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WO2007114997A2 - Composition de revêtement résistant à l'usure - Google Patents

Composition de revêtement résistant à l'usure Download PDF

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Publication number
WO2007114997A2
WO2007114997A2 PCT/US2007/063953 US2007063953W WO2007114997A2 WO 2007114997 A2 WO2007114997 A2 WO 2007114997A2 US 2007063953 W US2007063953 W US 2007063953W WO 2007114997 A2 WO2007114997 A2 WO 2007114997A2
Authority
WO
WIPO (PCT)
Prior art keywords
methacrylate
glycol diacrylate
acrylate
acid
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2007/063953
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English (en)
Other versions
WO2007114997A3 (fr
Inventor
Stephanie A. Crette
Alexander J. Conte
Inez N. De Oliveira
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WestRock MWV LLC
Original Assignee
Meadwestvaco Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Meadwestvaco Corp filed Critical Meadwestvaco Corp
Publication of WO2007114997A2 publication Critical patent/WO2007114997A2/fr
Publication of WO2007114997A3 publication Critical patent/WO2007114997A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D121/00—Coating compositions based on unspecified rubbers
    • C09D121/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the coating composition contains relatively large quantities of solvent that must be evaporated after application.
  • U.S. Patent No. 5,232,964 teaches a method of preparing wear resistant coating compositions including photopolymerization of a mixture containing one multi-functional acrylate monomer, one silane, and colloidal silica dispersed in a solvent. Again, the coating compositions contain volatile organic solvent that must be evaporated after application.
  • exfoliated structure is obtained when the silicate layers are fully and uniformly dispersed in a continuous polymer matrix, but there is random and disordered in the nature of the silicate sheets.
  • the exfoliated clay-polymer nanocomposites are known to demonstrate higher degrees of strength, stiffness and barrier properties with much lower clay content than those of conventional clay-polymer microcomposites.
  • VOC volatile organic content
  • This invention relates to wear resistant coating compositions containing exfoliated clay-polymer emulsion obtained by emulsion polymerization of monomers in the present of layered clay, also known as in situ emulsion polymerization.
  • the layered clay may be added to the aqueous phase of the polymerization or introduced to the polymerization along with monomers through monomer feed.
  • FIG.l is a schematic X-ray diffraction patterns of clay-polymer composites having different structures (immiscible, intercalated and exfoliated) as published in Macromolecules (1997), volume 30, page 8000-8009;
  • FIG 2 is an X-ray diffraction of Sample 1 of the present invention.
  • FIG 3 is an X-ray diffraction of Sample 2 of the present invention
  • FIG 4 is an X-ray diffraction of Sample 3 of the present invention
  • FIG 5 is an X-ray diffraction of a post-blend of surface-treated montmorillonite clay and polymer. DESCRIPTION OF THE INVENTION
  • the emulsion used in the wear resistant coating composition of the present invention is an exfoliated clay-polymer emulsion obtained by emulsion polymerization of monomers in the present of layered clay, also known as in situ emulsion polymerization.
  • the clay is added into an aqueous phase of the polymerization.
  • the clay is introduced to the polymerization along with monomer(s) through monomer feed, also known as "monomer co-feed.”
  • the emulsions used in the wear resistant coating compositions of the present invention comprise: (a) polymerization product of a mixture comprising at least one free radical polymerizable monomer;
  • Suitable silicate clays for use in the present invention include, but are not limited to, smectite, phyllosilicate, montmorillonite, saponite, beidellite, montronite, hectorite, stevensite, vermiculite, kaolinite, hallosite, and synthetic phyllosilicate.
  • the clay may be surface treated or non-surface treated.
  • Suitable polymers for use in the present invention are polymerization products of a mixture comprising at least one free radical polymerizable monomer such as acrylic- based monomer, styrenic-based monomer, vinylic-based monomer, and ⁇ , ⁇ -unsaturated monomer.
  • acrylic-based monomers include, but are not limited to, acrylic acid; methacrylic acid; itaconic acid; maleic acid; fumaric acid; acryloxypropionic acid; (meth)acryloxypropionic acid; sulphonic acid-bearing monomers such as styrene sulfonic acid, sodium vinyl sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, ethylmethacrylate- 2-sulphonic acid, and 2-acrylamido-2-methylpropane sulphonic acid; phosphoethylmethacrylate; methacrylic anhydride; maleic anhydride; itaconic anhydride; succinic anhydride; acrylate; and methacrylate.
  • Acrylate monomers include, but are not limited to, Ci -C30 alkyl ester of acrylic acid monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, allyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, n-lauryl acrylate, stearyl acrylate, n-decyl acrylate, isodecyl acrylate, isobornyl acrylate; phenoxyethyl acrylate; 2-phenoxy acrylate; 2-methoxyethyl acrylate; lactone modified esters of acrylic acid; tetrahydrofuryl acrylate; 2-(2-ethoxyeth
  • Methacrylate monomers include, but are not limited to, methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isopropyl methacrylate; isobutyl methacrylate; n-amyl methacrylate; n-hexyl methacrylate; isoamyl methacrylate; 2-hydroxyethyl methacrylate; 2- hydroxypropyl methacrylate; lactone modified esters of methacrylic acid; N ,N- dimethylamino ethyl methacrylate; N,N-diethylaminoethyl methacrylate; t-butylaminoethyl methacrylate; 2-sulfoethyl methacrylate; trifluoroethyl methacrylate; glycidyl methacrylate; benzyl methacrylate; allyl methacrylate; 2-n-
