AQUEOUS DISPERSIONS OR EMULSIONS OF INTERPOLYMERS OF ALPHA-OLEFIN(S)/HINDERED VINYLIDENE AROMATIC MONOMER(S)

Abstract: A film-forming, aqueous dispersion comprising at least one substantially random interpolymer comprising (A) polymer units derived from: (1) at least one vinylidene aromatic monomer, or (2) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (3) a combination of at least one aromatic vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (4) at least one C2-20 alpha -olefin; and (B) a surfactant. The aqueous dispersions or emulsions of the present invention are useful as barrier paper coatings, corrosion resistance coatings, carpet backing and carpet fiber binders, in some instances, precursors for high molecular weight polymers, composites and membranes for separation systems, coatings and binders for paints, inks, moisture barriers in packaging, fabric coatings, synthetic gloves, adhesives, foams, composite flooring tiles and layers, sound deadening composite foams and pads, automotive protective exterior coatings, and removable temporary protective coatings.

Description: AQUEOUS DISPERSIONS OR EMULSIONS OF INTERPOLYMERS OF ALPHA- OLEFIN(s) /HINDERED VINYLIDENE AROMATIC MONOMER(S) This application relates to aqueous dispersions or emulsions of interpolymers of α-olefin (s) /hindered vinylidene monomer (s) . These dispersions or emulsions may be film forming at room temperature and possess excellent physical and mechanical properties. In U.S. Patent 3,734,686, Douglas et al. disclose a mechanically stable aqueous emulsion of polyethylene particles having an average molecular weight ranging from 7,000 to 40,000. These dispersions are taught to be useful for treating carpets . In U.S. Patent 3,418,265, McClain teaches that aqueous film-forming ethylene polymer latexes containing ethylene polymer particles of submicron size can be prepared by dispersing in water an ethylene polymer and a water-soluble block copolymer of ethylene oxide and propylene oxide. No examples of stable dispersions of ethylene polymers having a molecular weight above 27,000 are reported. The polyolefin latexes previously described are actually not purely polyolefinic, but rather contain polar groups, such as acids, halogens or halides, acetate, ester, ether, amine, alcohol, acrylic, methacrylic, nitrile, nitro, sulfate, phosphate, or mercaptan latex groups. Since the film-forming properties of these so-called polyolefin latexes are often adversely influenced by the presence of these polar substituents, it would be desirable to prepare latexes derived from higher molecular weight polyethylenes that did not contain polar groups. It would be of further value if these latexes were film forming at room temperatures . In U.S. Patent 5,574,091 alther et al . disclose latexes that are film forming at room temperature; do not contain polar groups; and which are prepared from copolymers of ethylene and C 3 -C 20 α-olefins higher in molecular weight. While the ethylene/alpha olefin materials described in US 5,574,091 do eventually form films at room temperature, it generally takes longer to form strong films at room temperature unless some external heating is provided. It would therefore be desirable to have available, interpolymers which can be dispersed into water and the resulting emulsions can be subsequently employed to form strong, cohesive films and coatings at room temperature with no external heating required and over a relatively short period of time. It would be further desirable if such films demonstrated a wide latitude in properties ranging from extremely high tensile strength to very high elongation, with very high toughness for the entire polymer range. It would be further desirable if objects coated with these emulsions would be rendered resistant to water, acids and alkali's, and show excellent energy dissipation properties . We have found that alpha olefin vinylidene aromatic interpolymer emulsions are capable of forming tough, cohesive films at room temperature, developing near-ultimate strength in 12-48 hours, with no externally applied heat. The present invention is directed to film-forming, aqueous dispersions comprising at least one substantially random interpolymer comprising (A) polymer units derived from; (1) at least one vinylidene aromatic monomer, or (2) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (3) a combination of at least one aromatic vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (4) at least one C 2 - 2 o α-olefin; and (B) a surfactant. The aqueous dispersions or emulsions of the present invention are useful as barrier paper coatings, corrosion resistance coatings, carpet backing and carpet fiber binders, coatings and binders for paints, inks, moisture barriers in packaging, fabric coatings, synthetic gloves, adhesives, foams, composite flooring tiles and layers, sound deadening composite foams and pads, automotive protective exterior coatings, removable temporary protective coatings, and, in some instances, precursors for high molecular weight polymers, composites and membranes for separation systems. 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, or time 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 term "interpolymer" is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. The interpolymers can comprise, consist essentially of, or consist of any two or more of the enumerated polymerizable monomers . The term "hydrocarbyl" means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic groups. The aliphatic or cycloaliphatic groups are preferably saturated. Likewise, the term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached. The term "monomer residue" or "polymer units derived from such monomer" means that portion of the polymerizable monomer molecule which resides in the polymer chain as a result of being polymerized with another polymerizable molecule to make the polymer chain. The term "film forming aqueous dispersion" as used herein describes the result of dispersing the interpolymers used in the present invention in water resulting in a mixture which when dried is able to form a film. The term "emulsion" as used herein is used interchangeably with the term "dispersion" to describe the result of dispersing the interpolymers used in the present invention in water. The term "latex" as used herein is in its generic form which is used to describe most emulsion polymers and polymer colloids . The term "substantially random" in the substantially random interpolymer comprising an α-olefin and a vinylidene aromatic monomer or hindered aliphatic vinylidene monomer 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 comprising an α-olefin and a vinylidene aromatic monomer 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 was not characterized by a high degree of either isotacticity or syndiotacticity . This means that in the 13C-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. The