methanol and further washed with methanol. The polymer was redissolved in 900 mL of methanol; 40 mL of this solution was left aside for further analysis and the remaining polymer was neutralized with 40 mL of a 1.44 M methanolic LiOH solution for 3 hours at 70 ° C. This polymer was then washed with a 2L methanol precipitate and washed with methanol. Elemental analysis for sulfur gave 0.12 percent or sulfonation of 2.7 molar percent. Elemental analysis for lithium gave 0.056 percent by weight, or 5.8 mole percent. This sulfonated polymer was then referred to as SEOS-1. C. Sulfonation of Example 1A (SEOS-2). The same procedure was used as above for the sulfonation of EOS-1 using the following: 50 g of polymer (EOS-2), 500 ml of dichloroethane, 50 ml of cyclohexane, 80 ml of sulfonating agent. The reaction was terminated with 50 mL of 2-propanol. It was neutralized with 70 mL of a 1.517 M methanolic LiOH solution. Sulfur analysis: 3.3 molar percent sulfonation. Li analysis: 2.6 mole percent of Lithium. This sulfonated polymer is referred to hereafter as SEOS-2. D. Preparation of Ethylene / Styrene Interpolymer (ES-1) (51.7 / 48.3 weight percent ES). The ethylene / styrene copolymer was prepared in a stirred batch reactor of 1512.0 liters. The reaction mixture consisted of approximately 945 liters, a solvent comprising a mixture of cyclohexane (85 weight percent) and isopentane (15 weight percent) and styrene. Before the addition, the solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in styrene was also removed. The inert substances were removed by purging the container with ethylene. The container was then pressurized to a fixed point with ethylene. Hydrogen was added to control the molecular weight. The temperature in the container was controlled to the fixed point by varying the temperature of the water jacket of the container. Prior to polymerization, the vessel was heated to the desired operating temperature and the flow of titanium catalyst components was controlled: (N-1, 1-dimethylethyl) dimethyl (1 - (1, 2,3,4, 5, eta) -2,3,4,5-tetramethyl-2,4-cyclo-pentadien-1-yl) -sianaminate)) (2-) N) -dimethyl, CAS # 135072-62-7 and Tps (pentafluorophenyl) ) -boron, CAS # 001109-15-5, Modified Type 3A methylaluminoxane, commercially available from CAS # 146905-79-5 on a 1/3/5 molar ratio basis respectively, were combined and added to the vessel. After starting, the polymerization was allowed to proceed with ethylene supplied to the reactor as required to maintain the pressure in the vessel. In some cases, hydrogen was added to the upper reactor space to maintain a molar ratio to the ethylene concentration. At the end of the operation, the catalyst flow was stopped, ethylene was removed from the reactor and then about 1000 ppm of IRGANOX ™ 1010 antioxidant was added to the solution and the polymer was isolated from the solution. The resulting polymers were isolated from the solution either by separating them by steam in a vessel or by the use of a devolatilizing extruder. In the case of the steam-separated material, additional processing was required in the extrusion equipment to reduce the residual moisture and any unreacted styrene.

E. Sulfonation of Example 1D (SES-1). The same procedure that was used before to sulfonate EOS-1 using the following: 50 g. of polymer, 500 mL of dichloromethane, 50 mL of cyclohexane, 80 mL of sulfonating agent. The reaction was terminated with 50 mL of 2-propanol. It was neutralized with 70 mL of 1.517 M methanolic LiOH solution. Sulfur Analysis: 5.3 molar percent sulfonation. Li analysis: 5.4 mole percent of Lithium. This suiflated polymer is referred to hereinafter as SES-1. F. Polyamide 6 (PA6) (Nylon 6) This polyamide 6 has a melting point of 222 ° C and a percent crystallinity of 30 available from Allied Signal as Capron ™ 8207F. G. Polypropylene (PP).

