WO2009100786A1 - Procédé de fabrication de poly(méth)acrylate bloqué par orthoester, et utilisation comme réticulant dans des résines pour vernis à base d’isocyanates - Google Patents

Procédé de fabrication de poly(méth)acrylate bloqué par orthoester, et utilisation comme réticulant dans des résines pour vernis à base d’isocyanates Download PDF

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Publication number
WO2009100786A1
WO2009100786A1 PCT/EP2008/065537 EP2008065537W WO2009100786A1 WO 2009100786 A1 WO2009100786 A1 WO 2009100786A1 EP 2008065537 W EP2008065537 W EP 2008065537W WO 2009100786 A1 WO2009100786 A1 WO 2009100786A1
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WO
WIPO (PCT)
Prior art keywords
orthoester
meth
acrylate
methacrylate
alkyl
Prior art date
Application number
PCT/EP2008/065537
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German (de)
English (en)
Inventor
Bardo Schmitt
Marianne Omeis
Martina Ebert
Original Assignee
Evonik Röhm Gmbh
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
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Application filed by Evonik Röhm Gmbh filed Critical Evonik Röhm Gmbh
Publication of WO2009100786A1 publication Critical patent/WO2009100786A1/fr

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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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups

Definitions

  • the invention relates to processes for preparing a poly (meth) acrylate having at least two hydroxyl groups blocked by an orthoester and to the use of blocked poly (meth) acrylates obtainable in coating resins, preferably as a solution polymer for preparing an isocyanate-based paint coating.
  • Document (1) describes isocyanate-based coating compositions in which orthoester groups at least partially block the hydroxyl groups of poly (meth) acrylates, whereby the orthoester groups can be removed by hydrolysis, for example by traces of water present in the coating composition, to remove the Promote crosslinking in the reaction with isocyanate compounds.
  • the procedure is such that, for example, a copolymer of, for example, HEMA (hydroxyethyl methacrylate), MMA (methyl methacrylate) and IBOA (isobornyl acrylate) for about 1 hour at about 150 0 C oil bath temperature with a Orthoester, for example 2 Ethoxy-1,3-dioxalane, reacting; and then the thus-obtained orthoester "blocked" copolymer is used for film-forming with an isocyanate, and films and coatings obtained in this way already have a very good hardness (measured as pendulum hardness according to DIN EN ISO 1522) as well as a very good flexibility (measured as Erichsen cupping according to DIN 53156).
  • HEMA hydroxyethyl methacrylate
  • MMA methyl methacrylate
  • IBOA isobornyl acrylate
  • the resins are thus susceptible to hydrolysis and their storage stability is lower than for formulations without this component.
  • the resulting viscosity increase is described, for example, in (2).
  • the orthoester as a water scavenger probably has the function in this formulation to delay the reaction of crosslinking. In contrast, water interferes with isocyanate crosslinking.
  • the orthoester as a water scavenger serves to optimize the cross-linking by reducing side reactions such as urea formation and thus blistering in the film.
  • references (4) and (5) suggest Si-containing copolymer as a crosslinker for the production of film coatings. According to (4), however, work is carried out with the addition of water.
  • a poly (meth) acrylate having at least two hydroxyl groups blocked by an orthoester by adding at least one polymerizable (meth) acrylate monomer comprising at least one OH functionality or a precursor thereof in the presence of at least one orthoester compound Temperatures greater than 23 0 C Polymehsiert, one obtains surprisingly a polymer which, as an additive to paints based on isocyanates to obtain coatings, films or paints that have a balanced range of properties in terms of hardness, flexibility and resistance.
  • isocyanate coatings obtained with the additive according to the invention have an approximately comparable hardness compared to the prior art (determined as Pendelhärte) and only slightly deteriorated or approximately the same flexibility (determined as Erichsen depression). However, they are clearly superior to the chemical resistance to alcohols and ketones.
  • the procedure according to the invention differs from the prior art, for example in the form of D1 in particular by the type of blocking of the OH groups with the orthoester compound.
  • blocking or “blocking” is used, it is to be understood in the context of the invention that it is a reaction between the orthoester compound and at least two hydroxyl groups of a poly (meth) acrylate during the process of polymerization, i. the production of the poly (meth) acrylate comes.
  • hydrolyzable orthoester groups can preferably be formed.
  • at least two hydroxyl groups of a poly (meth) acrylate is not to be understood restrictively, but in particular also two hydroxyl groups which are not attached to a chain of the polymer but which are attached to two different chains of the poly ( meth) acrylate.