interpolymers suitable for use in preparing the aqueous dispersions or emulsions 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 vinylidene aromatic monomers, or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, or a combination thereof, and optionally with other polymerizable ethylenically 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. Preferred such monomers are aliphatic α-olefins such as ethylene, propylene, butene-1, 4-methyl-l-pentene, hexene-1 and octene-1. Most preferred are ethylene or a combination of ethylene with C 2 _e α-olefins. These α-olefins do not contain an aromatic moiety. Suitable vinylidene aromatic monomers which can be employed to prepare the interpolymers employed in the dispersions include, for example, those represented by the following formula: Ar I (CH 2 ) n R i — c = C(R 2 ) 2 wherein R 1 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 R 2 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 or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, Cι_ 4 -alkyl, and Cι_ 4 -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, α-methyl styrene, the lower alkyl- (Ci - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para- vinyl toluene or mixtures thereof. A more preferred aromatic monovinylidene monomer is styrene. By the term "hindered aliphatic or cycloaliphatic vinylidene compounds", it is meant addition polymerizable vinylidene monomers corresponding to the formula: A 1 I 1 — C = C(R 2 ) 2 wherein A 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons, R 1 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 R 2 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 R 1 and A 1 together form a ring system. By the term "sterically bulky" 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. α-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 hindered aliphatic or cycloaliphatic vinylidene compounds are monomers 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, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, and norbornyl . Most preferred hindered aliphatic or cycloaliphatic vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2- norbornene. Especially suitable are 1-, 3-, and 4- vinylcyclohexene . Other optional polymerizable ethylenically unsaturated monomer (s) include strained ring olefins such as norbornene and Ci-io alkyl or C 6 -ιo aryl substituted norbornenes, with an exemplary interpolymer being ethylene/styrene/norbornene . The number average molecular weight (Mn) 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 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. For example, while preparing the substantially random interpolymer, an amount of atactic vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinylidene aromatic monomer at elevated temperatures. The presence of vinylidene aromatic homopolymer is in general not detrimental for the purposes of the present invention and can 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. For the purpose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent based on the total weight of the interpolymers of vinylidene aromatic homopolymer is present. The substantially random interpolymers 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 can be prepared as described in US Application Number 07/545,403 filed July 3, 1990 (corresponding to EP-A-0, 416, 815) by James C. Stevens et al. and in allowed US Application Number 08/469,828 filed June 6, 1995. Preferred operating conditions for such polymerization reactions are pressures from atmospheric up 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 disclosed in U.S. Application No. 07/545,403, filed July 3, 1990 corresponding to EP-A-416, 815; U.S. Application No. 07 /702 , 475, filed May 20, 1991 corresponding to EP-A-514 , 828 ; U.S. Application No. 07/876,268, filed May 1, 1992 corresponding to EP-A-520, 732 ; U.S. Application No. 08/241,523, filed May 12, 1994; as well as U.S. Patent Numbers: 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. The substantially random α-olefm/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) . Also suitable are the substantially random interpolymers which comprise at least one α-olefin/vinyl aromatic/vmyl aromatic/α-olefin tetrad disclosed m U. S. Application No. 08/708,809 filed 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 in the chemical shift range 43.70-44.25 ppm and 38.0-38.5 ppm. Specifically, major peaks are observed at 44.1, 43.9 and 38.2 ppm. A proton test NMR experiment indicates that the signals in the chemical shift region 43.70- 44.25 ppm are methine carbons and the signals in the region 38.0-38.5 ppm are methylene carbons. In order to determine the carbon-13 NMR chemical shifts of the interpolymers described, the following procedures and conditions are employed. A five to ten weight percent polymer solution is prepared m a mixture consisting of 50 volume percent 1, 1, 2 , 2-tetrachloroethane-d2 and 50 volume percent 0.10 molar chromium tris (acetylacetonate) m 1,2,4- tπchlorobenzene . NMR spectra are acquired at 130°C using an inverse gated decoupling sequence, a 90° pulse width and a pulse delay of five seconds or more. The spectra are referenced to the isolated methylene signal of the polymer assigned at 30.000 ppm. It is believed that these new signals are due to sequences involving two head-to-tail vinyl aromatic monomer preceded and followed by at least one α-olefin insertion, for example, an ethylene/styrene/styrene/ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1,2 (head to tail) manner. It is understood by one skilled in the art that for such tetrads involving a vinyl aromatic 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 -13 NMR peaks but with slightly different chemical shifts. These interpolymers are prepared by conducting the polymerization at temperatures of from -30°C to 250°C in the presence of such catalysts as those represented by the formula wherein: each Cp is independently, each occurrence, a substituted cyclopentadienyl group π-bound to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms; each R' is independently, each occurrence, H, halo, hydrocarbyl, hyrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R' groups together can be a Cι-ιo hydrocarbyl substituted 1,3- butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst such as, for example, ammonium-, sulfonium-, phosphonium-, oxonium-, ferrocenium-, or silylium- 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 occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group. Preferably, R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such 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- (dimethylsilanediyl (2-methyl-4-phenylindenyl) ) - zirconium dichloride, racemic- (dimethylsilanediyl (2-methyl-4- phenylindenyl) ) zirconium 1, 4-diphenyl-l, 3-butadiene, racemic- (dimethylsilanediyl (2-methyl-4-phenylindenyl) ) zirconium di- Ci-4 