This propylene has a melting point of 165 ° C and a percentage crystallinity of 46 available from Himont Inc. as PP 6331. H. Polyethylene (PEBDL) This linear low density polyethylene has a density of 0.92 g / cc and a rate of melt flow of 1.00 g / 10 min (ASTM D-1238, condition E, 190 ° C) and available from The Dow Chemical Company as Dowlex ™ 2045A. The properties of the polymers used as compatibilizers for other polymers are given in Table 1.

Table 1 a The degree of sulfonation was determined by elemental analysis. b Tv is the glass transition temperature. c Tf is the crystalline melting point. d Percent crystallinity is based on the heat of crystallization of 277 J / g for polyethylene. e The molar percent sulfonation is the percent of the aromatic rings that are sulphonated.

MIXTURE PREPARATION Mixtures of various polymers were prepared by drying the polymers at 80 ° C in a vacuum oven for at least 12 hours before mixing by a melt blending method or an extrusion method. Fusion Mixing Method About 200 grams of the blend components were manually mixed first and then fed into a 250 cc Haake Buchler mixer equilibrated at 260 ° C and operated at 60 rpm. The feeding of a temperature equilibrium normally took approximately 10 min. Once the melting temperature reached 240 ° C, mixing was continued for another 3 minutes so that the total residence time in the mixer was about 13 min. The mixed samples were reduced to fine particles in a Wiley mill.

Extrusion Mixing Method About 200 grams of the mixed components were first manually mixed and then fed at a rate of 0.9072 kg / hour in a 2.54 cm C.W. counter-rotating twin screw extruder. of Brabender graduated at 260 ° C and operated with a screw speed of 75 rpm. Material. The extruded mixtures were then formed into pellets for injection molding. The properties of various mixtures are given in Table 2.

Table 2 * It is not an example of the present invention. to Polyamide (Nylon 6). b Polypropylene. c Linear low density polyethylene. d Tf (PO) is the melting temperature of the poly-olefin phase used as polymer B. e Percent crystallinity of the polyamide phase. f Percent of crystallinity of the polyolefin phase. g Blend of fusion, h Extrusion mixture. Table 3 gives the size of dispersed particles in the mixture measured by scanning electron microscopy. Injection molded strain specimens were grooved with a shaver and subsequently submerged in liquid nitrogen. The samples were fractured in a compact tension mold. The freeze fracture morphology of the palladium-coated samples was examined with a Hitachi S-400 scanning electron microscope (SEM) operating at 10 KV. The digital image analyzes were carried out in a series of microphotographs to determine the particle size and particle size distribution.

Table 3 * It is not an example of the present invention. to Polyamide (Nylon 6). b Polypropylene. c Linear low density polyethylene d Minimum diameter e Maximum diameter f Average diameter g The average average particle diameter determined by measuring the particle size by scanning electron microscopy and quantifying the particle size. The average particle size in volume was determined using the following equation: D ^ -t? N ^ 4] / [? N, D, 3] where D, is the diameter of its particle. h D43 / average. i Fusion mixture. J Extrusion mixture.