  • hydroxyl groups of the poly (meth) acrylate which are capable of reacting with an orthoester compound are blocked. Even more preferably, at least about 40%, more preferably about 65%, and even more preferably, greater than about 75% of the hydroxyl groups present and available for reaction are blocked. The percentages are based on mole percent. If one mole of a monomer containing two hydroxyl groups is used, the indication is 75%, hydrolyzable orthoester compounds or equivalent bonds thereof have been formed with 1.5 moles of a total of 2 moles of hydroxyl groups available for bond formation.
  • the time of addition of the orthoester to block the OH groups of a monomeric mixture of (meth) acrylate monomers to be polymerized, at least one of which has an OH functionality or a precursor thereof, is on the one hand critical (compared to the prior art), on the other hand also relatively uncritical, compared with the reference point of the polymerization process of the monomers.
  • addition prior to initiation of polymerization is possible, as well as addition during polymerization is possible.
  • the invention provides that a) an orthoester is introduced; b) then adding to the template a) at least one polymerisable (meth) acrylate monomer which comprises at least one OH functionality or a precursor thereof; and c) the mixture obtained in b) polymehsiert at temperatures greater than 23 0 C.
  • the reaction with the orthoester is a thermal reaction.
  • the process of polymerization in the presence of at least one orthoester can therefore be carried out in principle over a wide temperature range. In general, you can achieve usable results even at room temperature. However, preference is given to elevated temperatures, ie temperatures of greater than room temperature, in particular greater than 23 ° C. room temperature.
  • the process of the invention is characterized in that the mixture b) is polymerized at temperatures in the range of 70 0 C to 180 0 C over a period of 1 h to 10 h.
  • the reaction proceeds without the use of a catalyst, only via the supply of thermal energy, be it externally or through energy released from the polymerization reaction. If desired and / or required, a catalyst can also be used.
  • any suitable orthoester compound can be used for the process of the invention.
  • the orthoester is a compound of the formula (I):
  • R 1 and R 2 independently of one another are C 1 -C 6 -alkyl or C 5 -C 7 -cycloalkyl, where optionally the two radicals R 1 and R 2 can be joined together to form a five to seven membered ring containing two oxygen atoms, R 3 is hydrogen, C 1 -C 6 -alkyl or an aromatic radical, and R 4 is C 1 -C 6 alkyl.
  • C 1 -C 6 alkyl is understood here and throughout the disclosure to mean a linear or branched alkyl radical having one to six carbon atoms. These include, inter alia, the radicals methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, tert-butyl, n-pentyl, 2-pentyl, iso-pentyl, n-hexyl, 2-hexyl and iso-hexyl.
  • the preferred radicals C 5 -C 7 cycloalkyl include, for example, the cyclopentyl, cyclohexyl and cycloheptyl radicals.
  • the aromatic radicals preferably include the phenyl and the benzyl radical.
  • the aromatic radicals may be substituted up to four times by C 1 -C 6 alkyl.
  • Trimethylorthoformate, triethylorthoformate, trimethylorthopropionate, thethylorthopropionate and / or 2-ethoxy-1,3-dioxalane are among the orthoester compounds which are particularly preferred in the context of the invention.
  • Processes according to the invention of particular interest are those which are distinguished by the use of triethyl orthoformate and / or thethyl orthopropionate as the orthoester.
  • the monomer mixture to be polymethylated has at least one polymerizable (meth) acrylate monomer, which in turn has at least one hydroxyl group or OH functionality.
  • (meth) acrylate is understood to mean both acrylate and methacrylate.
  • the OH functionality may be present on the single monomer of the mixture. Examples include monomers such as HEMA (hydroxyethyl (meth) acrylate).
  • R 5 is hydrogen or methyl and R 6 is linear or branched C 1 -C 60 alkyl, C 5 -C 7 cycloalkyl, which may optionally be mono- or polysubstituted by C 1 -C 6 alkyl, or may be an aromatic radical which may be one - or more than once, at most up to fourfold, may be substituted by C1-C6 alkyl radicals,
  • At least two different polymerizable monomers are used, one of which has a blockable OH group.
  • Equally useful are mixtures of monomers polymehsiert, wherein at least two monomers are used without blockable OH groups together with at least one monomer which has an OH group.
  • Equally preferred are processes in which two different monomers with blockable OH groups are polymerized with at least one monomer without a blockable OH group.
  • the monomers without a blockable OH group are, for example, acrylic acid or methacrylic acid esters of straight-chain or branched monoalcohols having one to 60 carbon atoms. Particularly preferred are acrylic acid or methacrylic acid esters of straight-chain or branched monoalcohols having one to 20 carbon atoms. Preferred esters are alkyl acrylates and methacrylates having one to 12 carbons in the alkyl groups, even more preferred are alkyl acrylates and methacrylates having two to 8 carbons in the alkyl groups.
  • the particularly useful (meth) acrylate monomers include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, Hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate and the like.