alkyl, racemic- (dimethylsilanediyl (2-methyl-4- phenylindenyl) ) zirconium di-Ci-4 alkoxide or any combination thereof. Also included are the titanium-based catalysts, [N- (1,1-dimethylethyl) -1, 1-dimethyl-l- [ ( 1, 2, 3, 4, 5-η) -1, 5, 6,7- tetrahydro-s-indacen-1-yl] silanaminato (2-) -N] titanium dimethyl; ( 1-indenyl) (tert-butylamido) dimethyl- silane titanium dimethyl; ( (3-tert-butyl) ( 1, 2, 3, 4 , 5-η) -1- indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; and ( (3-iso-propyl) ( 1, 2 , 3, 4 , 5-η) -1-indenyl) (tert-butyl amido) dimethylsilane titanium dimethyl, or any combination thereof. Further 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 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 (CpTiCl 3 ) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem. Soc . , Div. Polym. Chem. ) Volume 35, pages 686,687 [1994]) have reported copolymerization using a MgCl 2 /TiCl 4 /NdCl 3 /Al (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 TiCl 4 /NdCl 3 / MgCl 2 /Al(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 Me 2 Si (Me 4 Cp) (N-tert-butyl) TiCl 2 /methylaluminoxane Ziegler-Natta catalysts. The manufacture of α-olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996, issued to Mitsui Petrochemical Industries Ltd. The interpolymers which contain hindered cycloaliphatic monomer residues or polymer units derived from such monomer are usually prepared by subjecting an interpolymer containing monovinylidene aromatic monomer residues or polymer units derived from such monomer to hydrogenation thereof converting some or all of the aromatic rings to cycloaliphatic rings which can be saturated (for example, cyclohexane ring) or unsaturated (cyclohexene ring) . The interpolymers of one or more α-olefins and one or more monovinylidene aromatic monomers or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, or a combination thereof, employed in the present invention are substantially random polymers. These interpolymers usually contain from 0.5 to 18 or from 25 to 65, preferably from 5 to 17 or from 27 to 65, more preferably from 10 to 16 or from 29 to 65 mol percent of at least one vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer, or a combination thereof, and from 99.5 to 82 or from 75 to 35, preferably from 95 to 83 or from 73 to 35, more preferably from 90 to 84 or from 71 to 35 mol percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. The dispersions of the present invention are prepared in the presence of a stabilizing and an emulsifying amount of a suitable surfactant. The surfactant used to from the aqueous dispersion may be anionic, cationic or nonionic. The surfactants may also be a combination of anionic and nonionic, anionic and anionic, nonionic and nonionic, cationic and cationic, or cationic and nonionic surfactants. Examples of such surfactants include sulfonates of an alkylphenyl or alkylbenzene moiety represented by the formula : X-Φ-SO-fZ + wherein X is a Cε-Cis linear or branched alkyl group, preferably decyl, dodecyl or tridecyl, more preferably dodecyl; Φ is phenylene, preferably p-phenylene; and Z is sodium, potassium, or ammonium, preferably sodium. Some of the preferred sulfonates of alkylbenzenes are commercially available, for example, sodium dodecylbenzene sulfonate, commercially available under the trade name RHODACAL™ DS-10 from Rhone Poulenc, North Amer. Chem. Surfactants and Specialties, NJ. Other representative classes of surfactants include alkali metal or ammonium fatty acid salts such as alkali metal oleates and stearates; alkali metal or ammonium alkyl sulfates such as sodium lauryl sulfate or the dimethyl ethanolamine salt of isostearic acid; or C_o - C35 fatty alkyl alkoxylates, or their corresponding sulfate or phosphates such as sodium laureth-4 sulfate; or quaternary C10-C20 alkylammonium salts such as cetyl trimethylammonium bromide; or alkali metal or ammonium sulfates or phosphates of ethoxylated phenols, such as the ammonium salt of poly (oxy-1, 2-ethanediyl) a-sulfo- (nonylphenoxy) or the sodium salt of nonyl nonoxynol-10 phosphate; or alkali metal or ammonium salts of alkyl amphodicarboxylates, such as sodium cocoamphodipropionate; or alkali metal or ammonium salts of alkyl, alkylphenoxy or alkyloxynol sulfosuccinates, such as disodium deceth-6 sulfosuccinate . The most preferred surfactant is sodium dodecylbenzene sulfonate . In addition to being used singly, these surfactants may be advantageously used in combination with one another, or with other co-surfactants. Many suitable surfactants for the dispersion process can be found in "Handbook of Industrial Surfactants", compiled by Michael and Irene Ash, Gower Publishing Company, Brookfield, Vermont (1993). The particular choice of surfactant is very much a function of the character of the solvent chosen for the dispersion process, the temperature at which the process is conducted, and other operating conditions, as well as a strong function of the end- use requirements. A suitable amount of such surfactant may be any amount sufficient to form a useable aqueous dispersion, but is usually from 0.5 to 10, preferably from 1 to 6, more preferably from 2 to 4 percent by weight based on polymer solids . The aqueous dispersions of the present invention can be prepared by any suitable technique, including those described in U.S. Patents 3,360,599; 3,503,917; 4,123,403; and 5,037,864. A film having a substantially uniform thickness across a substrate or form can be prepared at room temperature (that is, from 20°C to 30°C) from the aqueous dispersion or emulsions of the present invention as described herein above. The film is further characterized by an absence of cracking or foramina . The film can be prepared by any suitable means such as casting, coagulating, or spraying. If films are prepared by coagulation, it is generally preferred to use fatty acid based surfactants, such as the sodium salt of oleic acid. The aqueous dispersions or emulsions of the present invention are useful as barrier paper coatings, corrosion resistance coatings, carpet backing and carpet fiber binders, in some instances, precursors for high molecular weight polymers, composites and membranes for separation systems, coatings and binders for paints, inks, moisture barriers in packaging, fabric coatings, synthetic gloves, adhesives, foams, composite flooring tiles and layers, sound deadening composite foams and pads, automotive protective exterior coatings, and removable temporary protective coatings. If coatings are to be prepared, such coatings may be either dried or cured, or a combination thereof, and may partially or completely cover the object to be coated. The objects to be prepared using the aqueous dispersions of the present invention may contain other additives such as antioxidants (for example, hindered phenols such as, for example, Irganox ® 1010), phosphites (for example, Irgafos ® 168), UV stabilizers, wetting