Table 4 a Molten mixture. b Extrusion mixture. The data in Tables 3 and 4 show that the sulfonated interpolymers act as a compatibilizer for the mixture of nylon with polypropylene or PEBDL. The mixture with sulfonated interpolymers have small particle size and better rigidity than mixtures without sulfonated interpolymers. For example, in the Nylon / PP mixture the sample with sulfonated interpolymer (mixture C) shows smaller average diameter of particular PP size, higher fracture energy, and higher maximum load in the Dynatup test of mixture A (without sulphonated interpolymers). Similarly, in the mixture of Nylon LDPE, the addition of sulfonated interpolymers reduces the average particle size of LDPE and increases the maximum load in the Dynatup test (comparison of mixture D and mixture F). The unmodified polymer also acts as a compatibilizer but is less effective than the sulfonated interpolymer. EXAMPLE 2 A. Preparation of Ethylene / Styrene Copolymer (52 weight percent styrene (22.6 moles)) Description of the Reactor The only reactor used was a tank reactor with continuous agitation (RTAC) and autoclave, with oil jacket 22.7 liters. A stirrer magnetically coupled with Lightening A-320 propellers provides mixing. The reactor runs all the liquid at 3,275 kPa. The process flow was in the lower part and outside the upper part. A heat transfer oil was circulated through the reactor jacket to remove some heat of reaction. After the reactor outlet, a micromotion flow meter measured the solution flow and density. All the lines at the reactor outlet were drawn with 344.7 kPa of steam and were isolated. Procedure The ethylbenzene solvent was supplied to the mini-plant at 207 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. At the discharge of the solvent pump, a side stream was taken to provide rinsing flows for the catalyst injection line (0.45 kg / hr) and the reactor agitator (0.34 kg / hr). These flows were measured by differential pressure flow meters and controlled by manual adjustment of microflow needle valves. Uninhibited styrene monomer was supplied to the mini-plant at 207 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. The styrene streams were mixed with the rest of the solvent stream. Ethylene was supplied to the miniplant at 4,137 kPa. The ethylene stream was measured by a Micro-Motion mass flow meter just before the Research valve will control the flow. A Brooks flow meter / controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture was combined with the solvent / styrene stream at room temperature. The solvent / monomer temperature as it enters the reactor was lowered to about 5 ° C by a glycol exchanger at -5 ° C in the jacket. This current entered the lower part of the reactor. The three-component catalyst system and its solvent rinse also entered the reactor at the bottom, but through a different port than the monomer stream. The preparation of the catalyst components is carried out in a gloved box with an inert atmosphere. The diluted components were placed in cylinders padded in nitrogen and charged to the catalyst operation tanks in the process area. From these operating tanks the catalyst was pressurized with piston pumps and the flow was measured with Micro-Motion mass flow meters. These currents are combined with each of them and the catalyst rinsing solvent, just before entering through a single injection line in the reactor. The polymerization was stopped with the addition of the catalyst composition (water mixed with solvent) in the product line of the reactor after the micromotion flow meter measured the solution density. Other polymeric additives can be added with the catalyst composition. A static mixer in the line dispersed the catalyst composition and additives in the effluent stream of the reactor. This current then entered after the reactor heaters that supplied additional energy for the advance of solvent removal. This advance occurred as the effluent left the heater after the reactor and the pressure decreased from 3,275 kPa to less than approximately 250 mm absolute pressure in the reactor pressure control valve. This advanced polymer entered a hot oil jacket lined devolatorizer. Approximately 85 percent of the volatile substances were removed from the polymer in the devolatilizer. Volatile substances leave the top of the devolatilizer. The stream was condensed and with a glycol jacketed exchanger, it entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene / ethylene separation vessel. The solvent and styrene were removed from the bottom of the container and the ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for its composition. The measurement of the ventilated ethylene plus a calculation of the gases dissolved in the solvent / styrene stream were used to calculate the ethylene conversion. The polymer separated in the devolatilizer was pumped out with a gear pump to a devolatilizing vacuum extruder ZSK-30. The dried polymer came out of the extruder as a single cord. This cord cooled as it was pulled through a water bath. The excess water is blown from the cord with air and the cord is cut into pellets with a cord cutter. Catalysts used adi methyl [N- (1,1-di methyl ethyl) -1,1-di methyl- 1 - [(1,2, 3,4,5-eta.) -1,5,6,7-tetrahydro -3-phenyl-s- Reactor Data The resulting ethylene / styrene ether polymer contained 52.4 weight percent (22.9 mole percent) of styrene (total); 52.0 weight percent (22.6 mole percent) in the polymer; 1 weight percent atactic polystyrene; a melt index, l2 of 1. 0 and a ratio of 7.5. B. Copolymer Sulfonation 1. Unsulfonated (0 percent sulfonation) 2. 