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WO1999024492A1 - Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave - Google Patents

Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave Download PDF

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Publication number
WO1999024492A1
WO1999024492A1 PCT/US1998/024171 US9824171W WO9924492A1 WO 1999024492 A1 WO1999024492 A1 WO 1999024492A1 US 9824171 W US9824171 W US 9824171W WO 9924492 A1 WO9924492 A1 WO 9924492A1
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Prior art keywords
alkyl
film
alkali metal
vinylidene
forming
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PCT/US1998/024171
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English (en)
Inventor
John D. Oates
Ralph G. Czerepinski
Wendy D. Hoenig
John M. Kernstock
Brian W. Walther
James R. Bethea
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Dow Chemical Co
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Dow Chemical Co
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Priority to BR9814179-1A priority Critical patent/BR9814179A/pt
Priority to JP2000520497A priority patent/JP2001522911A/ja
Priority to EP98959429A priority patent/EP1030874A1/fr
Priority to CA002309821A priority patent/CA2309821A1/fr
Priority to MXPA00004599A priority patent/MXPA00004599A/es
Priority to KR1020007005117A priority patent/KR20010032006A/ko
Priority to AU15228/99A priority patent/AU1522899A/en
Publication of WO1999024492A1 publication Critical patent/WO1999024492A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0063—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
    • D06N7/0071—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing
    • D06N7/0073—Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing the back coating or pre-coat being applied as an aqueous dispersion or latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0838—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with monomers including an aromatic carbocyclic ring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0218—Vinyl resin fibres
    • D06N2201/0227—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/042—Polyolefin (co)polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant

Definitions

  • This application relates to aqueous dispersions or emulsions of interpolymers of ⁇ -olefin (s) /hindered vinylidene monomer (s) .
  • These dispersions or emulsions may be film forming at room temperature and possess excellent physical and mechanical properties.
  • 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 .
  • 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.
  • 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.
  • polar groups such as acids, halogens or halides, acetate, ester, ether, amine, alcohol, acrylic, methacrylic, nitrile, nitro, sulfate, phosphate, or mercaptan latex groups.
  • 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
  • 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.
  • 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.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • 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 .
  • 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.
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
  • 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.
  • film forming aqueous dispersion 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.
  • 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.
  • latex as used herein is in its generic form which is used to describe most emulsion polymers and polymer colloids .
  • substantially random in the substantially random interpolymer comprising an ⁇ -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.
  • the substantially random interpolymer comprising an ⁇ -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 .
  • 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.
  • 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 ⁇ -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 ⁇ -olefin monomers include for example, ⁇ -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 ⁇ -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 ⁇ -olefins. These ⁇ -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 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, C ⁇ _ 4 -alkyl, and C ⁇ _ 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, ⁇ -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, ⁇ -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.
  • hindered aliphatic or cycloaliphatic vinylidene compounds it is meant addition polymerizable vinylidene monomers corresponding to the formula:
  • 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
  • R 1 and A 1 together form a ring system.
  • 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.
  • ⁇ -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.
  • 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.
  • Particular suitable are 1-, 3-, and 4- vinylcyclohexene .
  • ethylenically unsaturated monomer examples include strained ring olefins such as norbornene and Ci-io alkyl or C 6 - ⁇ o 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.
  • 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.
  • 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.
  • 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 ⁇ -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) .
  • substantially random interpolymers which comprise at least one ⁇ -olefin/vinyl aromatic/vmyl aromatic/ ⁇ -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.
  • 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- t ⁇ chlorobenzene .
  • 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.
  • these new signals are due to sequences involving two head-to-tail vinyl aromatic monomer preceded and followed by at least one ⁇ -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.
  • 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
  • Suitable substituted cyclopentadienyl groups include those illustrated by the formula:
  • 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.
  • 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 .
  • 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.
  • titanium-based catalysts [N- (1,1-dimethylethyl) -1, 1-dimethyl-l- [ ( 1, 2, 3, 4, 5- ⁇ ) -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- ⁇ ) -1- indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; and ( (3-iso-propyl) ( 1, 2 , 3, 4 , 5- ⁇ ) -1-indenyl) (tert-butyl amido) dimethylsilane titanium dimethyl, or any combination thereof.
  • 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) .
  • interpolymers of one or more ⁇ -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.
  • 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 ⁇ -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.
  • surfactants include sulfonates of an alkylphenyl or alkylbenzene moiety represented by the formula :
  • X is a C ⁇ -Cis linear or branched alkyl group, preferably decyl, dodecyl or tridecyl, more preferably dodecyl; ⁇ is phenylene, preferably p-phenylene; and Z is sodium, potassium, or ammonium, preferably sodium.
  • alkylbenzenes are commercially available, for example, sodium dodecylbenzene sulfonate, commercially available under the trade name RHODACALTM DS-10 from Rhone Poulenc, North Amer. Chem. Surfactants and Specialties, NJ.
  • 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 salt
  • the most preferred surfactant is sodium dodecylbenzene sulfonate .
  • 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 .
  • 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.
  • 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.
  • antioxidants for example, hindered phenols such as, for example, Irganox ® 1010
  • phosphites for example, Irgafos ® 168
  • UV stabilizers for example, wetting aids, clays, starch,
  • 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.
  • 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.
  • additives are employed in functionally equivalent amounts known to those skilled in the art and depending upon the given application.
  • 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.
  • 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.
  • 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.
  • antistatic agents can be added separately, or in combination.
  • antistatic agents include but are not limited to the alkyl amines, such as ARMOSTATTM 410, ARMOSTATTM 450, ARMOSTATTM 475, all commercially available from Akzo Nobel Corporation; quaternary ammonium compounds, such as MARKSTATTM which is commercially available from The Argus Corporation, and salts such as LiPF ⁇ , 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 SurfynolTM surfactants (available from Air Products and Chemicals Inc, Allentown, PA) as wetting aids for some coating formulations; in particular, SurfynolTM 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.
  • SurfynolTM surfactants available from Air Products and Chemicals Inc, Allentown, PA
  • SurfynolTM 104 (2, 4 , 7, 9-tetramethyl 5-decyn- 4,7-diol)
  • lower (C 2 -C 8 ) aliphatic alcohols such as, for example, isopropanol.
  • 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.
  • 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
  • I 10 /i 2 the melt flow ratio
  • 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).
  • N.M.R. nuclear magnetic resonance
  • FTIR Fourier Transform Infrared spectroscopy
  • 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) .
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 ⁇ m 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 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.
  • 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.
  • 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. RhodacalTM 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.
  • 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
  • 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 RhodacalTM 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.
  • Example 14 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) .
  • the ball stopped dead where it landed, with no bounce, and a somewhat deadened sound.
  • 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, NopcoTM 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.
  • a filler calcium carbonate, CaC0 3
  • NopcoTM NDW available from Nopco Chemical
  • a surfactant/foaming agent ammonium lauryl sulfate
  • 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, KathonTM, (available from Rohm and Hass, Philadelphia PA), and 0.1 p.h.r. of the antioxidant, AquamixTM (available from Harwick Chemical, Akron, Ohio) . Nominal solids are 52 percent with the remainder being water.
  • 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 IgepalTM CO-730 (available from Rhone-Poulenc, Cranbury, NJ) as surfactant, and using ParagumTM 141 (available from Para Chem) as the thickener as summarized in Table 8.
  • 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, KathonTM, (available from Rohm and Hass,