aids, clays, starch, cling additives (for example, polyisobutylene) , antiblock additives, corrosion inhibitors, dispersants, biocides, coalescents, pacifiers, dyes colorants, pigments, and fillers can also be included in the interpolymers employed in the blends of or employed in the present invention, to the extent that they do not interfere with the enhanced properties discovered by Applicants. Preferred inorganic fillers may be crystalline or glassy, and either ionic or covalent in character. Preferred examples of inorganic fillers are, calcium carbonate, alumina trihydrate, fly ash, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, talc, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, glass microspheres or chalk. Of these fillers, barium sulfate, talc, calcium carbonate, silica/glass, glass fibers, alumina trihydrate, fly ash and titanium dioxide, and mixtures thereof are preferred. The most preferred inorganic fillers are, calcium carbonate, alumina trihydrate, fly ash or mixtures thereof. Additives such as fillers also play a role in the aesthetics of a final article providing a gloss or matte finish. These additives are employed in functionally equivalent amounts known to those skilled in the art and depending upon the given application. For example, the amount of antioxidant employed is that amount which prevents the polymers from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers. Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend. Similarly, the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend 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 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend. However, in the instance of fillers, they could be employed in amounts up to 90 percent by weight based on the weight of the polymer or polymer blend. The preferred amounts of inorganic filler depend on the desired end-use of the filled polymer compositions of the present invention. Additionally, antistatic agents can be added separately, or in combination. Examples of antistatic agents include but are not limited to the alkyl amines, such as ARMOSTAT™ 410, ARMOSTAT™ 450, ARMOSTAT™ 475, all commercially available from Akzo Nobel Corporation; quaternary ammonium compounds, such as MARKSTAT™ which is commercially available from The Argus Corporation, and salts such as LiPF δ , KPF 6 , lauryl pyridinium chloride, and sodium cetyl sulphate, which can be purchased from any ordinary chemical catalog. Wetting aids which can be used include Surfynol™ surfactants (available from Air Products and Chemicals Inc, Allentown, PA) as wetting aids for some coating formulations; in particular, Surfynol™ 104, (2, 4 , 7, 9-tetramethyl 5-decyn- 4,7-diol), as well as lower (C 2 -C 8 ) aliphatic alcohols such as, for example, isopropanol. In addition, flow and dispersions aids may be used including, titanates and zirconates, various processing oils and low molecular weight polymers and waxes such as poly (ethyleneoxide) , and organic salts such as zinc and calcium stearate. The following examples are illustrative of the invention, but are not to be construed as to limiting the scope of the invention in any manner. EXAMPLES Molecular weights of polymers can be conveniently indicated using a melt index measurement determined according to ASTM D-1238, Condition 190°C/2.16 kg (formally known as "Condition (E) " and also known as 12) . Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. Other useful physical property determinations made on the novel polymer compositions described herein include the melt flow ratio (MFR) : measured by determining "I 10 " (according to ASTM D-1238, Condition 190°C/10 kg (formerly known as "Condition (N)") and dividing the obtained I 10 by the I 2 . The ratio of these two melt index terms is the melt flow ratio and is designated as I 10 /i 2 In order to determine the 13 C NMR chemical shifts of the interpolymers described, the following procedures and conditions are employed. A five to ten weight percent polymer solution is prepared in a mixture consisting of 50 volume percent 1, 1, 2 , 2-tetrachloroethane-d2 and 50 volume percent 0.10 molar chromium tris (acetylacetonate) in 1,2,4- trichlorobenzene . NMR spectra are acquired at 130°C using an inverse gated decoupling sequence, a 90° pulse width and a pulse delay of five seconds or more. The spectra are referenced to the isolated methylene signal of the polymer assigned at 30.000 ppm. Atactic Polystyrene (aPS) concentration was determined by a nuclear magnetic resonance (N.M.R.) method, and the total styrene content was determined by Fourier Transform Infrared spectroscopy (FTIR). Delamination was determined by ASTM method D-3936. Tuft lock was determined by ASTM method D-1335. Rewet delamination was determined by ASTM method D-3936 with a one minute soak in water prior to testing. Examples 1 to 12 are emulsions and the corresponding films prepared from ethylene/styrene interpolymers of varying styrene compositions (ESI-1 - ESI-12) . Preparation of Catalyst (dimethyl [N- ( 1, 1-dimethylethyl) -1, 1- dimethyl-1- [ (l,2,3,4,5-τ)-l,5,6, 7-tetrahydro-3-phenyl-s- indacen-1-yl] silanaminato (2-) -N] - titanium) . Preparation of 3 , 5, 6, 7-Tetrahydro-s-Hydrindacen-l (2H) -one . Indan (94.00 g, 0.7954 moles) and 3-chloropropionyl chloride (100.99 g, 0.7954 moles) were stirred in CH 2 C1 2 (300 mL) at 0 ° C as A1C1 3 (130.00 g, 0.9750 moles) was added slowly under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours . The volatiles were then removed. The mixture was then cooled to 0°C and concentrated H 2 S0 (500 mL) slowly added. The forming solid had to be frequently broken up with a spatula as stirring was lost early in this step. The mixture was then left under nitrogen overnight at room temperature. The mixture was then heated until the temperature readings reached 90°C. These conditions were maintained for a 2 hour period of time during which a spatula was periodically used to stir the mixture. After the reaction period crushed ice was placed in the mixture and moved around. The mixture was then transferred to a beaker and washed intermittently with H 2 0 and diethyl ether and then the fractions filtered and combined. The mixture was washed with H 2 0 (2 x 200 mL) . The organic layer was then separated and the volatiles removed. The desired product was then isolated via recrystallization from hexane at 0 ° C as pale yellow crystals (22.36 g, 16.3 percent yield). H NMR (CDC1 3 ) : d2.04-2.19 (m, 2 H) , 2.65 (t, 3 JHH=5-7 Hz, 2 H) , 2.84-3.0 (m, 4 H) , 3.03 (t, 3 JHH=5.5 Hz, 2 H) , 7.26 (s, 1 H) , 7.53 (s, 1 H). 13 C NMR (CDC1 3 ) : d25.71, 26.01, 32.19, 33.24, 36.93, 118.90, 122.16, 135.88, 144.06, 152.89, 154.36, 206.50. GC- MS: Calculated for C 12 H 12 0 172.09, found 172.05. Preparation of 1, 2, 3 , 5-Tetrahydro-7-phenyl-s-indacene . 