0.37 percent sulfonation by weight 100.0 g of ethylene-styrene copolymer (52 percent by weight of styrene, 1.0 MI) prepared in ( A) previous in 600 mL of 1,2-dichloroethane in a 1000 mL 4-necked flask equipped with a mechanical stirrer, reflux condenser and a thermocouple. The mixture was heated at 60 ° C for two hours until all the polymer dissolved. In a separate flask, 100 mL of dichloroethane (Aldrich, 99 percent) and 8.7 g of acetic anhydride (0.085 mol) (Aldrich) were mixed. The solution was cooled in an ice water bath and 5.5 g of concentrated sulfuric acid (0.0532 molar) were added dropwise to the solution. The acetyl sulfate solution was then added to the solution of dissolved ethylene-styrene polymer and the mixture turned purple and then brown. The reaction was stirred at 60 ° C for 2 hours. 3. Sulfonation of 2.3 weight percent The same procedure used for 2 was used, however, 17.8 g of acetic anhydride (0.175 mol) and 11.3 of concentrated sulfuric acid (0.1095 mol) were used in the sulfonation reaction. Neutralization was carried out as described in part C using 14.4g (0.0657 moles) of zinc dihydrate-acetate. 4, Sulfonation of 3.2 weight percent The same procedure used for 2 was used, however, 35.7 g of acetic anhydride (0.35 mole) and 22.6 of concentrated sulfuric acid (0.219 mole) were used in the sulfonation reaction. The neutralization was carried out as described in part C using 36.0 g (0.16 moles) of zinc dihydrate-acetate. C. Conversion to Zinc salt After the sulfonation reaction (B) was completed, 14.4 g (0.0657 mol) of zinc acetate dihydrate (Aldrich) dissolved in 60 mL of methanol were added. The solution turned white, and then stirred at 60 ° C for an additional 30 minutes. The solution was removed from the heat and the polymer was isolated via methanol precipitation in a Waring Mixer. The polymer was isolated and washed repeatedly with methanol. The polymer was filtered and dried in a vacuum oven at 80 ° C for 24 hours. Several properties were determined in the non-sulfonated copolymer and the sulfonated copolymers. The results are given in Table 5. Table 5 * Not an example of the present invention a The total weight percent sulfonation (-SO3H) in the sample was determined by X-ray fluorescence. B The upper service temperature was determined by thermomechanical analysis. c the glass transition temperature was determined by differential scanning calorimetry. d Weak means that the intensity of the transition Tv was signintly reduced compared to the non-sulfonated sample. As shown in Table 5, the zinc salts of the sulfonated ethylene / styrene copolymers show a substantial increase in heat resistance relative to the non-sulfonated polymer. The upper surface temperature, measured by the temperature of which the AMT probe shows a penetration of 1MM, increases substantially under sulfonation. This increase allows sulphonated polymers to be used in high heat elastomeric applications. The resistance to heat is further indicated by the comparison of the G 'values for the polymers at 20 ° C and 180 ° C. The non-sulfonated polymer exhibits a signint drop in modulus by increasing the temperature from 20 ° C to 180 ° C, while the sulphonated ionomers show little decrease in the plateau modulus compared to the non-sulfonated sample, still shows significant improvement in temperature resistance. EXAMPLE 3 Description of the reactor The only reactor used was a tank reactor with continuous agitation (RTAC) and autoclave, with a 22.7 liter oil jacket. A stirrer magnetically coupled with Lightening A-320 propellers provides mixing. The reactor operates full of liquid at 3,275 kPa. The process flow was at the bottom and outside the top. A heat transfer oil was circulated through the reactor jacket to remove some heat of reaction. After the reactor outlet there was a micromotion flow meter that measured the solution flow and density. All lines at the reactor outlet were steam traced at 344.7 kPa and isolated. Procedure The ethylbenzene solvent was supplied at 107 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. At the discharge of the solvent pump a side stream was taken to provide wash flows for the catalyst injection line (0.45 kg / hr) and the reactor stirrer (0.34 kg / hr). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. The uninhibited styrene monomer was supplied at 207 kPa. The feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. The styrene streams were mixed with the remaining solvent stream. The ethylene was supplied at 4,137 kPa. The ethylene stream was measured by a Micro-Motion mass flow meter just before the Research valve controlling the flow. A Brooks flow meter / controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene / hydrogen mixture is combined with the solvent / styrene stream at room temperature. The temperature of the measured solvent / monomer entering the reactor decreased to about 5 ° C by a glycol exchanger at -5 ° C on the jacket. This current entered the lower part of the reactor. The three-component catalyst system and its solvent rinse also enter the reactor at the bottom but through a different port than the monomer stream. The preparation of the catalyst components takes place in an inert atmosphere and is charged to the catalyst operation tanks in the process area. From these operating tanks the catalyst was pressurized with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst rinsing solvent just before entering through a single injection line into the reactor. The polymerization was stopped with the addition of a catalyst inhibitor mixture (water mixed with solvent) in the reactor product line after the micromotion flow meter measured the solution density. Other polymer additives can be added with catalyst inhibitor mixture. A static mixer in the line dispersed the catalyst and additive combination in the reactor effluent stream. This current then entered the heaters located after the reactor, which provide additional energy for the advance of solvent removal. This advance occurred as the effluent left the heater located after the reactor and the pressure was dropped from 3,275 kPa to approximately 250 mm absolute pressure in the reactor pressure control valve. This advanced polymer entered a hot oil jacket devolatilizer.