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Abstract

L'invention concerne une dispersion aqueuse filmogène contenant au moins un interpolymère sensiblement aléatoire comprenant (A) des unités polymères dérivées de (1) au moins un monomère aromatique de vinylidène, ou (2) au moins un monomère de vinylidène aliphatique ou cycloaliphatique entravé, ou (3) une combinaison d'au moins un monomère de vinylidène aromatique et d'au moins un monomère de vinylidène aliphatique ou cycloaliphatique entravé, et (4) au moins une α-oléfine C2-20; et (B) un tensioactif. Les dispersions ou émulsions aqueuses de la présente invention sont utiles en tant que revêtements d'arrêt pour papier, revêtements anticorrosion, liants pour dossier et fibre de moquette, et dans certains cas en tant que précurseurs pour polymère de masse moléculaire élevée, composites et membranes pour systèmes de séparation, revêtements et liants pour peintures, encres, écrans humidifuges dans les emballages, revêtements pour tissu, gants synthétiques, adhésifs, mousses, carreaux et couches de planchéiage composite, mousses et plaques composites antisoniques, garnitures extérieures protectrices pour automobile et garnitures protectrices temporaires amovibles.
PCT/US1998/024171 1997-11-12 1998-11-12 Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave Ceased WO1999024492A1 (fr)

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BR9814179-1A BR9814179A (pt) 1997-11-12 1998-11-12 Dispersoes ou emulsoes aquosas de interpolimeros de monomero (s) aromatico ( s) de alfa olefina (s) vinilideno impedido (s) e seu uso
JP2000520497A JP2001522911A (ja) 1997-11-12 1998-11-12 アルファ−オレフィン（類）／ヒンダードビニリデン芳香族モノマー（類）から作られたインターポリマー類の水分散液もしくはエマルジョン
EP98959429A EP1030874A1 (fr) 1997-11-12 1998-11-12 Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave
CA002309821A CA2309821A1 (fr) 1997-11-12 1998-11-12 Dispersions ou emulsions aqueuses d'interpolymeres d'alpha-olefine(s)/monomere(s) aromatique(s) de vinylidene entrave
MXPA00004599A MXPA00004599A (es) 1997-11-12 1998-11-12 Dispersiones o emulsiones acuosas de interpolimeros de alfa-olefinas(s) /monomeros(s) aromatico(s) de vinilideno obstruido(s).
KR1020007005117A KR20010032006A (ko) 1997-11-12 1998-11-12 알파-올레핀/입체장애 비닐리덴 방향족 단량체의 상호중합체의 수분산액 또는 수성 에멀젼
AU15228/99A AU1522899A (en) 1997-11-12 1998-11-12 Aqueous dispersions or emulsions of interpolymers of alpha-olefin(s)/hindered vinylidene aromatic monomer(s)