3,5, 6,7-Tetrahydro-s-Hydrindacen-l (2H) -one (12.00 g, 0.06967 moles) was stirred in diethylether (200 mL) at 0°C as PhMgBr (0.105 moles, 35.00 mL of 3.0 M solution in diethylether) was added slowly. This mixture was then allowed to stir overnight at room temperature. After the reaction period the mixture was quenched by pouring over ice. The mixture was then acidified (pH=l) with HC1 and stirred vigorously for 2 hours. The organic layer was then separated and washed with H 2 0 (2 x 100 mL) and then dried over MgS0 4 . Filtration followed by the removal of the volatiles resulted in the isolation of the desired product as a dark oil (14.68 g, 90.3 percent yield). H NMR (CDC1 3 ) : d2.0-2.2 (m, 2 H) , 2.8-3.1 (m, 4 H) , 6.54 (s, 1H) , 7.2-7.6 (m, 7 H) . GC-MS : Calculated for C 18 H 16 232.13, found 232.05. Preparation of 1, 2 , 3, 5-Tetrahydro-7-phenyl-s-indacene, dilithium salt. 1,2,3, 5-Tetrahydro-7-phenyl-s-indacene (14.68 g, 0.06291 moles) was stirred in hexane (150 mL) as nBuLi (0.080 moles, 40.00 mL of 2.0 M solution in cyclohexane) was slowly added. This mixture was then allowed to stir overnight. After the reaction period the solid was collected via suction filtration as a yellow solid which was washed with hexane, dried under vacuum, and used without further purification or analysis (12.2075 grams, 81.1 percent yield). Preparation of Chlorodimethyl (1, 5, 6, 7-tetrahydro-3-phenyl-s- indacen-1-yl ) silane. 1, 2, 3, 5-Tetrahydro-7-phenyl-s-indacene, dilithium salt (12.2075 g, 0.05102 moles) in THF (50 mL) was added dropwise to a solution of Me 2 SiCl 2 (19.5010 g, 0.1511 moles) in THF (100 mL) at 0°C. This mixture was then allowed to stir at room temperature overnight. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. The removal of the hexane resulted in the isolation of the desired product as a yellow oil (15.1492 g, 91.1 percent yield). H NMR (CDC1 3 ) : dθ.33 (s, 3 H) , 0.38 (s, 3 H) , 2.20 (p, 3 JHH=7.5 HZ, 2 H) , 2.9-3.1 (m, 4 H) , 3.84 (s, 1 H) , 6.69 (d, 3 JRH=2.8 HZ, 1 H) , 7.3-7.6 (m, 7 H) , 7.68 (d, 3 JHH= .4 HZ, 2 H) . 13 C NMR (CDC1 3 ) : dθ.24, 0.38, 26.28, 33.05, 33.18, 46.13, 116.42, 119.71, 127.51, 128.33, 128.64, 129.56, 136.51, 141.31, 141.86, 142.17, 142.41, 144.62. GC- MS: Calculated for C 20 H 21 ClSi 324.11, found 324.05. Preparation of N- ( 1, 1-Dimethylethyl) -1, 1-dimethyl-l- (1, 5, 6, 7- tetrahydro-3-phenyl-s-indacen-l-yl) silanamine . Chlorodimethyl (1, 5, 6, 7-tetrahydro-3-phenyl-s-indacen-l- yl)silane (10.8277 g, 0.03322 moles) was stirred in hexane (150 mL) as NEt 3 (3.5123 g, 0.03471 moles) and t-butylamine (2.6074 g, 0.03565 moles) were added. This mixture was allowed to stir for 24 hours. After the reaction period the mixture was filtered and the volatiles removed resulting in the isolation of the desired product as a thick red-yellow oil (10.6551 g, 88.7 percent yield). H NMR (CDC1 3 ) : d0.02 (s, 3 H) , 0.04 (s, 3 H) , 1.27 (s, 9 H) , 2.16 (p, 3 JHH=7.2 HZ, 2 H) , 2.9-3.0 (m, 4 H) , 3.68 (s, 1 H) , 6.69 (s, 1 H) , 7.3-7.5 (m, 4 H) , 7.63 (d, 3 JHH=7.4 HZ, 2 H) . C NMR (CDC1 3 ) : d-0.32, - 0.09, 26.28, 33.39, 34.11, 46.46, 47.54, 49.81, 115.80, 119.30, 126.92, 127.89, 128.46, 132.99, 137.30, 140.20, 140.81, 141.64, 142.08, 144.83. Preparation of N- ( 1, 1-Dimethylethyl ) -1, 1-dimethyl-l- (1 , 5 , 6, 7- tetrahydro-3-phenyl-s-indacen-l-yl ) silanamine, dilithium salt. N- (1, 1-Dimethylethyl) -1 , 1-dimethyl-l- (1,5, 6, 7-tetrahydro- 3-phenyl-s-indacen-l-yl) silanamine (10.6551 g, 0.02947 moles) was stirred in hexane (100 mL) as nBuLi (0.070 moles, 35.00 mL of 2.0 M solution in cyclohexane) was added slowly. This mixture was then allowed to stir overnight during which time no salts crashed out of the dark red solution. After the reaction period the volatiles were removed and the residue quickly washed with hexane (2 x 50 mL) . The dark red residue was then pumped dry and used without further purification or analysis (9.6517 grams, 87.7 percent yield). Preparation of Dichloro [N- ( 1, 1-dimethylethyl) -1, 1-dimethyl-l- [ (1,2, 3, 4, 5-fl.)-!, 5,6, 7-tetrahydro-3-phenyl-s-indacen-l- yl] silanaminato (2-) -N] titanium. N- (1, 1-Dimethylethyl) -1, 1-dimethyl-l- (1,5, 6, 7-tetrahydro- 3-phenyl-s-indacen-l-yl) silanamine, dilithium salt (4.5355 g, 0.01214 moles) in THF (50 mL) was added dropwise to a slurry of TiCl 3 (THF) 3 (4.5005 g, 0.01214 moles) in THF (100 mL) . This mixture was allowed to stir for 2 hours. PbCl 2 (1.7136 g, 0.006162 moles) was then added and the mixture allowed to stir for an additional hour. After the reaction period the volatiles were removed and the residue extracted and filtered using toluene. Removal of the toluene resulted in the isolation of a dark residue. This residue was then slurried in hexane and cooled to 0 ° C . The desired product was then isolated via filtration as a red-brown crystalline solid (2.5280 g, 43.5 percent yield). H NMR (CDC1 3 ) : dθ.71 (s, 3 H) , 0.97 (s, 3 H) , 1.37 (s, 9 H) , 2.0-2.2 (m, 2 H) , 2.9-3.2 (m, 4 H) , 6.62 (s, 1 H) , 7.35-7.45 (m, 1 H) , 7.50 (t, 3 JHH= .8 Hz, 2 H) , 7.57 (s, 1 H) , 7.70 (d, 3 JHH= .1 Hz, 2 H) , 7.78 (s, 1 H) . X H NMR (C 6 D 6 ) : dθ.44 (s, 3 H) , 0.68 (s, 3 H) , 1.35 (s, 9 H) , 1.6-1.9 (m, 2 H) , 2.5-3.9 (m, 4 H) , 6.65 (s, 1 H) , 7.1- 7.2 (m, 1 H) , 7.24 (t, 3 JHH= .1 Hz, 2 H) , 7.61 (s, 1 H) , 7.69 (s, 1 H) , 7.77-7.8 (m, 2 H) . "c NMR (CDC1 3 ) : dl.29, 3.89, 26.47, 32.62, 32.84, 32.92, 63.16, 98.25, 118.70, 121.75, 125.62, 128.46, 128.55, 128.79, 129.01, 134.11, 134.53, 136.04, 146.15, 148.93. "c NMR (C 6 D 6 ) : dθ.90, 3.57, 26.46, 32.56, 32.78, 62.88, 98.14, 119.19, 121.97, 125.84, 127.15, 128.83, 129.03, 129.55, 134.57, 135.04, 136.41, 136.51, 147.24, 148.96. Preparation of Dimethyl [N- ( 1, 1-dimethylethyl) -1, 1-dimethyl-l- [ (l,2,3,4,5-ττ . )-l,5,6, 7-tetrahydro-3-phenyl-s-indacen-l- yl] silanaminato (2-) -N] titanium. Dichloro [N- (1, 1-dimethylethyl) -1, 1-dimethyl-l- [(l,2,3,4,5-η)-l,5,6, 7-tetrahydro-3-phenyl-s-indacen-l- yl] silanaminato (2-) -N] titanium (0.4970 g, 0.001039 moles) was stirred in diethylether (50 mL) as MeMgBr (0.0021 moles, 0.70 mL of 3.0 M solution in diethylether) was added slowly. This mixture was then stirred for 1 hour. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a golden yellow solid (0.4546 g, 66.7 percent yield). H NMR (C 6 D 6 ) : dθ.071 (s, 3 H) , 0.49 (s, 3 H) , 0.70 (s, 3 H) , 0.73 (s, 3 H) , 1.49 (s, 9 H) , 1.7-1.8 (m, 2 H) , 2.5-2.8 (m, 4 H) , 6.41 (s, 1 H) , 7.29 (t, 3 HH= .4 Hz, 2 H) , 7.48 (s, 1 H) , 7.72 (d, 3 JHH= .4 Hz, 2 H) , 7.92 (s, 1 H) . 