  • the styrenic-based monomers suitable for use in the present invention may be substituted or unsubstituted.
  • Representative examples of styrene monomers include, but are not limited to, styrene, ⁇ -methyl styrene, p-methyl styrene, ⁇ - ethyl styrene and ⁇ - isopropyl styrene.
  • vinylic-based monomers include, but are not limited to, ethylene, propylene, vinyl chloride, vinyl acetate, acrylonitrile, butene, hexene, heptene, isobutylene, and octane.
  • Examples of ⁇ , ⁇ -unsaturated monomers include, but are not limited to, butadiene, isoprene, chloroprene, and other dienes.
  • Any emulsif ⁇ er known for its use in an emulsion polymerization may be employed in the present invention. These include nonionic emulsif ⁇ ers, anionic emulsifiers, and combinations thereof. Suitable anionic emulsifiers include, but are not limited to, alkyl sulfates, ether sulfates, phosphate esters, sulfonates, and the like. Suitable nonionic emulsifiers include, but are not limited to, fatty acids, alcohol ethoxylates, alkylphenol ethoxylate, phenol ethoxylate, block copolymers, and the like. Anionic and non-ionic emulsif ⁇ ers containing polymerizable groups (known in the art as "polymerizable surfactants”) are also suitable for use in the present invention. Furthermore, gemini surfactant may be used in the present invention.
  • water-dispersible stabilized polymer is used as an emulsif ⁇ er.
  • the water-dispersible stabilized polymer is added to the initial aqueous phase prior to an addition of monomers and/or clay.
  • Suitable water- dispersible stabilized polymers for use in the present invention have an average molecular weight in the range of about 2,000 to about 12,000. In some embodiments, the water- dispersible stabilized polymers have an average molecular weight in the range of about 5,000 to about 11,000.
  • the water-dispersible stabilized polymers suitable for use in the present invention have an acid number of about 200 to about 290. In some embodiments, the acid number is about 200 to about 280. In some other embodiments, the acid number is about 200 to about 275. Polar, non-ionic water-dispersible polymers may also be employed in the present invention.
  • the water-dispersible stabilized polymers are low molecular weight styrene acrylic copolymer.
  • the water- dispersible stabilized polymers are low molecular weight hybrid resin of acrylic monomers, rosins and fatty acids.
  • Examples of water-dispersible stabilized polymers include, but are not limited to, any hybrid resin of acrylic monomers, rosins and fatty acids, styrene-acrylic copolymers or acrylic hard resins known for their dispersion capabilities in emulsion polymerization reactions.
  • a catalytic amount of at least one polymerization initiator is used in the polymerization reaction.
  • Traditional polymerization initiators such as thermal initiators, redox initiators, and combinations thereof are suitable for use in the emulsion polymerization of the present invention.
  • the type of polymerization initiator is known in the art to depend upon the desired temperature for the reaction.
  • Thermal initiators which are suitable for use include, but are not limited to, hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, t-butyl peracetate, azobisisobutyronitrile, ammonium persulfate, sodium persulfate, potassium persulfate, isopropyl peroxycarbonate, and combinations thereof.
  • Suitable redox initiators include, but are not limited to, sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulf ⁇ te, potassium persulfate-sodium metabisulfite, potassium persulfate-sodium bisulfite, cumene hydroperoxide-iron (II) sulfate, and combinations thereof.
  • At least one chain transfer agent may be incorporated during polymerization to control the molecular weight of the polymer.
  • chain transfer agents include, but are not limited to, mercaptans, polymercaptans, and polyhalogen compounds.
  • chain transfer agents include alkyl mercaptans such as ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, t-butyl mercaptan, n-amyl mercaptan, isoamyl mercaptan, t-amyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan; mercapto carboxylic acids and their esters, such as methyl mercaptopropionate and 3- mercaptopropionic acid; alcohols such as isopropanol, isobutanol, lauryl alcohol and t-octyl alcohol; and halogenated
  • crosslinkers may be added to the polymerization reaction mixture.
  • suitable crosslinkers include, but are not limited to, divinyl benzene, butylene glycol dimethacrylate, alkanepolyol-polyacrylates, alkanepolyol-polymethacrylates, ethylene glycol di(meth)acrylate, butylene glycol diacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimeth-acrylate, trimethylol-propane diacrylate, trimethylolpropane dimeth-acrylate, trimethylol-propane triacrylate, trimethylolpropane trimethacrylate, and unsaturated carboxylic acid allyl.
  • the emulsion containing polymer and clay completely exfoliated within the polymer matrix is produced using an in-situ polymerization process comprising the steps of:
  • the emulsion containing polymer and clay completely exfoliated within the polymer matrix is produced using an in-situ polymerization process comprising the steps of: (i) providing an initial aqueous phase containing emulsif ⁇ er;
  • emulsion polymerization procedures may be used in preparing the invention emulsions.