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WO2000022226A1 (fr) * 1998-10-15 2000-04-20 The Dow Chemical Company Interpolymeres aromatiques d'alpha-olefine/vinyle ou de vinylidene et/ou interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene a empechement sterique destines a la fabrication de tapis
WO2000027936A1 (fr) * 1998-11-06 2000-05-18 The Dow Chemical Company Compositions de revetement contenant des interpolymeres aromatiques d'alpha-olefine/vinyle ou vinylidene et/ou des interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene steriquement encombres
WO2007078537A1 (fr) 2005-12-15 2007-07-12 Dow Global Technologies Inc. Articles ameliores en cellulose contenant une composition d’additif
US7645521B2 (en) 2005-12-15 2010-01-12 Dow Global Technologies, Inc. Compositions and aqueous dispersions
AU2012202310B2 (en) * 2003-08-25 2013-10-10 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US9321884B2 (en) 2010-10-29 2016-04-26 Asahi Kasei Chemicals Corporation Process for producing polycondensation polymer, and polymerizer
US10959928B2 (en) * 2015-04-22 2021-03-30 Henkel Ag & Co. Kgaa Foamable personal care composition and the use thereof
US11370704B2 (en) 2017-10-27 2022-06-28 Owens Corning Intellectual Capital, Llc Sizing compositions including weakly-coordinating anion salts and uses thereof

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US8216678B2 (en) * 2006-01-26 2012-07-10 TPC Technologies Inc. Temporary protective polymer coating and removal system
CN111321628A (zh) * 2020-03-04 2020-06-23 广东通力定造股份有限公司 一种应用高阻隔性材料生产纸张的方法

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US5574091A (en) * 1995-06-05 1996-11-12 The Dow Chemical Comapny Aqueous dispersions of olefin copolymers

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DE2937268A1 (de) * 1979-09-14 1981-04-02 Showa Denko K.K., Tokyo Waessrige emulsion aus einem synthetischen mehrkomponentenharz und verfahren zu ihrer herstellung
US5574091A (en) * 1995-06-05 1996-11-12 The Dow Chemical Comapny Aqueous dispersions of olefin copolymers

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000022226A1 (fr) * 1998-10-15 2000-04-20 The Dow Chemical Company Interpolymeres aromatiques d'alpha-olefine/vinyle ou de vinylidene et/ou interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene a empechement sterique destines a la fabrication de tapis
WO2000027936A1 (fr) * 1998-11-06 2000-05-18 The Dow Chemical Company Compositions de revetement contenant des interpolymeres aromatiques d'alpha-olefine/vinyle ou vinylidene et/ou des interpolymeres aliphatiques ou cycloaliphatiques de vinyle ou de vinylidene steriquement encombres
AU2012202310B2 (en) * 2003-08-25 2013-10-10 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2012202313B2 (en) * 2003-08-25 2013-12-05 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2012202317B2 (en) * 2003-08-25 2013-12-05 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2012202314B2 (en) * 2003-08-25 2013-12-05 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
AU2012202323B2 (en) * 2003-08-25 2013-11-28 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US7947379B2 (en) * 2005-12-15 2011-05-24 Dow Global Technologies Llc Compositions and aqueous dispersions
US20110308751A1 (en) * 2005-12-15 2011-12-22 Moncla Brad M Cellulose articles containing an additive composition
US8177939B2 (en) 2005-12-15 2012-05-15 Dow Global Technologies Llc Cellulose articles containing an additive composition
CN101356314B (zh) * 2005-12-15 2012-07-04 陶氏环球技术有限责任公司 含添加剂组合物的改进纤维素制品
AU2006329959B2 (en) * 2005-12-15 2012-08-30 Dow Global Technologies Llc Compositions and aqueous dispersions
US8043713B2 (en) * 2005-12-15 2011-10-25 Dow Global Technologies Llc Compositions and aqueous dispersions
US8029646B2 (en) 2005-12-15 2011-10-04 Dow Global Technologies Llc Cellulose articles containing an additive composition
US7799864B2 (en) 2005-12-15 2010-09-21 Dow Global Technologies Inc. Compositions and aqueous dispersions
US7645521B2 (en) 2005-12-15 2010-01-12 Dow Global Technologies, Inc. Compositions and aqueous dispersions
WO2007078537A1 (fr) 2005-12-15 2007-07-12 Dow Global Technologies Inc. Articles ameliores en cellulose contenant une composition d’additif
US9321884B2 (en) 2010-10-29 2016-04-26 Asahi Kasei Chemicals Corporation Process for producing polycondensation polymer, and polymerizer
US10959928B2 (en) * 2015-04-22 2021-03-30 Henkel Ag & Co. Kgaa Foamable personal care composition and the use thereof
US11370704B2 (en) 2017-10-27 2022-06-28 Owens Corning Intellectual Capital, Llc Sizing compositions including weakly-coordinating anion salts and uses thereof

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AU1522899A (en) 1999-05-31
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CN1282346A (zh) 2001-01-31
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BR9814179A (pt) 2000-09-26
CA2309821A1 (fr) 1999-05-20
MXPA00004599A (es) 2003-09-10

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