WO1999013011A1 - Nouvelles compositions de couleurs a phase dispersee - Google Patents

Nouvelles compositions de couleurs a phase dispersee Download PDF

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Publication number
WO1999013011A1
WO1999013011A1 PCT/FI1998/000699 FI9800699W WO9913011A1 WO 1999013011 A1 WO1999013011 A1 WO 1999013011A1 FI 9800699 W FI9800699 W FI 9800699W WO 9913011 A1 WO9913011 A1 WO 9913011A1
Authority
WO
WIPO (PCT)
Prior art keywords
monoether
dicyclopentadiene
composition according
diol
propane diol
Prior art date
Application number
PCT/FI1998/000699
Other languages
English (en)
Inventor
Nina Orttenvuori
Karri Airola
Salme Koskimies
Original Assignee
Neste Chemicals Oy
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 Neste Chemicals Oy filed Critical Neste Chemicals Oy
Priority to AU91635/98A priority Critical patent/AU9163598A/en
Publication of WO1999013011A1 publication Critical patent/WO1999013011A1/fr

Links

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
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/06—Copolymers with styrene
    • C09D109/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/196—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • 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
    • C09D113/00—Coating compositions based on rubbers containing carboxyl groups
    • C09D113/02—Latex
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols

Definitions

  • the present invention relates to an aqueous dispersion color composition according to the preamble of claim 1 , the composition containing an aqueous polymer dispersion as a binder.
  • the invention also relates to the use according to claim 10 and the novel monoethers according to claims 11-14.
  • coalescent agents are added to latex paints. These chemicals are often organic solvents which, as the paint dries and hardens, evaporate into ambient air.
  • Polyalcohols and their derivatives are used a great deal as coalescent agents because of their properties.
  • Polyalcohols can be used in several different paint types and applications, since their hydroxyl groups can participate in different reactions and the structure of polyalcohols can be modified.
  • Polyalcohols are usable for water-based and solvent-based paints, both powder-based and solids-based.
  • Polyalcohols can be used as raw materials for many products, and their properties can be modified by preparing from them various ester or ether derivatives.
  • coalescent agent - such as polyol - evaporates and may cause problems of odor and pollution.
  • the development of coalescent agents will in the future be aimed at preparing reactive compounds having different ways of action.
  • These reactive compounds would not evaporate from the paints in the manner of conventional products but would react to become part of the paint coating.
  • Such reactive groups would include reactive double bonds and derivatives of isocyanates or of epoxy compounds.
  • In efforts to achieve a reactive coalescent agent it has been necessary to use highly reactive isocyanates or epoxides, which are toxic to the users even at low concentrations.
  • olefin monoethers of diols as coalescent agents has been proposed previously.
  • the ethers are prepared by causing a 1,3- diol which contains 2 - 6 carbon atoms, such as ethylene glycol, to react with a dienic compound.
  • monoethers containing a double bond have, however, a tendency to tu ⁇ i yellow, for which reason hydrogenation of the compounds is recommended in the prior art.
  • the invention relates specifically to the use of olefin ethers of sterically hindered 1,3-diols, such as 2,2-dimethyl-l,3-propane diol (NPG) and 2-butyl-2-ethyl-l,3-propane diol (BEPD), as coalescent agents. More precisely, the dispersion color compositions according to the invention are characterized in what is stated in the characterizing part of claim 1.
  • products according to the invention can be used in the manner of coalescent agents in alkyd and latex paint compositions in which the proportion of coalescent agent is typically 0.5-30 % of the dry matter content.
  • the preparation and use of the compounds are based on the lesser detrimental effects of olefins as compared with normal reactive coalescent agents and on the reactivity of the double bonds of the compounds under normal oxidative hardening conditions, as well as on the known good dispersion properties of 1,3-diols (e.g. NPG, BEPD).
  • the monoethers described in the invention act as coalescent agents of dispersion polymers and, as the coating hardens under the effect of oxygen in the air, the double bond of the olefin residue takes part in the hardening process, thus becoming part of the paint coating. Also, the solvent residues (VOC) released during the hardening process are minimized owing to the high boiling point and low volatility of the reactive coalescent agent.
  • asymmetric diols such as 2-butyl-2-ethyl-l,3-propane diol (BEPD), 2-methyl-l ,3-propane diol (MP), hydroxypivalyl-hydroxypivalate (HPHP) and 2,2,4-trimethyl-l ,3-hydroxypentane (TMPD) dissolve well, which is important in terms of coat- forming properties.
  • BEPD 2-butyl-2-ethyl-l,3-propane diol
  • MP 2-methyl-l ,3-propane diol
  • HPHP hydroxypivalyl-hydroxypivalate
  • TMPD 2,2,4-trimethyl-l ,3-hydroxypentane
  • polyols which are sterically strongly hindered are etherized.
  • 2- monoalkylated, 2,2-dialkylated 1 ,3-propane diols and 2,2,4-trialkylated pentane diols are especially preferred for use in the invention.
  • the alkyl groups in position 2 in the 1,3-diols may be the same or different, and generally they represent substituted or unsubstituted alkyl or cycloalkyl groups.
  • alkyl groups are straight or branched alkyl groups containing 1 - 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. butyl, amyl, isoamyl or hexyl groups.
  • preferred 1,3-diols are NPG, BEPD, MP, HPHP and 2,2-diethyl- 1,3-propane diol.
  • TMPD can be mentioned as an example of pentane diols.
  • diols mentioned above are also called “sterically hindered diols.”
  • the present ethers can be prepared by allowing the 1 ,3-diol and olefin to react with each other acid-catalytically at 30-180 °C, in particular at approx. 90 - 160 °C.