13 C NMR (C 6 D 6 ) : d2.19, 4.61, 27.12, 32.86, 33.00, 34.73, 58.68, 58.82, 118.62, 121.98, 124.26, 127.32, 128.63, 128.98, 131.23, 134.39, 136.38, 143.19, 144.85. CoCatalyst (bis (hydrogenated-tallowalkyl) methylamine) (B-FABA) Preparation . Methylcyclohexane (1200 mL) was placed in a 2L cylindrical flask. While stirring, bis (hydrogenated- tallowalkyl) methylamine (ARMEEN ® M2HT, 104 g, ground to a granular form) was added to the flask and stirred until completely dissolved. Aqueous HC1 (1M, 200 mL) was added to the flask, and the mixture was stirred for 30 minutes. A white precipitate formed immediately. At the end of this time, LiB(C 6 F 5 ) 4 • Et 2 0 • 3 LiCl (Mw = 887.3; 177.4 g) was added to the flask. The solution began to turn milky white. The flask was equipped with a 6 inch (152 mm) Vigreux column topped with a distillation apparatus and the mixture was heated (140 °C external wall temperature) . A mixture of ether and methylcyclohexane was distilled from the flask. The two- phase solution was now only slightly hazy. The mixture was allowed to cool to room temperature, and the contents were placed in a 4 L separatory funnel. The aqueous layer was removed and discarded, and the organic layer was washed twice with H 2 0 and the aqueous layers again discarded. The H 2 0 saturated methylcyclohexane solutions were measured to contain 0.48 wt percent diethyl ether (Et 2 0) . The solution (600 mL) was transferred into a 1 L flask, sparged thoroughly with nitrogen, and transferred into the drybox. The solution was passed through a column (1 inch (25 mm) diameter, 6 inch (152 mm) height) containing 13x molecular sieves. This reduced the level of Et 2 0 from 0.48 weight percent to 0.28 weight percent. The material was then stirred over fresh 13X sieves (20 g) for four hours. The Et 2 0 level was then measured to be 0.19 w eight percent. The mixture was then stirred overnight, resulting in a further reduction in Et 2 0 level to approximately 40 ppm. The mixture was filtered using a funnel equipped with a glass frit having a pore size of 10-15 μm to give a clear solution (the molecular sieves were rinsed with additional dry methylcyclohexane) . The concentration was measured by gravimetric analysis yielding a value of 16.7 wt percent. A 6 gallon (22.7 L) , oil jacketed, Autoclave continuously stirred tank reactor (CSTR) was used as the reactor. A magnetically coupled agitator with Lightning A-320 impellers provides the mixing. The reactor ran liquid full at 475 psig (3,275 kPa) . Process flow was in the bottom and out the top. A heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction. After the exit from the reactor was a Micro-Motion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated. Ethylbenzene solvent was supplied to the reactor at 30 psig (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 flush flows for the catalyst injection line (1 lb./hr. (0.45 kg/hr) ) and the reactor agitator (0.75 lb./hr. ( 0.34 kg/ hr) ) . These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves. Uninhibited styrene monomer was supplied to the mini-plant at 30 psig (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 was mixed with the remaining solvent stream. Ethylene was supplied to the mini-plant at 600 psig (4,137 kPa) . The ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow. A Brooks flow meter/controllers was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature. The temperature of the solvent/monomer as it enters the reactor was dropped to ~5 °C by an exchanger with -5°C glycol on the jacket. This stream entered the bottom of the reactor. The three component catalyst system and its solvent flush also enter the reactor at the bottom but through a different port than the monomer stream. Preparation of the catalyst components took place in an inert atmosphere glove box. The diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured up with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst flush solvent just prior to entry through a single injection line into the reactor. Polymerization was stopped with the addition of catalyst kill (water mixed with solvent) into the reactor product line after the micromotion flow meter measuring the solution density. Other polymer additives can be added with the catalyst kill. A static mixer in the line provided dispersion of the catalyst kill and additives in the reactor effluent stream. This stream next entered post reactor heaters that provide additional energy for the solvent removal flash. This flash occurred as the effluent exited the post reactor heater and the pressure was dropped from 475 psig (3,275 kPa) down to ~250mm of pressure absolute at the reactor pressure control valve. This flashed polymer entered a hot oil jacketed devolatilizer . Approximately 85 percent of the volatiles were removed from the polymer in the devolatilizer. The volatiles exit the top of the devolatilizer. The stream was condensed and with a glycol jacketed exchanger, entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top. The ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses 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 ZSK-30 devolatilizing vacuum extruder. The dry polymer exits the extruder as a single strand. This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper. Table 1 - Catalysts Employed A dimethyl [N- (1, 1-dιmethylethyl) -1, 1-dιmethyl-l- [d,2,3,4,5-η-l,5,6, 7-tetrahydro-3-phenyι-s-mαacen-l- yl] silanaminato (2-) -N] - titanium B (t-butylamido) dimethyl (tetramethylcyclopenta- dienyl) -silane-titanium (II) 1, 3-pentadιene prepared as described in U.S. Patent # 5,556,928, Example 17. c bis-hydrogenated tallowalkyl methylammonium tetrakis (pentafluorop enyl) bor te. d a modified methylaluitiinoxane commercially available from Akzo Nobel as MMAO-3A. e tris (pentafluorophenyl ) borane (CAS# 001109-15-5). Table 2 Reactor Data Table 3 - Polymer Properties Latex dispersions were made by first preparing a mixture of between 20 and 30 percent by weight ethylene/styrene interpolymer in toluene. Surfactant was added to this mixture at between 2 to 4 parts surfactant per 100 parts polymer. N- propanol was also added to this mixture at a level between 3 and 5 parts per 100 parts polymer. The polymer concentration, and amounts of surfactant and n-propanol used in preparing the polymer solution for each example dispersion are listed in Table 4. Rhodacal™ DS-10 (available from Rhone-Poulenc, North Amer. Chem. Surfactants and Specialties, NJ) was the surfactant used in all examples except Example 5, which used sodium oleate. Table 4 - Polymer Solution Compositions Used to Make Dispersions The above mixture was then heated to approximately 100°C to form a homogeneous solution. An emulsion was made by continuously pumping 16 g/min of the solution and 1.5 g/min of water into a small-stainless steel vessel, where the two streams were mixed together under conditions of shear using an IKA T-25 ULTRA-TORRAX rotor-stator mixer operating at about 7,000 rpm and approximately 60°C. The mixture emptied from the mixing vessel was a highly viscous dispersion, with water as the continuous phase. Water was immediately added to the emulsion to reduce its viscosity and maintain emulsion stability. The toluene and propanol were removed from the dispersion by rotary evaporation. The final latex dispersion was approx. 