  • emulsion polymerization procedures include, but are not limited to, core-shell, single stage, multi-stage, mini-emulsion, and grad- add polymerizations.
  • Montmorillonite clay is an aluminisilicate smectite clay. It is a cation-poor layered silicate; therefore, its layers can be easily separated.
  • X-ray diffraction XRD
  • XRD X-ray diffraction
  • the clay-polymer composite is formed and an X-ray diffraction is taken for the composite. The change in the d- spacing between the clay itself and the d- spacing of the clay-polymer composite is used to determine the morphology of the clay-polymer composite.
  • the three main types of clay-polymer composites can be characterized using XRD as shown in FIG.1.
  • the structure of the clay-polymer emulsions of the present invention was analyzed using X-ray diffraction (XRD) and compared to that of the clay-polymer composition obtained from known preparation process.
  • Sample 1 of the present invention was prepared by an in-situ emulsion polymerization of styrene and acrylic monomers in the presence of surface treated montmorillonite clay, wherein the clay was added to the aqueous phase of the polymerization.
  • the X-ray diffraction of montmorillonite clay itself shows a d- spacing peak of 1.86 nm.
  • Sample 3 was prepared by an in-situ emulsion polymerization of styrene and acrylic monomers in the presence of surface treated montmorillonite clay, wherein the clay was mixed with monomer and added to the reaction mixture through monomer feed.
  • the X-ray diffraction of Sample 3 showed no XRD peak at the 2 ⁇ of about 4-6 degree, indicating that the in-situ clay-polymer emulsion of Sample 3 has an exfoliated clay structure.
  • the wear resistant coating composition of the present invention comprises the aforementioned emulsions containing polymer and clay completely exfoliated in the polymer matrix.
  • the invention wear resistant compositions may contain one or more crosslinkers capable of crosslinking at room temperature or elevated temperature.
  • crosslinkers include, but are not limited to, polycarbodiimide, functional silane, and melamine resin.
  • a film-forming aid such as coalescence agents, plasticizers, and the like may be added to the coating composition. It is well within the ability of one skilled in the art to determine the appropriate pH range, solids level, and film-forming characteristics for such applications.
  • the invention coating compositions may further include additives such as buffers, neutralizers, thickeners or rheology modifiers, humectants, wetting agents, biocides, plasticizers, antifoaming agents, colorants, fillers, waxes, water repellants, slip or mar aids, anti-oxidants, and the like.
  • additives such as buffers, neutralizers, thickeners or rheology modifiers, humectants, wetting agents, biocides, plasticizers, antifoaming agents, colorants, fillers, waxes, water repellants, slip or mar aids, anti-oxidants, and the like.
  • the invention coating composition may be applied by any conventional application methods. Examples of these include, but are not limited to, brushing, spraying, roll coating, doctor-blade application, air knife coating, trailing blade coating, curtain coating, and extrusion.
  • the invention coating compositions may be applied to any flooring materials.
  • flooring examples include, but are not limited to, wood, vinyl, slate, concrete, and stone.
  • the resulting latex composition had a solids content of 49.4%, Brookfield viscosity of 500 cps at 25°C, and an average particle size of 78.3 nm.
  • Sample 3 To a round-bottomed flask fitted with a mechanical stirrer, a heating mantle and inlet tubes for monomer feed, was charged, with stirring, 380.2 g of deionized water, 82 g of a low molecular weight alkali-soluble, water-dispersible styrene acrylic polymer and 20.5 g of a 28-30 % ammonium hydroxide solution. The mixture was heated to 71 0 C until the low molecular weight polymer was completely dissolved. Oleic acid (37.4 g) and ammonium hydroxide (7.1 g) were added to the initial charge, followed by an increase in temperature to 8O 0 C.
  • the monomer feed was then prepared, composed of a mixture of 136.8 g of 2-ethylhexyl acrylate, 143.3 g of methyl methacrylate, and 5.5 g of glycidyl methacrylate.
  • 3 wt % (based on monomers) of Cloisite® 25A surface treated montmorillonite provided by Southern Clay Products Inc.
  • the monomer feed was added to the flask over a period of two hours.
  • the mixture was held at 8O 0 C for an additional half hour. Thereafter, a solution of 0.5 g of ammonium persulfate in 21.4 mL of deionized water was added to the flask, and the temperature of the mixture was held at 8O 0 C for an additional hour. Following a cooling period, a solution of 0.6 g of biocide (Proxel GXL manufactured by Avecia) in 1.2 mL of deionized water was added to the mixture.
  • biocide Proxel GXL manufactured by Avecia
  • the resulting latex composition had a solids content of 49.4%, Brookfield viscosity of 3350 cps at 25°C, and an average particle size of 74.3 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne des compositions de revêtement résistant à l'usure, contenant une émulsion argile-polymère exfoliée, obtenue par polymérisation par émulsion de monomères en présence d'argile stratifiée, connue également sous le nom de polymérisation par émulsion in situ. L'argile stratifiée peut être ajoutée à la phase aqueuse de la polymérisation, ou introduite à la polymérisation en même temps que des monomères par une charge monomère.
PCT/US2007/063953 2006-03-30 2007-03-14 Composition de revêtement résistant à l'usure Ceased WO2007114997A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US78756906P 2006-03-30 2006-03-30
US60/787,569 2006-03-30