Approximately 85 percent of the volatile substances were removed from the polymer in the devolatilizer. Volatile substances leave the top of the devolatilizer. The stream was condensed and with a glycol jacket exchanger, sucked with a vacuum pump and discharged to a glycol jacket solvent and styrene / ethylene separation vessel. The solvent and styrene were removed from the bottom of the container and ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow meter and its composition was analyzed. The measurement of the ventilated ethylene plus a calculation of the gases dissolved in the solvent / styrene stream were used to calculate the ethylene conversion. The polymer separated in the devolatilizer was pumped out with a gear pump to a devolatilizing vacuum extruder of ZSK-30. The dried polymer leaves the extruder as a single cord. This cord cooled as it is pulled through a water bath. The excess water was blown from the cord with air and the cord was cut into pellets with a normal cutter.

Catalyst Employees a dimethyl [N- (1,1-di methylethyl) -1,1-di methyl- 1 - [((1,2, 3,4, 5-, eta,) - 1, 5,6,7-tetrahydro -3-phenyl-s-indacen-1-yl)] silanaminate (2 -) - N] -titanium b tallowalkylammonium tetrakis (pentafluorophenyl) borate bis-hydrogenated. c Modified methylaluminoxane commercially available from Akzo Nobel as MMAO-3A. d tris (pentafluorophenyl) borane. Reactor Data The ethylene / styrene interpolymers had the following properties to amount of component in copolymer. b amount of styrene in the copolymer + the amount of styrene in atactic polystyrene. c amount of atactic polystyrene in polymerization product.