50 percent polymer solids by weight. Films were prepared by pouring a small quantity of latex on a glass plate and spreading the latex uniformly using a 0.020 inch (0.51 mm) drawdown bar. One set of films were dried at the temperature and for the time specified in Table 5. The other set of films were dried in an oven again at the temperature and for the time specified in Table 5. The films were removed from the glass plates and tested using an Instron tensile machine. Both the room temperature and the oven dried films showed good tensile properties. The results are given in Table 5. Table 5 - Film Tensile Data I J o I a Maximum tensile strength. b Tensile set. c Youngs modulus . d d = days; h = hours; m = minutes. The results in Table 5 show that good maximum tensile performance (that is, greater than about 800 psi (5,515 Kpa)) is observed at both low styrene interpolymer content (from 0.5 to 18, preferably from 5 to 17, more preferably from 10 to 16 mol percent styrene) and high styrene interpolymer content (of from 25 to 65 preferably from 27 to 65, more preferably from 29 to 65 mol percent styrene) . A latex comprised of ESI-1 interpolymer dispersed in water with Rhodacal™ DS-10 (available from Rhone-Poulenc, North Amer. Chem. Surfactants and Specialties, NJ) (Example 13) was prepared analogously to the Example 1-12 above. A sample of this latex was drawn onto a sheet of glass using a stainless steel drawdown bar having a 20 mil machined gap. The coated glass sheet was placed in an oven set for 80°C for a period of 30 minutes, and then allowed to cool back to room temperature. The film was translucent, but had sufficient optical clarity that typewritten text could be read through it with a separation of three feet. Various regions of the coating were individually treated with a drop of several solvents and corrosives. Each was allowed to evaporate to dryness. The sample of 20 percent caustic did not evaporate, but over a weekend, dried to a white button. It was rinsed off before evaluating the effects of each on the coating. As shown in Table 6, only the hydrocarbon solvents affected the film. * rinsed off with distilled water ** polymer film appeared to swell while solvent was present Glass plates (Example 14) similarly coated as for Example 13 with polymer films of ESI-4, 7, and 10 were subjected to an impact test by dropping a 3/8 inch (0.95 cm) steel ball bearing from a height of 15 inches (38 cm) . For each of the coated plates, the ball stopped dead where it landed, with no bounce, and a somewhat deadened sound. For a control sheet of uncoated glass, the ball rebounded to a height of about 6.5 inches (16.5 cm), and bounced several more times, with a much sharper sound. This illustrates the protective and energy dissipative nature of these materials as coatings. Examples 15-17 are the results of tests of the aqueous dispersions of the present invention as carpet backings. Carpet backing compounding was performed by adding (a) a filler (calcium carbonate, CaC0 3 ) to the latex while it is being agitated, and, after the filler has been completely mixed in, (b) a defoamer, Nopco™ NDW (available from Nopco Chemical) and (c)a surfactant/foaming agent (ammonium lauryl sulfate) , and, after thorough mixing, (d) the thickener (METHOCEL 228 available from the Dow Chemical Company) . The product was then mixed until the viscosity stabilized. The carpets were crafted by roller coating the compounded latex described above directly to the under side of the tufted carpet greige goods. The secondary backing was similarly coated with the same compound. The two coated sides were then brought together and lightly pressed with a roller. This was followed immediately by drying/curing in a forced air oven until the surface temperature of the back using an IR thermometer reached 120 degrees Celsius (making sure the carpet composite remains flat until it is dry) . Testing was completed after cooling and cutting the carpet to the appropriate size, and weighing to determine the coating weight . Example 15 is a carpet backing prepared from the ESI interpolymer having 40.9 mol percent styrene, and a melt index (I 2 ) of 1.3. The latex dispersion was with 4 percent DS-10 as surfactant and 4 percent n-propanol, using a 23 percent by weight polymer solution in toluene and using the additives summarized in Table 7. Comparative Experiment 1 is a carpet backing prepared from the latex LXC800F NA (available from the Dow Chemical Company) using the additives summarized in Table 7. This latex is a carboxylated styrene/butadiene emulsion copolymer which is 62 weight percent styrene as charged to the reactor. It has, as post reaction additives, 0.5 p.h.r. of the dispersant, tetrasodium pyrophosphate, 50 ppm of the antimicrobial, Kathon™, (available from Rohm and Hass, Philadelphia PA), and 0.1 p.h.r. of the antioxidant, Aquamix™ (available from Harwick Chemical, Akron, Ohio) . Nominal solids are 52 percent with the remainder being water. Table T 'Carpet : Nylon 6, face fiber, 1/10 gauge loop pile, 8 pick woven propylene secondary phr - parts per hundred resin solids Example 16 is a carpet backing prepared as for Example 15 from an ESI interpolymer having 49.8 mol percent styrene, and a melt index (I 2 ) of 1.54 g/10 minutes. The latex dispersion was made with 4 percent DS-10 as surfactant and 4 percent n-propanol, using a 23 percent by weight polymer solution in toluene but using Igepal™ CO-730 (available from Rhone-Poulenc, Cranbury, NJ) as surfactant, and using Paragum™ 141 (available from Para Chem) as the thickener as summarized in Table 8. Table 8 + *Carpet: textured level loop. Nylon 6 yarn, 8 pick secondary phr - parts per hundred resin solids Example 17 is a carpet backing prepared as for Example 16 from the ESI interpolymer having 49.8 mol percent styrene, and a melt index (I 2 ) of 1.54. The latex dispersion was made with 4 percent DS-10 as surfactant and 4 percent n-propanol, using a 23 percent by weight polymer solution in toluene, and using the various additives summarized in Table 9. Comparative Experiment 2 is a carpet backing prepared from the latex LXC8429NA (available from the Dow Chemical Company) using the additives summarized in Table 7. This latex is a carboxylated styrene/butadiene emulsion copolymer which is 57 wt percent styrene as charged to the reactor. It has, as post reaction additives, 0.5 p.h.r. of the dispersant, tetrasodium pyrophosphate, 50 ppm of the antimicrobial, Kathon™, (available from Rohm and Hass, Philadelphia PA), and 0.1 p.h.r. of the antioxidant, Aquamix TM (available from Harwick Chemical, Akron, Ohio) . Nominal solids are 52 percent with the remainder being water. Table 9 + * Carpet: Level loop, nylon 6,6 fiber, 8 pick secondary phr - parts per hundred resin solids These results demonstrate that in all cases the inventive formulations when used as carpet backings show very little rewet delamination compared to other commercially available resins used in this application.

