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WO2002012359A2 - Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse - Google Patents

Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse Download PDF

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Publication number
WO2002012359A2
WO2002012359A2 PCT/BR2001/000098 BR0100098W WO0212359A2 WO 2002012359 A2 WO2002012359 A2 WO 2002012359A2 BR 0100098 W BR0100098 W BR 0100098W WO 0212359 A2 WO0212359 A2 WO 0212359A2
Authority
WO
WIPO (PCT)
Prior art keywords
multipolymer
aqueous dispersion
monomers
fact
dispersion
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/BR2001/000098
Other languages
English (en)
Other versions
WO2002012359A3 (fr
Inventor
Odair Araujo
Eduardo V. DIAZ
Eduardo A. Kawamura
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.)
Rhodia Brasil SA
Original Assignee
Rhodia Brasil SA
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 Rhodia Brasil SA filed Critical Rhodia Brasil SA
Priority to AU2001277424A priority Critical patent/AU2001277424A1/en
Publication of WO2002012359A2 publication Critical patent/WO2002012359A2/fr
Publication of WO2002012359A3 publication Critical patent/WO2002012359A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene

Definitions

  • the invention refers to a multipolymer in aqueous dispersion, which is useful for application in the fields of coating, textile, adhesive, paper, civil construction, etc., and more specifically paint.
  • the invention also refers to compositions containing a multipolymer and a process to obtain a multipolymer.
  • Polymers in aqueous dispersion are well-known and widely used products. Efforts to develop the application of such polymers are known, e. g. since the water base is less polluting than the organic solvent base.
  • the invention aims at a multipolymer in aqueous dispersion which improves mechanical properties of paint formulated therewith, as well as a process to obtain such polymer.
  • the invention therefore relates, in a first embodiment, to a multipolymer in aqueous dispersion, said multipolymer being comprised of at least four monomers under the following weight percentage distribution: - from about 40% to 80% of a hard monomer,'
  • multipolymers of the invention are advantageously comprised of only four monomers.
  • the multipolymers of the invention as mentioned above particularly include : from about 50% to 70% of a hard monomer; from about 15% to 30% of a soft monomer, ethylenically unsaturated carboxylic acid ester at the positions ⁇ , ⁇ ; - from about 10% to 20% of a monomer selected from the group comprising conjugated dienes and butene; from about 3% to 5% of an acid selected from the group comprising acrylic acid and methacrylic acid, or amides from those acids, particularly selected from the group comprising acrylamide and methacrylamide.
  • Hard monomer is understood as the one that originates a polymer with Tg greater than about 40 °C.
  • Soft monomer designates monomers that originate a polymer with a Tg lower than about 25 °C.
  • Hard monomers are preferably selected from the group comprising styrene, ⁇ -methyl styrene, p-tert-butyl styrene, 3 _ ethyl styrene and methyl vinyl toluene. Styrene is particularly preferred.
  • An ethylenically unsaturated carboxylic acid ester at the positions ⁇ , ⁇ is advantageously selected from the group comprising alkyl esters, preferably methyl, ethyl, butyl and 2-ethylhexyl, of acrylic or methacrylic acids. Butyl acrylate and methyl acrylate are preferred.
  • a conjugated diene monomer is advantageously selected from butadiene and isoprene.
  • Butadiene is the preferred conjugated diene.
  • the ethylenically unsaturated carboxylic acid amide is preferably acrylamide.
  • Tg glass transition temperature
  • Polymers of the invention are used as aqueous dispersions, obtained by means of a process which is also an object of the invention, and which is different from the state of the art for not making use of the addition of polymeric dispersing agents with molecular weight of more than 1000 for the esteric stabilization of the polymer dispersed particles, for instance as disclosed in the patent US 4,322,328, or the addition of emulsifiers such as a salt of acyl ester of a hidroximethanephosphonic acid to optimize the adherence of the paint to the substrates, for instance as disclosed in the patent US 4,169,086.
  • - surfactants may be anionic or non-ionic ' - chain transfer agent is not added initially, but subsequently with the monomers or the remainder of the monomers;
  • Process ingredients such as surfactants, chain transfer agent, initiator, coalescent, antifoaming and biocide agents, are products well-known by one skilled the art and do not, in their generality, limit the scope of the invention.
  • process variables directly or indirectly affect final product characteristics.
  • Variables such as temperature, chain transfer agent concentration and monomer composition can affect properties such as Tg, minimum film formation temperature, gel content (insolubles), etc.
  • Surfactant composition, initial quantity of monomers at the start of the reaction and the initial quantity of initiator can directly affect particle size distribution.
  • the monomer mix composition added during the process can affect the polymer particle structure.
  • compositions of matter including the multipolymer as described are compositions presenting better mechanical resistance as such, better resistance to the loss of such mechanical and color properties.
  • paint compositions it is observed that in comparison to similar paints containing other state of the art polymers, in the washing capacity test as described by the U. S. standard ASTM 2486-96, there is an unforeseen increase in wear resistance.
  • ultraviolet light exposure tests for whitening and yellowing as per the U. S. standard ASTM G-53-96 show that the white color is better maintained and there is stronger resistance to the appearance of yellow color.
  • composition comprising a multipolymer according to the aforementioned characteristics. It is particularly a latex paint composition for civil constructions, containing about 3% to about 10% of the multipolymer of the invention, providing for a high cost-benefit relation in comparison to other paints as obtained with prior art polymers.
  • paint 3 mixing of two polymers, namely styrene-butadiene and styrene- butyl acrylate, so as to present about the same weight of styrene, butadiene and butyl acrylate as in paint 1.
  • Paints 1, 2 and 3 were evaluated for their washing resistance and UV resistance regarding whiteness and yellowing (paint 4 was also evaluated in this criteria), as per the attached figures.
  • Figure 1 presents washing resistance results just for paints 1, 2 and 3, according to method ASTM 2486-96, after curing in oven at 60 °C for 16 hours.
  • the X axis shows paint reference while the Y axis show cycle numbers up to which a film made with the paint resists.
  • Figures 2 and 3 respectively present whiteness and yellowing results for up to a 35 day-exposure of ultraviolet light according to the test ASTM G-53-96, measured by a Elrepho Datacolor 2000 device.
  • the whiteness of paint 1 reaches a very close value, despite a bit lower than paint 4, which is considered as excellent, i. e. with styrene/butyl acrylate polymer.
  • the whiteness of paint 1 after longer periods is better than paints 2 and 3.
  • 35-day yellowing of paint 1 containing the multipolymer of the invention is significantly lower than paints 2 and 3, based on styrene -butadiene or styrene-butadiene plus styrene-butyl acrylate, being closer to the performance of paint 4, based on styrene-butyl acrylate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention porte sur un multipolymère en dispersion aqueuse utilisable dans les domaines des revêtements, des textiles, des adhésifs, du papier, du bâtiment et des peintures plus spécifiques, sur des compositions contenant ledit multipolymère, et sur son procédé de préparation. Ledit multipolymère en dispersion aqueuse comporte au moins quatre monomères dont: un monomère sur; un ester d'acide carboxylique non saturé en éthylène aux positions α, β; un monomère choisi parmi des diènes conjugées ou un butène congugé; et un ester d'acide carboxylique non saturé en éthylène aux positions α, β ou ses amides. Les peintures économiques pour bâtiments contenant le multipolymère de l'invention présentent une meilleure résistance au lavage et une moindre décoloration que celles contenant les polymères utilisés habituellement.
PCT/BR2001/000098 2000-08-08 2001-08-08 Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse Ceased WO2002012359A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001277424A AU2001277424A1 (en) 2000-08-08 2001-08-08 Multipolymer in aqueous dispersion, water-based composition and process to obtain a multipolymer in aqueous dispersion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BR0003660-9A BR0003660A (pt) 2000-08-08 2000-08-08 Multipolìmero em dispersão aquosa, composição de base aquosa, e processo de obtenção de multipolìmero em dispersão aquosa
BRPI0003660-9 2000-08-08