B. Sulphonation of ES-3 200 grams of ESI pellets (cylindrical pellets of 3 mm height and 1.5 mm diameter of an ethylene / styrene copolymer containing 72 percent styrene with 30 percent aPS and has an IM l2 1.0) were loaded in a 1,000 mL 4-neck glass reaction pot with a stainless steel mechanical stirrer, a pressure gauge, a thermometer and an outlet port which is connected to a vacuum / gas manifold. The reaction vessel was rinsed with nitrogen, then evacuated to 25 torr. In a separate glass vessel, a 20 percent solution of sulfur trioxide gas in nitrogen was prepared. Sulfur trioxide was generated by heating fumed sulfuric acid (30 percent Oleum purchased from Aldrich Chemical Co.) at 95 ° C and recovering the sulfur trioxide vapor that was produced. The mechanical stirrer in the reaction pot was turned on and operated at a sufficient rate so that a rapid change of the polymer pellets was achieved. The sulfur trioxide / nitrogen mixture was slowly transferred to the reaction vessel by measuring through a needle valve while monitoring the vapor pressure in the reaction vessel. In this example, the sulfur trioxide mixture was poured into the reaction mixture until 0.50 g (6.25 mmole) of sulfur trioxide had been delivered. After the addition of sulfur trioxide, the reaction was stirred for one minute, then the reaction chamber was evacuated. After evacuation of the chamber, the sulfonated ESI pellets were rinsed repeatedly with nitrogen. C. Neutralization of ES-E Sulfonated from B The pellets of Example 3B were neutralized by supplying ammonium gas in the evacuated reaction chamber. This was achieved by evacuating the reaction vessel to 25 torr after sulfonation. Then, ammonium gas was supplied in the reaction chamber until a pressure of about 500 torr (large excess of ammonium) was observed. The neutralization is instantaneous and after approximately 5 seconds, the chamber was evacuated again and rinsed with nitrogen. The SO3NH4 + content of the ESI pellets was determined by x-ray fluorescence and found to be 2200 ppm. D. Sulfonation and Neutralization of ES-3 In this example, 200 grams of ESI pellets (ES-3: 72 weight percent styrene, 3 weight percent aPS, 1.0 IM l2) were sulfonated as described in example 3B, except that the mixture of sulfur trioxide was supplied in the reaction chamber until 0.20 g (2.5 mmol) had been delivered. This sample was neutralized with ammonium as described in example 3C. The SO3NH4 + content of the ESI pellets was determined by x-ray fluorescence and found to be 610 ppm. E. Sulfonation and Neutralization of ES-4 In this example, 200 grams of ESI pellets (ES-4 52 percent by weight of styrene, 1.0 percent by weight of aPs, 1.0 MI l2) were sulfonated as described in example 3B. This sample was neutralized with ammonium as described in example 3C. The SO3NH4 + content of ESI pellets was determined by x-ray fluorescence and found to be 1200 ppm. F. Sulfonation and Neutralization of ES-3 In this example, 200 grams of ESI pellets (ES-3 72 weight percent styrene, 3 weight percent aPs, 1.0 MI l 2) were sulfonated as described in Example 3B except that the sulfur trioxide mixture was supplied in the reaction chamber until 0.20 g (2.5 mmol) had been delivered. After sulfonation the non-neutralized pellets were removed from the reaction chamber and poured into a 1M solution of Zinc Acetate in water. After 30 seconds, the pellets were isolated by filtration and dried in a vacuum oven. The SO3Zn content of the ESI pellets was determined by x-ray fluorescence and found to be 450 ppm.

G. Sulfonation and Neutralization of ES-3 In this example, 200 grams of ESI pellets (ES-3: 72 weight percent styrene, 3 weight percent aPS, 1.0 IM l 2) were sulfonated as described in Example 3B, except that the mixture of sulfur trioxide was supplied in the reaction chamber until 0.20 g (2.5 mmol) had been delivered. This sample was neutralized with ammonium as described in example 3C. The SO3NH4 + content of the ESI pellets was determined by x-ray fluorescence and found to be 16 ppm. The blocking tendency of several samples was investigated using the pellet blocking method described in the Test Method section. Talc (Microtalc MP 12-50-Specialty Minerals Inc) was added dry to the pellets and stirred in a 250 mL glass jar. It was found that surface sulfonation significantly reduces the blocking tendency of polymer pellets.

The results are given in Table 6.

Table 6 * is not an example of the present invention. ** mole percent of mer units containing - SO3"M + group in total polymer The data in Table 6 show that surface sulfonation can be used to reduce the blocking tendency of polymer pellets. Contact The aqueous wettability of the surface sulfonated ESI samples was evaluated by measuring the contact angle between the water and the sulfonated ESI plates The surface sulfonation was found to significantly improve the aqueous wettability of the samples.

Table 7 * Mole percent of the polymer units containing a -SO3"M + group in the total polymer.

It is evident from these data that very low levels of sulfonation (16 ppm) can have an effect on the water's ability to wet the surface of ESI samples. This increase in surface polarity should result in better paint capacity, improved glass and metal adhesion and increased resistance to gasoline and other organic solvents. X-Ray Photoelectron Spectroscopy (EFX) The sulfonated ESI pellets were examined by EFX to verify that sulfonation only occurs on the surface of ESI pellets and plates. The outer surface of the individual pellets of Example 1B were examined. The pellets were cut in half and the internal matrix of the pellets was observed by EFX.