Publications (2)

Publication Number Publication Date
WO2007114997A2 true WO2007114997A2 (fr) 2007-10-11
WO2007114997A3 WO2007114997A3 (fr) 2008-05-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2067752A1 (fr) * 2007-12-06 2009-06-10 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Matériau de construction
CN101864023A (zh) * 2010-05-25 2010-10-20 武汉理工大学 聚含氟丙烯酸酯/蒙脱土复合乳液的制备工艺
CN102585208A (zh) * 2011-12-30 2012-07-18 浙江工业大学 p-全氟壬烯氧基苯磺酸聚乙二醇酯及其制备方法和应用
CN103641670A (zh) * 2013-12-13 2014-03-19 南京理工大学 一种包覆rdx和hmx的方法及其包覆材料

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024760A2 (fr) * 2000-09-21 2002-03-28 Rohm And Haas Company Dispersions nanocomposites aqueuses: procedes, compositions, et utilisations mettant en oeuvre celles-ci

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2067752A1 (fr) * 2007-12-06 2009-06-10 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Matériau de construction
WO2009072888A1 (fr) * 2007-12-06 2009-06-11 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Libération contrôlée d'actifs pour des matériaux utilisés en construction
US8986445B2 (en) 2007-12-06 2015-03-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Controlled release of actives for materials used in construction
CN101864023A (zh) * 2010-05-25 2010-10-20 武汉理工大学 聚含氟丙烯酸酯/蒙脱土复合乳液的制备工艺
CN102585208A (zh) * 2011-12-30 2012-07-18 浙江工业大学 p-全氟壬烯氧基苯磺酸聚乙二醇酯及其制备方法和应用
CN103641670A (zh) * 2013-12-13 2014-03-19 南京理工大学 一种包覆rdx和hmx的方法及其包覆材料

Also Published As

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