  • R and R' may be the same or different and represent substituted or unsubstituted alkyl or cycloalkyl groups, or one (R or R') of them is hydrogen.
  • suitable olefins to which the above-mentioned 1,3-diols can be bonded by the addition reaction described include dienes, such as cyclopentadiene, dicyclopentadiene, butadiene and its Diels-Alder derivatives, and other diene derivatives which have been prepared by Diels-Alder addition.
  • dienes such as cyclopentadiene, dicyclopentadiene, butadiene and its Diels-Alder derivatives
  • diene derivatives include vinylcyclohexene and vinyl-norbornene.
  • the catalyst is used in an amount of 1 - 40 % of the amount of the etherification agent.
  • Suitable etherification catalysts in terms of the invention include mineral acids, sulfonic acids and in particular acid ion exchange resins. Especially suitable acids include p-toluene sulfonic acid, benzene sulfonic acid, sulfuric acid, and acid ion exchangers which contain sulfonic groups.
  • an acid ion exchanger When used as the catalyst, it is preferably strongly acidic. According to the invention it has been observed that both gel-like and macroporous strong cation exchange resins can advantageously be used as catalysts of the etherification reaction.
  • the functional group in strongly acidic cation exchange resins is, for example, a sulfonic acid group or a fluorosulfonic acid group.
  • Hammett's acid function (H 0 ) for an ion exchange resin is typically -1...-15. Comonomers prepared from vinyl monomers or conventional condensation polymers can be used as the resin matrix.
  • Especially preferred ion exchange resins include copolymers of styrene and polyvinyl benzene and perfluorosulfonic acid polymers (copolymer of tetrafluoroethylene and perfluoro[2-(fluorosulfonylethoxy)] polyvinyl ether).
  • Examples of commercial resins include resins sold under the trade names AMBERLITE, DOWEX, FINEX and NAFION, e.g. Nafion-H, Amberlyst-15, Amberlyst XN-1010, Amberlyst 38, Dowex 50W-X2, Dowex 50W-X4 and Dowex 50W-X12.
  • Diols and diene are fed into the reaction at a molar ratio of 10:1...1 :10, preferably 5: 1...1 :5 and especially preferably in equimolar amounts or by using a small (approx. 5-30 %) excess of diene.
  • the etherification is carried out in molten state or in a non-polar hydrocarbon solvent, such as toluene, xylene or chlorinated hydrocarbons. If the diol is liquid at the etherification temperature, the reaction can also be carried out without a separate medium.
  • the reaction can be carried out at a temperature of 30 - 180 °C, preferably 30 - 160 °C.
  • the upper limit for the temperature is set, for example, by the heat stability of the cation exchange resin used.
  • the diene is added gradually to a mixture formed by the diol and the catalyst, in which case the reaction is continued for at least some time after the adding of the diene.
  • the reaction temperature is set at 90 - 160 °C, at which value it is maintained during the adding of the diene and thereafter, until the reaction has proceeded to its end.
  • reaction time is 1 min - 24 hours, e.g. 2 - 10 hours.
  • the etherification reaction can be carried out as a batch or semi-batch process or as a continuous process. Continuous processes are preferably carried out in solid bed reactors by using a column-grade ion exchange resin. In batch and semi-batch processes the resin is separated after the reaction from the reaction medium by filtration and is regenerated by a method known per se. The final product is separated from the raw product by, for example, distillation.
  • Coalescent agents usable in water-soluble paint compositions are obtained from the monoethers of 2-alkyl and 2,2-dialkyl- 1,3-diols according to the invention.
  • the ethers according to the invention can be formulated as water-based and/or solvent-based dispersions which contain a binder, as well as additives and auxiliaries known per se. Especially preferably, water-based dispersions are prepared.
  • the possible binders include binders of latex paints, such as polyvinyl acetates and polyacrylates.
  • the last-mentioned binders comprise synthetic latex, which is an ethylenically unsaturated polymer or copolymer, such as a butadiene-styrene type copolymer which further may have a comonomer which contains a carboxyl group, such as acrylic acid, ithaconic acid or maleic acid.
  • the polyvinyl acetate may contain comonomers which contain carboxylic groups.
  • Other binders dispersible in water include various water-soluble polymers (e.g. PVA), starch, CMC, hydroxyethyl cellulose and polyvinyl alcohol.
  • alkyds can be used as binders. They usually contain a condensate product formed from bivalent polyol and a fatty acid or a natural oil. The amount of binder is 40 - 80 % by weight of the dispersion.
  • the amount of coalescing agents according to the present invention in the dispersions is approx. 0.01 - 5 % by weight, in particular approx. 0.1 - 1 % by weight.
  • the monoether of 1 ,3-diol according to the invention can be used in a normal manner to lower the coalescing temperature.
  • the monoether of 1 ,3-diol according to the invention can be used in a normal manner to lower the coalescing temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des monoéthers d'oléfine de 1,3-diols entravés par effet stérique, un procédé pour la préparation de ces derniers et leur utilisation. L'invention permet d'obtenir, de manière avantageuse, de nouvelles compositions de couleurs à phase dispersée qui contiennent des monoéthers de 2,2-diméthyle-1,3-propane diol (NPG), 2-butyle-2-éthyle-1,3-propane diol (BEPD), 2-méthyle-1,3-propane diol (MP), hydroxypivalyl-hydroxypivalate (HPHP) ou 2,2,4-triméthyle-1,3-hydroxypentane (TMPD) avec un liant aqueux. Les monoéthers fonctionnent comme agents de coalescence dans ces compositions.
PCT/FI1998/000699 1997-09-08 1998-09-08 Nouvelles compositions de couleurs a phase dispersee WO1999013011A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU91635/98A AU9163598A (en) 1997-09-08 1998-09-08 Novel dispersion colour compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI973631A FI973631A (fi) 1997-09-08 1997-09-08 1,3-diolipohjaiset eetterit, menetelmä 1,3-diolipohjaisten eetterien valmistamiseksi sekä eetterien käyttö
FI973631 1997-09-08