Claims: CLAIMS 1. A film-forming, aqueous dispersion comprising at least one substantially random interpolymer comprising (A) polymer units derived from; (1) at least one vinylidene aromatic monomer, or (2) at least one hindered aliphatic or cycloaliphatic vinylidene monomer, or (3) a combination of at least one aromatic vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinylidene monomer, and (4) at least one C 2 - 2 o α-olefin; and (B) a surfactant. 2. The film-forming, aqueous dispersion of Claim 1 wherein; (A) said substantially random interpolymer has a number average molecular weight, M n , of greater than 5,000; and comprises (1) from 0.5 to 18 or from 25 to 65 mol percent of polymer units derived from; (a) at least one of said vinylidene aromatic monomers, or (b) at least one of said hindered aliphatic or cycloaliphatic vinylidene monomers, or (c) a combination of at least one of said aromatic vinylidene monomers and at least one of said hindered aliphatic or of said cycloaliphatic vinylidene monomers, and (2) from 99.5 to 82 or from 75 to 35 mol percent of polymer units derived from at least one of said C 2 - 20 α-olefins; and (B) said surfactant is present in an amount of from 0.5 to 10 weight percent based on the total weight of polymer solids . 3. The film-forming, aqueous dispersion of Claim 1; wherein (A) said substantially random interpolymer has a number average molecular weight, M n , of from 20,000 to 1,000,000; and comprises (1) from 5 to 17 or from 27 to 65 mol percent of polymer units derived from; (a) at least one of said vinylidene aromatic monomers represented by the following general formula; Ar I R i — C = CH 2 wherein R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing three carbons or less, and Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, Cι- 4 -alkyl, and Cι- 4 -haloalkyl; or (b) at least one of said hindered aliphatic or cycloaliphatic vinylidene monomers represented by the following general formula; A' I R i — c = C(R 2 ) 2 wherein A 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons, R 1 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 R 2 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 R 1 and A 1 together form a ring system; or (2) from 95 to 83 or from 73 to 35 mol percent of polymer units derived from ethylene or a combination of ethylene and at least one C 3 -C 8 α- olefin; and (B) said surfactant is present in an amount of from 1 to 6 weight percent based on the total weight of polymer solids and comprises (1) one or more sulfonates of an alkylphenyl moiety represented by the formula: X-Φ-S0 3 ~ Z + wherein X is a C6-C 18 linear or branched alkyl group, Φ is phenylene or p-phenylene; and Z is sodium, potassium, or ammonium, or (2) one or more alkali metal or ammonium fatty acid salts, or; (3) one or more alkali metal or ammonium alkyl sulfates, or; (4) one or more C 10 -C- 35 fatty alkyl alkoxylates, or; (5) one or more alkali metal or ammonium salts of alkyl ethoxylate sulfates or; (6) one or more alkali metal or ammonium salts of alkylphenol ethoxylate sulfates, or; (7) one or more alkali metal or ammonium salts of alkyl ethoxylate phosphates or; (8) one or more alkali metal or ammonium salts of alkylphenol ethoxylate phosphates, or; (9) one or more quaternary C 8 -C 20 alkyl or alkaryl ammonium salts, or; (10) one or more alkali metal or ammonium salts of Cιo-C 2 o alkyl amphodicarboxylates , or; (11) one or more alkali metal or ammonium salts of C 5 -C- 20 alkyl sulfosuccinates , or; (12) one or more alkali metal or ammonium salts of C 5 -C 2 o ethoxylated alkyl sulfosuccinates, or; (13) one or more alkali metal or ammonium salts of ethoxylated alkylphenol sulfosuccinates . (14) a combination of any of (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), or (13). 4. The film-forming, aqueous dispersion of Claim 1; wherein; (A) said substantially random interpolymer has a number average molecular weight, M n , of from 50,000 to 500,000; and comprises (1) from 10 to 16 or from 29 to 65 mol percent; of polymer units derived from; (a) the group consisting of styrene, α-methyl styrene, ortho-, meta-, and para-methylstyrene, and the ring halogenated styrenes, or (b) the group consisting of 5-ethylidene-2- norbornene or 1-vinylcyclo-hexene, 3- vinylcyclohexene, and 4-vinylcyclohexene; or (c) a combination of at least one of (1) and one of (2) ; and (2) from 90 to 84 or from 71 to 35 mole percent of said α-olefin which contains polymer units derived from ethylene or a combination of ethylene with one or more of propylene, 4-methyl pentene, butene-1, hexene-1 or octene-1; and (B) said surfactant is present in an amount of from 2 to 4 weight percent based on the total weight of polymer solids and is (1) sodium decylbenzene sulphonate, sodium dodecylbenzene sulphonate, or sodium tridecyl- benzene sulphonate; or (2) an alkali metal or ammonium oleate or stearate; or (3) sodium lauryl sulfate or the dimethyl ethanolamine salt of isostearic acid; or (4) sodium laureth-4 sulfate; or (5) cetyl trimethylammonium bromide or cetylpyridinium chloride; or (6) the ammonium salt of poly (oxy-1, 2- ethanediyl) α-sulfo-ω (nonylphenoxy) or the sodium salt of nonyl nonoxynol-10 phosphate; or (7) sodium cocoamphodipropionate; or (8) disodium deceth-6 sulfosuccinate; or (9) a combination of any of (1), (2), (3), (4) , (5), (6) , (7), or (8) . 5. The film-forming, aqueous dispersion of Claim 4; wherein 1) said substantially random interpolymer contains polymer units derived only from styrene and ethylene; 2) said substantially random interpolymer is prepared using a constrained geometry catalyst; and 3) said surfactant is sodium dodecylbenzene sulfonate. 6. The film-forming, aqueous dispersion of Claim 1 that is film forming at room temperature. 7. A barrier paper coating, a paint, an ink, a corrosion resistant coating, a sound deadening coating, or an energy absorbing coating comprising the film-forming, aqueous dispersion of Claim 1. 8. A carpet backing comprising the film-forming, aqueous dispersion of Claim 1. 9. The carpet backing of Claim 8 containing an inorganic filler. 10. The carpet backing of Claim 9 wherein said filler comprises one or more of calcium carbonate or alumina trihydrate, or fly ash. 11. A paper roll or sheet fabricated from paper coated with the film-forming, aqueous dispersion of Claim 1.

Inventors: BETHEA JAMES R, CZEREPINSKI RALPH G, HOENIG WENDY D, KERNSTOCK JOHN M, OATES JOHN D, WALTHER BRIAN W, BETHEA, JAMES, R., CZEREPINSKI, RALPH, G., HOENIG, WENDY, D., KERNSTOCK, JOHN, M., OATES, JOHN, D., WALTHER, BRIAN, W.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1998
Main classification: C08J3
IPC codes: C08F12, C08F210, C08J3, C08J5, C08K5, C08L23, C09D123, C09D125, D06M15, D06N7, D21H19