  • cycloaliphatic (meth) acrylates for example trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and similar monomers.
  • benzyl acrylate and / or benzyl methacrylate as component A, i. Monomers of the formula II.
  • the polymerizable monomers of component B are those monomers which have one or a plurality of hydroxyl groups or OH functionality or precursors thereof.
  • ethylenically unsaturated monomers having hydroxyl groups or OH functionality or precursors thereof include hydroxyalkyl acrylates and hydroxyalkyl methacyrylates.
  • Particularly suitable monomers include, but are not limited to, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyisopropyl acrylate, 2, 3-dihydroxypropyl acrylate, hydroxybutyl acrylate, dihydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisopropyl methacrylate, hydroxybutyl methacrylate, dihydroxypropyl methacrylate, dihydroxybutyl methacrylate, either alone or in admixture of two or more.
  • hydroxyl group or OH functionality via a precursor compound into the monomer mixture to be polymethylated. This happens, for example, via the epoxy group of a glycidyl methacrylate. A such epoxy group can be converted to an OH group by traces of water via hydrolysis during polymerization.
  • Suitable other monomers include in a non-exhaustive list of acrylic acid and methacrylic acid, acrylamide and methacyrylamide, and derivatives such as alkoxymethyl (meth) acrylamide monomers such as methacrylamide, N-isobutoxymethylmethacrylamide and N-methylolmethacrylamide; Amino (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; Maleic, itaconic and fumaric anhydrides and their diesters and half esters; Vinylaromatics such as styrene, alpha-methylstyrene and vinyltoluene and Polyethylenglycolmonoacrylate and - monomethacrylate.
  • the method of the invention is characterized in that no Si-containing monomers are used as the polymerizable monomers, resulting in the resulting polymer or copolymer silane groups, which could act as crosslinkers in the film production.
  • a special and very expedient variant of the process according to the invention uses as polymerizable monomers a mixture of isobornyl methacrylate, methacrylic acid, 2-ethylhexyl methacrylate and hydroxyethyl methacrylate.
  • the process of the invention may be carried out in bulk or in a solvent.
  • the polymerization is carried out in a solvent, most suitably in an organic solvent.
  • inert solvents are suitable here, such as aliphatic or alicyclic hydrocarbon compounds or slightly more polar solvents such as ethers or esters.
  • Particularly useful as a solvent is, for example, n-butyl acetate.
  • the solution polymer according to the invention is particularly suitable as a crosslinker in coating resins based on isocyanate.
  • it can either be isolated from the solution or used directly in solution directly with a suitable solids content.
  • Preferred is the use of the solution polymer having a solids content in the range of 20 to 80% (w / w) to prepare an isocyanate-based coating.
  • the layer thickness of the obtained film was 30 ⁇ 1.5 ⁇ m on aluminum flakes
  • Reagents to be tested were brake fluid, diesel, 2-propanol and methyl ethyl ketone (MEK).
  • the films produced were examined for their resistance by pressing 0.70 g of pulp, soaked with 5.0 g of the respective test liquid and covered with a watch glass, on the film for 15 minutes.
  • the watch glasses were loaded with 500 g.
  • the films were dried at room temperature for 24 h, then the pendulum hardness was again determined at the treated sites and compared with the values of the untreated films.
  • Polymer films were made as described.
  • the substrate used was hostaphan film. After drying at 80 ° C. for 1 day, the films were detached from the film and test specimens (mass: 3.0 ⁇ 1.5 cm) were cut to size.
  • the hardness (measured as pendulum hardness) of both the film V2 and the film B1, each obtained using polymers prepared with 5% orthoester, is significantly greater than the hardness of the film V1 using a polymer was obtained, which was prepared without the addition of an orthoester.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Procédé de fabrication d’un poly(méth)acrylate avec au moins deux groupes hydroxyle bloqués par un orthoester, selon lequel on polymérise à des températures supérieures à 23 °C, en présence d’au moins un composé orthoester, au moins un monomère polymérisable de (méth)acrylate qui comprend au moins une fonctionnalité OH ou un précurseur de celle-ci. Les polymérisats obtenus, par exemple des copolymères de méthacrylate d’isobornyle, d’acide méthacrylique, de méthacrylate de 2-éthylhexyle et de méthacrylate d’hydroxyéthyle bloqués par orthoester, conviennent remarquablement bien comme additifs de réticulation pour des résines pour vernis à base d’isocyanates, et fournissent des vernis ou des revêtements ayant des propriétés améliorées en termes de dureté, de flexibilité et de résistance aux solvants polaires.
PCT/EP2008/065537 2008-02-11 2008-11-14 Procédé de fabrication de poly(méth)acrylate bloqué par orthoester, et utilisation comme réticulant dans des résines pour vernis à base d’isocyanates WO2009100786A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008000268.2 2008-02-11
DE200810000268 DE102008000268A1 (de) 2008-02-11 2008-02-11 Verfahren zur Herstellung von Orthoester geblocktem Poly(meth)acrylat sowie Verwendung als Vernetzer in Lackharzen auf Isocyanatbasis