Table 8 * Molar percent of the mer units containing a group - SO3"M + in the total polymer These results show that the sulfonation occurs predominantly on the surface of the ESI pellets It also seems that there is a slight contamination of the TEFLON grease which was used to seal the reactor reaction pot.

Claims (19)

1. CLAIMS 1. A substantially random polymer having a sulfonated aromatic or cycloaliphatic ring or a sulfonated polymer backbone or a combination thereof comprising (1) from 1 to 65 mole percent of polymer units derived from (a) at least an aromatic vinyl or vinylidene monomer, or (b) a combination of at least one aromatic vinyl or vinylidene monomer containing an aromatic ring and at least one aliphatic or cycloaliphatic hindered vinylidene monomer; and (2) from 35 to 99 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (3) from zero to 20 mole percent of polymer units derived from a diene containing from 4 to 20 carbon atoms; and wherein said sulfonated interpolymer contains from 0.1 to 65 mole percent of one or more groups represented by the formula -SO3"M wherein M is hydrogen, NH4 + or a metal from the group of 1, 2, 7, 11 or 12 in ionic form 2. The substantially random sulfonated ether polymer of claim 1, wherein (i) component (1) is derived from styrene or vinyltoluene; (i) component (2) is derived from an α-olefin which has from 2 to 10 carbon atoms or any combination thereof, and (iii) M in the formula -SO3"M is hydrogen, NH4 + Li \ Na +, K +, MgA Ca * \ Mn", or ZnA Cu + or CuA 3. The substantially sulfonated random interpolymer of claim 1, wherein (i) component (1) is derived from styrene, (ii) component (2) is derived from ethylene, propylene, butene-1, hexene-1, pentene-1, octene-1 or any combination thereof, and (iii) M in the formula -S03"M is hydrogen, NH 4 + Li +, Na *, K +, Mg + +, or Zn." 4. The interpolymer subs sulfonated randomly portion of claim 3, comprising (i) from 1 to 50 mole percent of polymer units derived from component (1); (ii) from 50 to 99 mole percent of polymer units derived from component (2); and (iii) from 0 to 10 mole percent of polymer units derived from component (3); and (v) the polymer contains from 0.5 to 50 mole percent of the group represented by the formula -SO3"M 5. The substantially random sulfonated interpolymer of claim 3, comprising (i) from 1 to 50 mole percent of polymer units derived from component (1); (ii) from 50 to 99 mole percent of polymer units derived from component (2); and (i ii) from 0 to 10 mole percent of polymer units derived from component (3); and said polymer contains from 0.5 to 50 mole percent of the group represented by the formula -SO3"M. 6. A compatibilized blend of polymers comprising (A) from 1 to 99 weight percent of at least one polyamide; B) from 1 to 99 weight percent of at least one free olefin polymer of monomer units derived from aromatic vinyl or vinylidene monomers, and (C) from 1 to 99 weight percent of at least one interpolymer substantially sulfonated random having a sulfonated aromatic ring and is made of monomeric components comprising: (1) from 1 to 65 mole percent of (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic hindered vinylidene monomer, and (2) from 35 to 99 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. carbon; and (3) optionally Te, from zero to 20 mole percent of a diene containing from 4 to 20 carbon atoms; and wherein in said sulfonated interpolymer, 0.05 to 100 mole percent of the aromatic rings contain a substituent group represented by the formula -SO3"M wherein M is hydrogen, NH4 + or a metal of group 1, 2, 7 or 12 in ionic form or combination thereof 7. A mixture of claim 6, wherein the polymer of 0.05 to 25 mole percent of the aromatic rings contains a substituted group represented by the formula -S03"M. 8. A mixture of claim 6, wherein the component (C3) is present in an amount of zero mole percent. 