Publications (1)

Publication Number Publication Date
WO1999013011A1 true WO1999013011A1 (fr) 1999-03-18

Family

ID=8549497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1998/000699 WO1999013011A1 (fr) 1997-09-08 1998-09-08 Nouvelles compositions de couleurs a phase dispersee

Country Status (3)

Country Link
AU (1) AU9163598A (fr)
FI (1) FI973631A (fr)
WO (1) WO1999013011A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8440752B2 (en) 2001-02-22 2013-05-14 Valspar Sourcing, Inc. Coating compositions containing low VOC compounds
CN114394900A (zh) * 2022-01-19 2022-04-26 山东瑞博龙化工科技股份有限公司 一种（甲基）丙烯酸双环戊二烯基氧乙酯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111881A (en) * 1977-09-01 1978-09-05 The Dow Chemical Company Polyoxyhydrocarbylene dihydrocarbyl ethers as coalescing agents for synthetic polymer latexes
US4140724A (en) * 1977-08-11 1979-02-20 Rohm And Haas Company Selective preparation of polyol monoethers of dicyclopentadiene
DE4211208A1 (de) * 1992-04-03 1993-10-07 Henkel Kgaa Wäßrige Dispersionsfarben mit Monoetherverbindungen des Dicyclopentadiens

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140724A (en) * 1977-08-11 1979-02-20 Rohm And Haas Company Selective preparation of polyol monoethers of dicyclopentadiene
US4111881A (en) * 1977-09-01 1978-09-05 The Dow Chemical Company Polyoxyhydrocarbylene dihydrocarbyl ethers as coalescing agents for synthetic polymer latexes
DE4211208A1 (de) * 1992-04-03 1993-10-07 Henkel Kgaa Wäßrige Dispersionsfarben mit Monoetherverbindungen des Dicyclopentadiens

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8440752B2 (en) 2001-02-22 2013-05-14 Valspar Sourcing, Inc. Coating compositions containing low VOC compounds
CN114394900A (zh) * 2022-01-19 2022-04-26 山东瑞博龙化工科技股份有限公司 一种（甲基）丙烯酸双环戊二烯基氧乙酯的制备方法

Also Published As

Publication number Publication date
AU9163598A (en) 1999-03-29
FI973631A (fi) 1999-03-09
FI973631A0 (fi) 1997-09-08

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