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WO2009100786A1 true WO2009100786A1 (fr) 2009-08-20

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WO (1) WO2009100786A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387591A2 (fr) * 1989-03-11 1990-09-19 BASF Aktiengesellschaft Polymères contenant du silicium, constitués d'esters acryliques et/ou méthacryliques
EP0493673A2 (fr) * 1990-12-06 1992-07-08 BASF Aktiengesellschaft Copolymères autoréticulables par l'humidité de l'air et mélanges

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60206802A (ja) 1984-03-30 1985-10-18 Dainippon Ink & Chem Inc 改良された加水分解性シリル基含有ビニル系重合体の製造法
JPS60206812A (ja) 1984-03-31 1985-10-18 Dainippon Ink & Chem Inc 改良された加水分解性シリル基含有ビニル系重合体を含む常温硬化性樹脂組成物
DE3776357D1 (de) 1986-02-04 1992-03-12 Dainippon Ink & Chemicals Beschichtungszusammensetzung.
JPS6475578A (en) 1987-09-18 1989-03-22 Showa Highpolymer One-pack curing type coating having excellent preservation stability
DE19850210A1 (de) 1998-10-31 2000-05-04 Basf Coatings Ag Die Verwendung von Methylpropan-1,3-diol-mono(meth)acrylat für die Herstellung oxidativ und/oder thermisch härtbarer Beschichtungsmittel, Klebstoffe und Dichtungsmassen
CA2531624A1 (fr) 2003-07-09 2005-01-27 D4D Technologies, Lp Bibliotheque de d'ebauches de rodage et procede informatise de selection efficace d'ebauches de rodage selon des criteres donnes
EP1732956A1 (fr) 2004-03-22 2006-12-20 E. I. du Pont de Nemours and Company Polyols proteges par orthoester pour revetements a faible teneur en composes organiques volatiles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387591A2 (fr) * 1989-03-11 1990-09-19 BASF Aktiengesellschaft Polymères contenant du silicium, constitués d'esters acryliques et/ou méthacryliques
EP0493673A2 (fr) * 1990-12-06 1992-07-08 BASF Aktiengesellschaft Copolymères autoréticulables par l'humidité de l'air et mélanges
EP0656394A1 (fr) * 1990-12-06 1995-06-07 BASF Aktiengesellschaft Copolymères autoréticulables par l'humidité de l'air et mélanges

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