9. A mixture of claim 8, wherein (i) component (C1) is styrene or vinyltoluene; and (ii) component (C2) is ethylene, propylene, butene-1, hexene-1, pentene-1, octene-1 or any combination thereof. The mixture of claim 8, wherein (i) the monomer (1) is styrene; (i) the monomer (2) is ethylene, propylene, butene-1, hexene-1, pentene-1, octene-1 or any combination thereof; and (iii) M in the formula SO3"M is hydrogen, NH4 + L¡ +, Na *, K +, MgA or ZnA 11. A modified interpolymer composition having an upper service temperature of at least 5 ° C greater than the unmodified interpolymer, the unmodified interpolymer comprising (A) from 1 to 65 mole percent of polymeric units derived of at least one vinyl or vinylidene aromatic monomer; and (B) from 35 to 99 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; the modified polymer resulting from (I) subjecting the unmodified interpolymer to sulfonation so that it is provided to the sulfonated polymer containing from 0.1 to 5 weight percent of -SO3H groups; and (II) reacting the sulfonated interpolymer of step (I) with an NH4 * or a metal compound of Group 1, 2, 7, 11 or 12 capable of reacting with the product of step (I) to convert at least some of the groups -SO3H to groups -SO3"M wherein M is NH4 + or a metal of group 1, 2, 7, 11 or 12. 12. A composition of claim 11, wherein (i) the aromatic monomer of vinyl or vinylidene is styrene, (ii) the aliphatic α-olefin has from 2 to 10 carbon atoms or any combination thereof: (iii) M in the formula SO 3"M is hydrogen, NH 4 + Li *, Na *, K + , MgA Ca **, Mn **, or Zn **, Cu * or Cu **; and (iv) the sulfonated polymer contains from 0.2 to 2.5 weight percent of -SO3 groups 13. A composition of claim 11, wherein (i) the aromatic vinyl or vinylidene monomer is styrene, and (ii) the aliphatic α-olefin is ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1 or any combination thereof, and (ii) M in the formula SO 3"M is hydrogen, NH 4 * Na *, K *, Zn **, Mg **, or Li *. 14. A surface-prepared sulfonated article of a substantially random interpolymer comprising: (1) from 1 to 65 mole percent of polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) a combination of at least one aromatic vinyl or vinylidene monomer containing an aromatic ring Ar, and at least one aliphatic or cycloaliphatic hindered vinylidene monomer; and (2) from 35 to 99 mole percent polymeric units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (3) from zero to 20 mole percent of polymer units derived from a diene containing from 4 to 20 carbon atoms; and wherein from 0.001 to 30 mole percent of the polymer units contained in the interpolymer contains one or more groups represented by the formula -SO3"M wherein M is hydrogen, NH4 * or a metal of the group of 1, 2, 7 , 11 or 12. 15. The article of claim 14, wherein (i) the component (1) is derived from styrene or vinyl toluene; (ii) component (2) is derived from an α-olefin having from 2 to 10 carbon atoms or any combination thereof; Y (iii) M in the formula -SO3"M is hydrogen, NH4 * Li *, Na *, K *, Mg **, Ca **, Mn **, Zn **, Cu * or Cu ** .16. The article of claim 14, wherein (i) component (1) is derived from styrene, (ii) component (2) is derived from ethylene, propylene, butene-1, pentene-1, hexene-1, octene -1 or any combination thereof, and (iii) M in the formula -SO3"M is hydrogen, NH4 * Na *, K *, Zn **, Mg **, or Li *. The article of claim 16, comprising (i) from 1 to 50 mole percent of polymer units derived from component (1); (ii) from 50 to 99 mole percent of polymer units derived from component (2); and (iii) from 0 to 10 mole percent of polymer units derived from component (3); and (iv) the polymer contains from 0.1 to 3 mole percent of the group represented by the formula -SO3"M 18. The article of claim 16 comprising (i) from 1 to 65 mole percent of polymer units derived from the component (1); (ii) from 35 to 99 mole percent of polymer units derived from component (2); and (¡ü) zero mole percent polymer units derived from component (3), and the polymer contains 0.1 to 1 mole percent of the group represented by the formula -SO3"M. 19. The article of claim 18 in the form of pellets, sheets or film.