Publications (2)

Publication Number Publication Date
WO2002012359A2 true WO2002012359A2 (fr) 2002-02-14
WO2002012359A3 WO2002012359A3 (fr) 2002-04-25

Family

ID=3944983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2001/000098 Ceased WO2002012359A2 (fr) 2000-08-08 2001-08-08 Multipolymere en dispersion aqueuse, composition aqueuse et procede d'obtention d'un multipolymere en dispersion aqueuse

Country Status (3)

Country Link
AU (1) AU2001277424A1 (fr)
BR (1) BR0003660A (fr)
WO (1) WO2002012359A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141596B2 (en) 2003-10-08 2006-11-28 Incyte Corporation Inhibitors of proteins that bind phosphorylated molecules
WO2008068066A3 (fr) * 2006-12-08 2008-11-20 Henkel Ag & Co Kgaa Agent fixatif pour fibres de kératine

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2939657A1 (de) * 1979-09-29 1981-04-16 Basf Ag, 6700 Ludwigshafen Bindemittel fuer papierstreichmassen
DE3708992A1 (de) * 1987-03-19 1988-09-29 Dow Chemical Co Waesserige polymerdispersion aus einem cyanoalkylester ungesaettigter carbonsaeuren enthaltenden polymer und ihre verwendung zum beschichten von papier
ES2121073T3 (es) * 1992-01-10 1998-11-16 Sumitomo Dow Ltd Procedimiento para la produccion de latex copolimero y utilizacion de este latex.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141596B2 (en) 2003-10-08 2006-11-28 Incyte Corporation Inhibitors of proteins that bind phosphorylated molecules
WO2008068066A3 (fr) * 2006-12-08 2008-11-20 Henkel Ag & Co Kgaa Agent fixatif pour fibres de kératine

Also Published As

Publication number Publication date
BR0003660A (pt) 2002-03-26
AU2001277424A1 (en) 2002-02-18
WO2002012359A3 (fr) 2002-04-25

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